Emulsion stabilizing fluorosurfactants with improved manufacturability

Abstract

This disclosure provides methods of synthesizing fluorosurfactants and fluorosurfactants produced by the disclosed methods. These fluorosurfactants can be used in various protocols, such as PCR protocols.

Description

[0001] EMULSION STABILIZING FLUOROSURFACTANTS WITH IMPROVED

[0002] MANUFACTURABILITY

[0003] CROSS-REFERENCE TO RELATED APPLICATION

[0004] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 583,423, filed September 18, 2023, the disclosure of which is hereby incorporated by reference in its entirety, including all figures, tables and amino acid or nucleic acid sequences.

[0005] BACKGROUND OF THE INVENTION

[0006] Traditional methods for synthesizing fluorosurfactants, including those for droplet digital PCR, are either difficult or limiting. For example, some fluorosurfactants for droplet digital PCR are made using dangerous and difficult-to-work-with chemicals and involve synthesizing a highly moisture sensitive acyl halogen intermediate product. A highly trained chemist and extensive preparation are required.

[0007] Another example includes a synthetic route where a nucleophilic nonfluorinated polymer directly reacts with a perfluorinated polymer activated by an alkyl-ester. This method has a major limitation: only small molecules or short oligomers can be used. The use of longer oligomers and polymers results in long reaction times and typically low yields and purity due to dilute reactions, phase separations, and / or decarbonylation of the perfluoro polymer. Moreover, removing both the unreacted and decarb onylated fluorinated polymer from the surfactant is complicated and difficult.

[0008] Thus, there is a need for improved fluorosurfactants and methods to synthesize them.

[0009] BRIEF SUMMARY OF THE INVENTION

[0010] This disclosure provides methods of synthesizing fluorosurfactants and fluorosurfactants produced by the disclosed methods. These fluorosurfactants can be used in various protocols, such as PCR protocols.

[0011] BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1. Various exemplary poly(hexafluoropropylene oxide) - oligo(ethylene oxide) intermediates. For these structures, n can be a value between 5 and 40, preferably between 5 and 35 (including fractional values), and i can be a value between 1 and 12 (including fractional values). FIG. 2. Exemplary poly(hexafluoropropylene oxide) - oligo(ether) intermediates with different oligo(ether) constructs. For these structures, n can be a value between 5 and 40, preferably between 5 and 35 (including fractional values).

[0013] FIG. 3. Examples of other perfluorinated polyether polymers reacted with diamine oligo(ethylene oxide). For these structures, m and n are, independently, a value between 1 and 40 (including fractional values) and m+n = a value between 5 and 40, preferably between 8 and 35, and the structure is a valid chemical structure, and i can be a value between 1 and 12 (including fractional values).

[0014] FIG. 4. Examples of other perfluorinated polyether polymers reacted with diamine polyalcohols. For these structures, n can be a value between 5 and 40, preferably between 5 and 35 (including fractional values).

[0015] FIGs. 5A-5B. 1H NMR: Spectra of example surfactant. Two amides shown at 8.38 and 7.59 ppm. Weak signal at 6.02 ppm shows ~1% decarbonylation (Fig. 5A). Fig. 5B: 19F NMR: fluorine NMR shows low decarbonylation at -146.8 and -85.6 ppm.

[0016] FIG. 6. Droplets made using one embodiment of a surfactant of the disclosure at the indicated weight % solutions in HFE 7500 both before and after thermal cycling using a standard PCR protocol. Droplets showed stability visually and were comparable to two different control surfactants made using different chemistries.

[0017] FIG. 7. Digital PCR performed in droplets made using one embodiment of a surfactant of the disclosure at the indicated weight %. Data showed genomic copy counts comparable to digital PCR performed in droplets formed with two different control surfactants using different chemistries. For each surfactant test (Control #1, Control #2, and the surfactant of the disclosure at each of the indicated weight percentages), two different targets were quantified by digital PCR (target 1 denoted as closed ovals, and target 2 denoted as open squares). Duplicate testing was performed (noted by the brackets).

[0018] FIG. 8. One embodiment of a surfactant of the disclosure at the indicated weight

[0019] % showed counts (number of droplets detected in a digital PCR instrument) comparable to two different control surfactants in duplicate testing of a duplex assay.

[0020] For Figures 5-8, the surfactant has the structure:

[0021] " 15.88

[0022] FIG. 9. A reaction scheme for the formation of an exemplary intermediate compound, “n” can be an average value selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 (including fractional values).

[0023] FIG. 10. A reaction scheme for the formation of an exemplary surfactant, “n” can be an average value selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 (including fractional values), and “i” can be any value between 1 and 10, 1 and 20, 1 and 30, or higher.

[0024] DETAILED DISCLOSURE OF THE INVENTION

[0025] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0026] The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”

[0027] The phrase “and / or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and / or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and / or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc. As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of’ or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of’, when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0028] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and / or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0029] It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.

[0030] In the claims, as well as in the specification herein, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of’ and “consisting essentially of’ shall be closed or semi-closed transitional phrases.

[0031] The term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, z.e., the limitations of the measurement system. For example, “about” can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, “about” can mean a range of up to 0-20%, 0 to 10%, 0 to 5%, or up to 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, preferably within 5-fold, and more preferably within 2-fold, of a value. Where particular values are described in the specification and claims, unless otherwise stated, the term “about” meaning within an acceptable error range for the particular value should be assumed. In the context of compositions containing amounts of ingredients where the terms “about” or “approximately” are used, these compositions contain the stated amount of the ingredient with a variation (error range) of 0-10% around the value (X±10%).

[0032] In the present disclosure, ranges are stated in shorthand, so as to avoid having to set out at length and describe each and every value within the range. Any appropriate value within the range can be selected, where appropriate, as the upper value, lower value, or the terminus of the range. For example, a range of 0.1-1.0 represents the terminal values of 0.1 and 1.0, as well as the intermediate values of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and all intermediate ranges encompassed within 0.1-1.0, such as 0.2-0.5, 0.2-0.8, 0.7-1.0, etc. Where ranges are recited in this disclosure, the range includes the terminal values of the range (for example, a range between 5 and 10 includes the values 5, 6, 7, 8, 9, and 10), as well as various fractional values within the range.

[0033] The present disclosure provides improved methods to synthesize fluorosurfactants, fluorosurfactants produced by such methods, as well as compositions, methods, and uses related thereto. The disclosed methods significantly decrease sensitivity to moisture, avoid the use of toxic reagents, and allow the modulation of size and geometry of the hydrophilic portion of the surfactant. The fluorosurfactants of the disclosure can be used in the preparation of compositions for use in various systems and protocols, for example PCR protocols. The disclosed fluorosurfactants can also be referred to as surfactants herein.

[0034] Thus, the disclosure provides a surfactant comprising a perfluorinated polyether (PFPE) block or other alkyl ester activated perfluorinated polymers (PFPAE) block coupled to a hydrophilic linker molecule (L) having at least two amine groups (for example, 2-(2- Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO) or a polyethylene glycol having at least two amine groups) via a first amide bond and the linker molecule (L) being coupled via a second amide bond to a hydrophilic polymer block, said hydrophilic polymer block being optionally alkylated. In some embodiments, the hydrophilic polymer block comprises a polyethylene glycol (PEG) block, the PEG block being optionally alkylated. The PEG block may comprise a formula of -(CnEkn O)y-H or -(CnH2nO)y-alkyl, wherein the alkyl is a Ci-Cio alkyl, n is an integer selected from 1, 2, 3, 4, 5, or 6, preferably 1, 2, 3 or 4, more preferably 2, and y is an integer selected from 2-75 or is an integer selected from 2, 3, 4, 5, 6,

[0035] 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, preferably 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, more preferably 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or y is an average repeat value between 2 and 75, including fractional values thereof, between 2 and 30, including fractional values thereof, between 5 and 25, including fractional values thereof, or between 8 and 20, including fractional values thereof.

[0036] In various other embodiments, the PFPAE block or PFPE block comprises: a) the formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCO-, wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 including fractional values thereof or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40.

[0037] In various aspects and embodiments, L may comprise: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9 or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3 or more preferably 2); or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH-, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5 (preferably, independently 0, 1, 2 or 3, or e and f are selected such that e + f = 0, 1, or 2); a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -NH(CH2)qO(CH2)rO(CH2)gNH-, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably q and s are, independently, 1, 2 or 3 and can be the same or different and r is 1, 2, 3, or 4); or f) L forms an amide bond with the PFPAE block or PFPE block to which it is coupled and an amide bond with the hydrophilic polymer block and is 2-(2- Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO), 1,1 l-diamino-3,6,9- trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine (l,14-Diamino-3,6,9,12- tetraoxatetradecane), or 4,9-dioxa-l,12-dodecanediamine (l,12-diamino-4,9-di oxadodecane). The disclosed fluorosurfactants and methodology provide several advantages. For example, the disclosed methods provide a synthesis methodology that is not extremely sensitive to moisture, making it easier to synthesize the desired fluorosurfactants. The intermediate formed in the two-step synthesis process is significantly more stable than the acyl fluoride or acyl chloride used in other methods, allowing more flexibility in timelines and decreased probability that the intermediate fouls before the final product is formed. Other advantages include low levels of decarbonylation, low phase separation issues, and easy cleanup. A further advantage is that the disclosed fluorosurfactants do not include a hydrophobic linker. Thus, the disclosed fluorosurfactants have, essentially, two parts (fluorinated and hydrophilic) as compared to three parts (fluorinated / hydrophobic / hydrophilic) for previously disclosed fluorosurfactants. Additionally, the linker molecule (for example, polyether linkers having at least two amine groups) can be chosen to closely resemble a desired hydrophilic polymer. Finally, by reacting a second hydrophilic polymer to the intermediate product, one can extend the hydrophilic side to tailor the size ratios between fluorinated and hydrophilic portions of the surfactant.

[0038] This disclosure provides a two-step synthetic route to make a fluorosurfactant from alkyl ester activated perfluorinated polymers (PFPAE). Any PFPAE polymer can be used to synthesize the disclosed fluorosurfactants. Non-limiting examples include, perfluoropoly ethers (PFPE), perfluoroalkyls, perfluorooctanoate, methyl perfluorooctanoate, and perfluoroalkyl-alkyl esters.

[0039] In the first step, a moisture-stable intermediate is formed by reacting the PFPAE (e.g., a perfluoropolyether (PFPE), perfluoroalkyl, perfluorooctanoate, methyl perfluorooctanoate, or perfluoroalkyl-alkyl ester) with a hydrophilic linker molecule, such as a polyethylene glycol (PEG) diamine, to form a PFPAE block-linker molecule. The PFPAE block-linker intermediate is then coupled to a hydrophilic polymer, such as PEG or alkylated PEG (for example methylated PEG (mPEG)) to provide a fluorosurfactant. A non-limiting example of the methodology is provided in Example 1, and exemplary reaction schemes are provided in Figures 9-10. In addition, the process uses excess amounts of the hydrophilic linker (e.g., a PEG diamine or a mPEG diamine) to limit the formation of a triblock having the chemical structure: PFPAE block-hydrophilic linker-PFPAE block. In various embodiments, amounts of the hydrophilic linker are added in amounts that are about 1.1X to about 100X of the amount of the PFPAE, including fractional values thereof, for example, about 1.5X, 2X, 3X, 4X, 5X, 6X, 7X, 8X, 9X, 10X, 11X, 12X, 13X, 14X, 15X, 16X, 17X, 18X, 19X, 20X, 21X, 22X, 23X, 24X, 25X, 26X, 27X, 28X, 29X, 30X, 3 IX, 32X, 33X, 34X, 35X, 36X, 37X, 38X, 39X, or 40X, or any fractional value thereof, can be added to limit the formation of the triblock. Quality control of the intermediate by NMR can also track the unintended formation of this triblock and quantify the formation of the triblock.

[0040] Thus, the disclosure provides a method of making a compound, comprising reacting a PFPAE with a hydrophilic linker molecule (L) comprising at least a first and a second amine group (for example, a polyethylene glycol comprising at least two amine groups or 2-(2- Aminoethoxy)ethylamine, or l,8-Diamino-3,6-dioxaoctane (DADOO)), and forming an amide bond between the PFPAE and the linker molecule (L) via the first amine group to form a compound represented by the formula PFPAE block-L, wherein represents the amide bond. In some embodiments, the linker is 2-(2-Aminoethoxy)ethylamine or l,8-Diamino-3,6- dioxaoctane (DADOO). Thus, the disclosure provides a method of making a compound, comprising reacting a PFPAE with a linker molecule (L) comprising at least a first and a second amine group, and forming an amide bond between the PFPAE and the linker molecule (L) via the first amine group to form a compound represented by the formula PFPAE block-L, wherein represents the amide bond.

[0041] In various embodiments, the PFPAE comprises: a) the formula of F(CF(CF3)CF2O)xCF(CF3)COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCOO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group, and wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 including fractional values thereof or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values. In various embodiments, L comprises a linker comprising at least two amine groups. Non-limiting examples include those having: a) the formula NH2(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from

[0042] 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (in some cases 1, 2, 3, 4, 5,

[0043] 6, 7, 8, or 9, and in other cases 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (in some cases 1, 2, or 3, and in other cases 2); or b) the formula NH2(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1,

[0044] 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) formula NH2((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6,

[0045] 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula NH2(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or f) L is 2-(2-Aminoethoxy)ethylamine, l,8-Diamino-3,6-di oxaoctane (DADOO), l,l l-diamino-3,6,9-trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine (1,14- Diamino-3,6,9,12-tetraoxatetradecane), or 4,9-dioxa-l,12-dodecanediamine (1,12-diamino- 4, 9 -di oxadodecane) .

[0046] In certain embodiments, compositions comprising the disclosed surfactants and optionally aqueous and / or non-aqueous components are provided by this disclosure. The composition can comprise a discontinuous aqueous and / or lipophilic (nonaqueous) phase and the composition may include one or more physiologically acceptable reagents. The reagents may be dissolved or suspended in the discontinuous phase. In another set of embodiments, the discontinuous aqueous and / or lipophilic phase of a droplet / emulsion may include one or more reagents that can participate in a chemical and / or in a biological reaction of interest. Nonlimiting examples of reagents that can be involved in a chemical and / or biological reaction, or other chemical and / or biological process, include: buffers, salts, nutrients, therapeutic agents, drugs, hormones, antibodies, analgesics, anticoagulants, anti-inflammatory compounds, antimicrobial compositions, cytokines, enzymes, a reverse transcriptase, growth factors, interferons, lipids, oligonucleotides polymers, polysaccharides, polypeptides, protease inhibitors, cells, nucleic acids, RNA, DNA, vasoconstrictors or vasodilators, vitamins, minerals, stabilizers and the like. In other embodiments, the discontinuous aqueous and / or lipophilic phase can contain toxins and / or other substances to be tested, assayed, or reacted within the droplet. Accordingly, chemical and / or biological reactions may be performed within compositions disclosed herein. In some cases, a polymerase chain reaction may be performed within compositions disclosed herein.

[0047] As used herein, “nonaqueous” is meant to define material (e.g., a hydrophobic material or liquid) such as a fluid that is immiscible with water. That is, a liquid that when mixed with water will form a stable two-phase mixture. The non-aqueous phase need not be liquid, but can be a solid or semi-solid lipid or other nonpolar substance that is not soluble in water. In some instances, the nonaqueous phase can include a lipophilic component (e.g., a hydrocarbon) or a fluorinated component (e.g., a fluorocarbon). The aqueous phase can be any liquid miscible with water; that is, any liquid that, when admixed with water, can form a room-temperature, single-phase solution that is stable. In some cases, the aqueous phase can comprise one or more physiologically acceptable reagents and / or solvents, etc. Non-limiting examples of aqueous phase materials include (besides water itself) methanol, ethanol, DMF (dimethylformamide), or DMSO (dimethyl sulfoxide).

[0048] The compositions or surfactants disclosed herein can form, or form part of, emulsions, and these emulsions may be formed using any suitable emulsification procedure known to those of ordinary skill in the art. In this regard, it will be appreciated that the emulsions can be formed using microfluidic systems, ultrasound, high pressure homogenization, shaking, stirring, spray processes, membrane techniques, or any other appropriate method. In one particular embodiment, a micro-capillary or a microfluidic device is used to form an emulsion in the form of a droplet. The size and stability of the droplets produced by this method may vary depending on, for example, capillary tip diameter, fluid velocity, viscosity ratio of the continuous and discontinuous phases, and interfacial tension of the two phases. Droplets of varying sizes and volumes may be generated within the microfluidic system. These sizes and volumes can vary depending on factors such as fluid viscosities, infusion rates, and nozzle size / configuration. Droplets may be chosen to have different volumes depending on the particular application. For example, droplets can have volumes of less than 1 pL (microliter), less than 0.1 pL (microliter), less than 10 nL, less than 1 nL, less than 0.1 nL, or less than 10 pL.

[0049] Examples of linker molecules suitable for use in the disclosed methods and the surfactants provided herein include, but are not limited, to PEG diamines with one to 10 repeat units, such as (a) 2-(2-Aminoethoxy)ethylamine, (b) l,8-Diamino-3,6-dioxaoctane (DADOO), (c) l,l l-Diamino-3,6,9-trioxaundecane, and (d) 3,6,9, 12-Tetraoxatetradecane-l,14-diamine (l,14-Diamino-3,6,9,12-tetraoxatetradecane), and other polyether diamines like 4,9-Dioxa- 1,12-dodecanediamine. Alternatively, branched / star / dendrimer polyether linkers with two (2) or more amines can be used as well. Non-limiting examples of such linkers include C21H48N4O8, 8-[2-(2-Aminoethylethoxy)ethylethoxy]-C,C,C,C-tetraethyl-3,6,10,13- tetraoxapentadecane-l,15-diamine, CAS 172355-14-5: 8,8-bis({[2-(2- aminoethoxy)ethoxy]methyl})-3,6,10,13-tetraoxapentadecane-l,15-diamine, and CAS 5045- 94-3 (Tetra-aminopropyloxyl)m ethylmethane. Yet other linkers can be polyalcohol molecules that contain two or more amine groups. Non-limiting examples of such polyalcohols include: l,6-diaminohexane-2,3,4,5-tetrol, (CAS: 41111-65-3), l,2-diaminoethane-l,2-diol (CAS: 103538-65-4), and l,4-diaminobutane-2,3-diol, (CAS: 32798-38-2).

[0050] Other exemplary linkers are: a) the formula NH2(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (in some cases 1, 2, 3, 4, 5, 6, 7, 8, or 9, and in other cases, 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 20 (in some cases 1, 2, or 3, and in other cases, 2); or b) the formula NH2(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula NH2((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or d) the formula NH2((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2 and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, and k can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or e) the formula NH2(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0051] The first step of reacting the PFPAE (e.g., a perfluoropoly ether (PFPE), perfluoroalkyl, perfluorooctanoate, methyl perfluorooctanoate, or perfluoroalkyl-alkyl ester) with a hydrophilic linker molecule (e.g., a PEG diamine) may be performed using any suitable conditions to allow formation of a PFPAE block-linker molecule or a PFPE block-linker molecule. For example, the reaction may be performed under neat conditions, or using a solvent, or a combination of solvents, for one or both of the PFPAE and the hydrophilic linker molecule. Any suitable solvent known in the art may be used, including, without limitation, organic solvents; aprotic solvents such as tetrahydrofuran (THF), acetone, acetonitrile, chloroform, dichloromethane, dimethylformamide, dimethylpropyleneurea, dimethyl sulfoxide, ethyl acetate, hexamethylphosphoramide, pyridine, and sulfolane; alcohols, such as ethanol or isopropanol; hydrophobic fluids, such as oils; a fluorinated solvent, such as fluorinated oils, e.g., HFE7500, HFE7200, and HFE7100. In some embodiments, the PFPAE (e.g., PFPE) is dissolved in a fluorinated solvent, such as HFE7500. In some embodiments, the linker molecule (e.g., a PEG diamine) is dissolved in an organic solvent, such as an aprotic solvent, e.g., THF. In some embodiments, the reaction may be performed at room temperature (e.g., at temperature of between about 20 °C and about 25°C). In other cases, the reaction may be performed at a temperature below room temperature, such as between about 0 °C and about 19°C. In other cases, the reaction may be performed at a temperature above room temperature, such as between about 26 °C and about 100°C. The reaction may be performed in the presence of oxygen or under an inert atmosphere (for example, a nitrogen atmosphere).

[0052] The intermediate formed by the first step is further reacted with a hydrophilic polymer of choice to form a surfactant with the desired hydrophilic tail length. Examples of hydrophilic polymers that may be used include, but are not limited to, monodisperse and polydisperse NHS- esters of PEG. Monodispersed PEGs can be used to reduce the variability between batches.

[0053] The second step of reacting the intermediate formed by the first step (PFPAE blocklinker molecule) with a hydrophilic polymer of choice may be performed using any suitable conditions to allow formation of the surfactant with the desired hydrophilic tail length. For example, the reaction may be performed under neat conditions, or using a solvent, or a combination of solvents, for one or both of the intermediate and the hydrophilic polymer. Any suitable solvent known in the art may be used, including, without limitation, organic solvents; aprotic solvents such as tetrahydrofuran (THF), acetone, acetonitrile, chloroform, dichloromethane, dimethylformamide, dimethylpropyleneurea, dimethyl sulfoxide, ethyl acetate, hexamethylphosphoramide, pyridine, and sulfolane; alcohols, such as ethanol or isopropanol; hydrophobic fluids, such as oils; a fluorinated solvent, such as fluorinated oils, e.g., HFE7500, HFE7200, and HFE7100. In some embodiments, the intermediate formed by the first step (PFPAE block-linker molecule) is dissolved in a fluorinated solvent, such as HFE7100. In some embodiments, the hydrophilic polymer is dissolved in an organic solvent, such as an aprotic solvent, e.g., THF. In some embodiments, the reaction may be performed at room temperature (e.g., at temperature of between about 20 °C and about 25°C). In other cases, the reaction may be performed at a temperature below room temperature, such as between about 0 °C and about 19°C. In other cases, the reaction may be performed at a temperature above room temperature, such as between about 26 °C and about 100°C. The reaction may be performed in the presence of oxygen or under an inert atmosphere (for example, a nitrogen atmosphere).

[0054] In one embodiment, a PFPAE (for example, a PFPE-methyl ester) is reacted with a PEG diamine to form an intermediate. The reaction can be performed in the presence of oxygen or under an inert atmosphere (for example, a nitrogen atmosphere). One non-limiting example is provided by the reaction scheme in Figure 9 (where n is an average repeat number between 5- 50, 5-45, preferably between 5-25).

[0055] The intermediate is then reacted with monodisperse or polydisperse functionalized hydrophilic polymers, such as functionalized monodisperse or polydisperse PEG molecules or functionalized alkyl-PEG molecules that are monodisperse or polydisperse, such as monodisperse or polydisperse NHS-mPEG, to provide a polyfluorinated surfactant. The monodisperse or polydisperse hydrophilic polymers may be functionalized with amine reactive groups, such as N-hydroxysuccinimide or otherwise activated carboxylic acids to facilitate linkage to an amine group found on the intermediate. Monodisperse hydrophilic polymers (e.g., monodisperse PEG polymers) are pure compounds with precise number of units (e.g., PEG units) and a single molecular weight. In contrast, a poly disperse hydrophilic polymer (e.g., polydisperse PEG polymers) is a polymer mixture with an average molecular weight, such as 5K, 10K, etc. Hydrophilic polymer shapes include linear, branched, star, with a combination of different chain lengths. In various aspects of this disclosure^ monodisperse or polydisperse polymers (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymers (e.g., alkylated PEG) have molecular weights (or average molecular weights) of about 500 Da to about 5000 Da, about 500 Da to about 2500 Da, about 500 Da to about 1000 Da, or about 500 Da to about 750 Da. In various other aspects of this disclosure, monodisperse or polydisperse polymers (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymers (e.g., alkylated PEG) have molecular weights (or average molecular weights) of about 350 Da to about 5000 Da, about 350 Da to about 2500 Da, about 350 Da to about 1000 Da, or about 350 Da to about 750 Da. In yet other aspects of this disclosure, monodisperse or poly disperse polymers (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymers (e.g., alkylated PEG) have molecular weights (or average molecular weights) of about 300 Da to about 5000 Da, about 300 Da to about 2500 Da, about 300 Da to about 1000 Da, or about 300 Da to about 750 Da. In other embodiments, monodisperse or polydisperse polymers (e.g., monodisperse or polydisperse PEG) or alkylated polymers (e.g., alkylated PEG) having between 2 and 75 repeating units (e.g., for PEG, of -(O-CH2-CH2)-) may be used in the methods provided herein. In some embodiments, there are 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 repeating units of-(O-CH2- CH2)-. In some embodiments, there are 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 repeating units of -(O-CH2-CH2)-. For polydisperse PEG or alkylated PEG, these polymers can have average molecular weights of about 350 Da to about 5000 Da, about 350 Da to about 2500 Da, about 350 Da to about 1000 Da, or about 350 Da to about 750 Da, or may be designated as having an average repeat value (also referred to as average repat units) between 2 and 75, including fractional values thereof; between 2 and 30, including fractional values thereof; between 5 and 25, including fractional values thereof; or between 8 and 20, including fractional values thereof.

[0056] As used herein, the term “alkyl” refers to a straight or branched, saturated, aliphatic molecule having between 1-10 carbon atoms. For example, Ci-Cio alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl groups and stereoisomers thereof, heptyl groups and stereoisomers thereof, octyl groups and stereoisomers thereof, nonyl groups and stereoisomers thereof, and decyl groups and stereoisomers thereof. The alkyl can include any number of carbons, such as 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7- 9, 7-10, 8-9, 8-10, 9-10, or 10 carbons.

[0057] Thus, various forms of monodisperse and polydisperse amine-reactive polymers, such as amine-reactive PEG-alkyl molecules, can be used. PEG-alkyl groups can be represented by the formula alkyl-(O-CH2-CH2)m-R, where m is an integer between 2 and 75 (inclusive of the end points of this range) or is any integer selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, R is an amine reactive group (such as N-hydroxysuccinimide or another activated carboxylic acid group), and the alkyl group is a Cl -CIO alkyl group, preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and / or hexyl group, more preferably a methyl, ethyl, or propyl group, and more preferably a methyl group or ethyl group. In some embodiments, m is an average repeat value (also referred to as average repeat units) between 2 and 75, including fractional values thereof; between 2 and 30, including fractional values thereof; between 5 and 25, including fractional values thereof; or between 8 and 20, including fractional values thereof.

[0058] In other embodiments, the intermediate formed by the first step is further reacted with a hydrophilic polymer block of choice to form a surfactant with the desired hydrophilic tail length. The hydrophilic polymer block may include polyethylene oxide (PEO), polyethyleneglycol (PEG), poly(N-isopropylacrylamide) (PNIPAM), polyvinyl caprolactam (PVCL), polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA) as well as some polyacids and polybases, and combinations of hydrophilic polymers. These hydrophilic polymers are functionalized so as to be reactive with an amine group on the linker molecule (e.g., with N- hydroxysuccinimide esters or another activated carboxylic acid group) and may be, optionally, alkylated as discussed above.

[0059] In various aspects of this disclosure, monodisperse or polydisperse hydrophilic polymer blocks (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymer blocks (e.g., alkylated PEG) have molecular weights (or average molecular weights) of about 500 Da to about 5000 Da, about 500 Da to about 2500 Da, about 500 Da to about 1000 Da, or about 500 Da to about 750 Da. In various other aspects of this disclosure, a monodisperse or polydisperse hydrophilic polymer block (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymer block (e.g., alkylated PEG) has a molecular weight (or average molecular weight) of about 350 Da to about 5000 Da, about 350 Da to about 2500 Da, about 350 Da to about 1000 Da, or about 350 Da to about 750 Da. In yet other aspects of this disclosure, monodisperse or polydisperse hydrophilic polymer blocks (e.g., monodisperse or polydisperse PEG polymers) or alkylated polymers (e.g., alkylated PEG) have molecular weights (or average molecular weights) of about 300 Da to about 5000 Da, about 300 Da to about 2500 Da, about 300 Da to about 1000 Da, or about 300 Da to about 750 Da. Polydisperse hydrophilic polymer blocks may also be designated as having an average repeat value (also referred to as average repeat units) of between 2 and 75, including fractional values thereof; between 2 and 30, including fractional values thereof; between 5 and 25, including fractional values thereof; or between 8 and 20, including fractional values thereof.

[0060] The disclosure provides the following non-limiting embodiments (claimable subject matter):

[0061] 1. A surfactant comprising a perfluorinated polyether (PFPE) block or a PFPAE block coupled to a linker molecule (L) via a first amide bond and the linker molecule (L) being coupled via a second amide bond to a hydrophilic polymer block, said hydrophilic polymer block being optionally alkylated.

[0062] 2. The surfactant of embodiment 1, wherein the hydrophilic polymer block comprises a polyethylene glycol (PEG) block, the PEG block being optionally alkylated.

[0063] 3. The surfactant of embodiment 1 or embodiment 2, wherein the PFPAE block or PFPE block comprises: a) the formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCO-, wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60, including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; c) the formula CF3O(CF2CF2O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values within each of the recited ranges; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values within each of the recited ranges.

[0064] 4. The surfactant of embodiment 2 or embodiment 3, wherein the PEG block comprises a formula of -(CnEEn O)y-H or -(CnH2nO)y-alkyl, wherein the alkyl is a Ci-Cio alkyl, n is an integer selected from 1, 2, 3, 4, 5, or 6, preferably 1, 2, 3 or 4, more preferably 2, and y is an integer selected from 2-75 or is an integer selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, preferably 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, more preferably 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or y is an average repeat value between 2 and 75, including fractional values thereof, between 2 and 30, including fractional values thereof, between 5 and 25, including fractional values thereof, or between 8 and 20, including fractional values thereof.

[0065] 5. The surfactant of any one of embodiments 1-4, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula - NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH -, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5 (preferably, independently 0, 1, 2 or 3, or e and f are selected such that e + f = 0, 1, or 2); a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -M I(CH2)q()(CH2)s()(CH2) M I-, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably q and s are, independently, 1, 2 or 3 and can be the same or different and r is 1, 2, 3, or 4); or f) L forms an amide bond with the PFPAE block or PFPE block to which it is coupled and an amide bond with the hydrophilic polymer block and L is 2-(2- Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO), 1,1 l-diamino-3,6,9- trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9-dioxa-l,12- dodecanediamine.

[0066] 6. The surfactant of any one of embodiments 1-5, wherein the hydrophilic polymer block is alkylated with a methyl or ethyl group.

[0067] 7. The surfactant of any one of embodiments 1-6, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, and 5, and z is an integer selected from 1, 2, or 3, or y is 2 or 3 and z is 1, 2, or 3, or y is 2 and z is 2; or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)(NH-, wherein: e is 0, 1, or 2, f is 0, 1, 2, or 3, or e and f are selected such that e + f = 0, 1, or 2; a is an integer selected from 1, 2, 3, 4, 5, or 6; b is an integer selected from 0 or 1; c is an integer selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, I, j, k, and m can be the same or different; -g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; I is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3; or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3.

[0068] 8. A compound comprising a perfluorinated polyether (PFPE) block or a PFPAE block coupled to a linker molecule (L) via a first amide bond and the linker molecule (L) comprising a second amine group, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from

[0069] 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1,

[0070] 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2 and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, and k can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -NH(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or f) L forms a single amide bond with the PFPE bock or the PFPAE block and L is 2-(2-Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO), 1,1 l-diamino-3,6,9- trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9-dioxa-l,12- dodecanediamine.

[0071] 9. The compound of embodiment 8, wherein the PFPAE block or PFPE block comprises: a) the formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCO-, wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60, including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values.

[0072] 10. The compound of embodiment 8 or embodiment 9, said compound being selected from the group consisting of: wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein i = 1-12 and wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is an average value between 5 and 50, preferably between 8 and 40; wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values; , wherein i is a value between

[0073] 1-12 and m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values;

[0074] 1-12 and m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; wherein n is a value between 5 and 40, preferably between 5 and 35, including fractional values; preferably between 5 and 35, including fractional values; and wherein n is a value between 5 and 40, preferably between 5 and 35, including fractional values. 11. The compound of embodiment 8 or embodiment 9, wherein L has the formula -NH(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from 1, 2, 3, 4, and 5 and z is an integer selected from 1, 2, or 3, y is 2 or 3 and z is 1, 2, or 3, or y is 2 and z is 2.

[0075] 12. The compound of embodiment 8 or embodiment 9, wherein L has the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 1, 2, or 3; a is an integer selected from 1 or 2; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0,1, 2, or 3; and d is an integer selected from 1, 2, 3, or 4.

[0076] 13. The compound of embodiment 8 or embodiment 9, wherein L has the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3.

[0077] 14. The compound of embodiment 8 or embodiment 9, wherein L has the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2 and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2 or 3.

[0078] 15. The compound of embodiment 8 or embodiment 9, wherein L has the formula -NH(CH2)qO(CH2)rO(CH2)sNH2, wherein q is an integer selected from 1, 2, 3, or 4; r is an integer selected from 1, 2, 3, or 4; and s is an integer selected from 1, 2, 3, or 4.

[0079] 16. A composition comprising the surfactant of any one of embodiments 1-7.

[0080] 17. The composition of embodiment 16, further comprising a hydrophobic liquid, optionally wherein the hydrophobic liquid is a fluorinated oil or a silicone oil, or a combination thereof.

[0081] 18. The composition of embodiment 16 or embodiment 17, further comprising an aqueous liquid.

[0082] 19. The composition of embodiment 16, further comprising a fluorinated oil and an aqueous liquid.

[0083] 20. The composition of embodiment 18 or embodiment 19, wherein the aqueous liquid additionally comprises biological molecules. 21. The composition of embodiment 20, wherein the biological molecules comprise nucleic acids.

[0084] 22. A method of forming aqueous droplets, comprising: providing a microfluidic device; providing an aqueous liquid to the microfluidic device; providing a fluorinated liquid to the microfluidic device; providing a surfactant of any one of embodiments 1-7, and forming aqueous droplets in the fluorinated liquid in the presence of the surfactant, said droplets comprising the surfactant, optionally wherein the fluorinated liquid is a fluorinated oil.

[0085] 23. A composition comprising the compound of any one of embodiments 8-15.

[0086] 24. A method of forming an emulsion comprising a plurality of droplets, the method comprising: (a) providing a composition comprising a fluid immiscible or substantially immiscible with water and the surfactant of any one of embodiments 1-7; (b) providing an aqueous fluid, optionally wherein the aqueous fluid comprises target nucleic acids or biological molecules; and (c) contacting said composition with the aqueous fluid, thereby generating an emulsion of a plurality of droplets of the aqueous fluid dispersed in the fluid immiscible or substantially immiscible with water.

[0087] 25. The method of embodiment 24, wherein the fluid immiscible or substantially immiscible with water is an oil, optionally a fluorinated oil, a silicone oil, or a combination thereof.

[0088] 26. An emulsion comprising: a) an aqueous liquid and a surfactant according to any one of embodiments 1-7 and, optionally, a fluid immiscible or substantially immiscible with the aqueous liquid; or b) a fluid immiscible or substantially immiscible with water and a surfactant according to any one of embodiments 1-7 and, optionally, an aqueous liquid.

[0089] 27. The emulsion of embodiment 26, wherein the emulsion further comprises biological or nucleic acid molecules.

[0090] 28. The emulsion of embodiment 26 or 27, wherein the emulsion comprises an aqueous liquid, a surfactant and a fluid immiscible or substantially immiscible with the aqueous liquid.

[0091] 29. An emulsion comprising: (a) a plurality of droplets of an aqueous liquid dispersed in a fluid immiscible or substantially immiscible with the aqueous liquid, and (b) a surfactant according to any one of embodiments 1-7. 30. The emulsion of embodiment 29, wherein at least a portion of the surfactant is present at an interface between the aqueous liquid and the fluid immiscible or substantially immiscible with the aqueous liquid.

[0092] 31. The emulsion of embodiment 29 or embodiment 30, wherein one or more of the droplets comprise biological or nucleic acid molecules.

[0093] 32. The emulsion of any one of embodiments 26-31, wherein the fluid is an oil, optionally a fluorinated oil, a silicone oil, or a combination thereof.

[0094] 33. A method of making a compound, comprising reacting a PFPAE with a linker molecule (L) comprising at least a first and a second amine group, and forming an amide bond between the PFPAE and the linker molecule (L) via the first amine group to form a compound represented by the formula PFPAE block-L, wherein represents the amide bond.

[0095] 34. The method of embodiment 33, wherein the PFPAE comprises: a) the formula of F(CF(CF3)CF2O)xCF(CF3)COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)y COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values.

[0096] 35. The method of embodiment 33 or embodiment 34, wherein L comprises: a) the formula NH2(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, or an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9, or is 2, and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or an integer selected from 1, 2, or 3, or is 2; or b) the formula NH2(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1,

[0097] 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) formula NH2((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula NH2((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula NH2(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or f) L is 2-(2-Aminoethoxy)ethylamine, l,8-Diamino-3,6-di oxaoctane (DADOO), l,l l-diamino-3,6,9-trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9- dioxa- 1 , 12-dodecanediamine.

[0098] 36. The method of any one of embodiments 33-35, wherein the reaction is carried out in the presence of excess L. 37. The method of embodiment 36, wherein excess L is provided in an amount between about 1.1X to about 100X of the amount of the PFPAE including fractional values thereof, for example, about 1.5X, 2X, 3X, 4X, 5X, 6X, 7X, 8X, 9X, 10X, 1 IX, 12X, 13X, 14X, 15X, 16X, 17X, 18X, 19X, 20X, 21X, 22X, 23X, 24X, 25X, 26X, 27X, 28X, 29X, 30X, 3 IX, 32X, 33X, 34X, 35X, 36X, 37X, 38X, 39X, or 40X.

[0099] 38. The method of any one of embodiments 33-37, said method further comprising reacting the PFPAE block-L compound with an activated hydrophilic polymer block to form a compound having the formula PFPAE block-L-hydrophilic polymer block, wherein the hydrophilic polymer block (HPB) is monodisperse or polydisperse.

[0100] 39. The method of embodiment 38, wherein the activated hydrophilic polymer block (HPB) is a functionalized polyethylene oxide (PEO), polyethyleneglycol (PEG), poly(N- isopropyl acrylamide) (PNIPAM), polyvinyl caprolactam (PVCL), polyvinyl pyrrolidone (PVP), or polyvinyl alcohol (PVA), or any combination thereof.

[0101] 40. The method of embodiment 38 or embodiment 39, wherein the activated hydrophilic polymer block is functionalized with a N-hydroxysuccinimide ester or an activated carboxyl group so as to be reactive with an amine group on the compound having the formula PFPAE block-L.

[0102] 41. The method of embodiment 40, wherein the activated hydrophilic polymer block is optionally alkylated and is functionalized with a N-hydroxysuccinimide ester.

[0103] 42. The method of any one of embodiments 38-41, wherein the formed compound has the formula PFPAE block-L-HPB, the HPB is a polyethylene glycol (PEG) block, the PEG block being optionally alkylated, wherein: the PFPAE block comprises a formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number between 5 and 50, including fractional values thereof; the PEG block comprises a formula of -(CnH2n O)y-H or -(CnH2nO)y-alkyl, wherein the alkyl is a Ci-Cio alkyl, n is an integer selected from 1, 2, 3, 4, 5, or 6, preferably 1, 2, 3 or 4, more preferably 2, and y is an integer selected from 2-75 or is an integer selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, preferably 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,

[0104] 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, more preferably 8, 9, 10, 11, 12, 13, 14, 15, 16,

[0105] 17, 18, 19, or 20; or y is an average repeat value between 2 and 75, including fractional values thereof, between 2 and 30, including fractional values thereof, between 5 and 25, including fractional values thereof, or between 8 and 20, including fractional values thereof, and

[0106] L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH-, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5 (preferably, independently 0, 1, 2 or 3 or e and f are selected such that e + f = 0, 1, or 2); a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -NH(CH2)qO(CH2)rO(CH2)sNH-, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably q and s are, independently, is 1, 2 or 3 and can be the same or different and r is 1, 2, 3, or 4); or f) L forms an amide bond with the PFPAE block to which it is coupled and an amide bond with the hydrophilic polymer block and L is 2-(2-Aminoethoxy)ethylamine, 1,8- Diamino-3,6-di oxaoctane (DADOO), 1,1 l-diamino-3,6,9-trioxaundecane, and 3,6,9,12- Tetraoxatetradecane-1, 14-diamine, or 4,9-dioxa-l, 12-dodecanediamine.

[0107] 43. The method of any one of embodiments 33-42, wherein the compound represented by the formula PFPAE block-L is any one of the compounds of embodiments 8- 15.

[0108] 44. A method of making a compound, comprising reacting the compound of any one of embodiments 8-15 with an activated hydrophilic polymer block that is monodisperse or polydisperse.

[0109] 45. The method of embodiment 44, wherein the hydrophilic polymer block is a functionalized polyethylene oxide (PEO), polyethyleneglycol (PEG), poly(N- isopropyl acrylamide) (PNIPAM), polyvinyl caprolactam (PVCL), polyvinyl pyrrolidone (PVP), or polyvinyl alcohol (PVA), or any combination thereof.

[0110] 46. The method of embodiment 44 or embodiment 45, wherein the hydrophilic polymer block is functionalized so as to be reactive with an amine group on the linker molecule (L).

[0111] 47. The method of embodiment 46, wherein the hydrophilic polymer block is optionally alkylated and is functionalized with a N-hydroxysuccinimide ester or an activated carboxylic acid group.

[0112] 48. The method of any one of embodiments 44-47, wherein the hydrophilic polymer block is a polyethylene glycol (PEG) block, the PEG block being optionally alkylated, wherein: the PFPAE block comprises a formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number between 5 and 50, including fractional values thereof; the PEG block following the reaction with the compound of any one of embodiments 8-15 comprises a formula of -(CnH2n O)y-H or -(CnH2nO)y-alkyl, wherein the alkyl is a Ci-Cio alkyl, n is an integer selected from 1, 2, 3, 4, 5, or 6, preferably 1, 2, 3 or 4, more preferably 2, and y is an integer selected from 2-75 or is an integer selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, preferably 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, more preferably 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 or y is an average repeat value between 2 and 75, including fractional values thereof, between 2 and 30, including fractional values thereof, between 5 and 25, including fractional values thereof, or between 8 and 20, including fractional values thereof; and

[0113] L following the reaction with the PEG block comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH-, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5 (preferably, independently 0, 1, 2 or 3 or e and f are selected such that e + f = 0, 1, or 2); a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -NH(CH2)qO(CH2)rO(CH2)sNH-, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably q and s are, independently, is 1, 2 or 3 and can be the same or different and r is 1, 2, 3, or 4); or f) L forms an amide bond with the PFPAE block to which it is coupled and an amide bond with the hydrophilic polymer block and L is 2-(2-Aminoethoxy)ethylamine, 1,8- Diamino-3,6-di oxaoctane (DADOO), 1,1 l-diamino-3,6,9-trioxaundecane, and 3,6,9,12- Tetraoxatetradecane-1, 14-diamine, or 4,9-dioxa-l, 12-dodecanediamine.

[0114] 49. The surfactant of embodiment 1, wherein the hydrophilic polymer block comprises polyethylene oxide (PEO), polyethyleneglycol (PEG), poly(N-isopropylacrylamide) (PNIPAM), polyvinyl caprolactam (PVCL), polyvinyl pyrrolidone (PVP), or polyvinyl alcohol (PVA), or any combination thereof, and optionally wherein the hydrophilic polymer block is monodisperse or polydisperse.

[0115] All patents, patent applications, provisional applications, and publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.

[0116] Following are examples which illustrate procedures for practicing the invention. These examples should not be construed as limiting. All percentages are by weight and all solvent mixture proportions are by volume unless otherwise noted.

[0117] EXAMPLE 1 - FLUOROSURFACTANT SYNTHESIS SCHEME

[0118] This Example provides an exemplary two-step process for synthesizing a fluorosurfactant.

[0119] Step 1) PFPE-ME + DADOO PFPE-DADOO (see Figure 9 for an exemplary reaction scheme)

[0120] 1) Determine molecular weight of PFPE-ME (methyl ester functionalized polyfluoro polyether polymer) using NMR.

[0121] 2) Dissolve PFPE-ME in HFE7500 (l,l,l,2,3,4,4,5,5,6,6,6-Dodecafluoro-2- (trifluoromethyl)hexan-3-yl ethyl ether) at a 2 g PFPE : 1 mL HFE 7500 (mass to volume) ratio.

[0122] 3) In Tetrahydrofuran (THF) (half the volume compared to HFE7500), dissolve 4 eq of DADOO (l,8-Diamino-3,6-di oxaoctane) in the reactor, using an anchor-type stirrer (or other configurations for mixing viscous liquids). 4) Slowly add the PFPE solution via dropping funnel (or pump) over 30 min at ambient conditions. This may also be performed under inert atmosphere.

[0123] 5) React until completion as observed via FT-IR.

[0124] 6) Transfer reaction mixture to a separatory funnel and add equal volume of ethanol relative to HFE7500. Shake until well mixed and allow to fully separate into two clear layers.

[0125] 7) Collect the lower layer in a weighed round bottom, leaving just a small bit in the separatory funnel.

[0126] 8) Rotovap the collected solution, working slowly to 40°C, 15 mbar. Rotovap until the weight equilibrates. Increase temperature slowly to 55°C and rotovap until weight stabilizes.

[0127] 9) Use NMR and FT-IR to assess purity (% decarb onylated, monofunctionalized compound, and bisfunctionalized compound) and if the structure conforms. LCMS can be used to detect excess DADOO. Monofunctionalized compound has the structure of PFPE-amide- linker-amine or in this case PFPE-DADOO-NH2 (the desired product). Bisfunctionalized compound has two PFPE molecules attached to the same linker (in this case DADOO) and has the structure, PFPE-DADOO-PFPE. This is an unintended side product.

[0128] Step 2) PFPE-DADOO + mPEG-NHS ester

[0129] Protocol - see Figure 10 for an exemplary reaction scheme

[0130] 1) Dissolve PFPE-DADOO in HFE7100 (Methoxy-nonafluorobutane); 1 g polymer to 2-2.5 mL solvent. Determine MW from NMR.

[0131] 2) Dissolve 1.9 eq mPEG-NHS ester in THF (anhydrous, unstabilized), same volume as HFE 7100.

[0132] 3) While stirring, slowly add PEG to PFPE. Solution will slowly increase in cloudiness as PEG is added before eventually decreasing in cloudiness.

[0133] 4) After PEG is added, check if the solution is still cloudy. If so, slowly add more THF until the solution is clear and only 1 phase.

[0134] 5) Allow reaction to proceed for 3 days at ambient conditions.

[0135] 6) Rotovap the solution until mass stabilizes.

[0136] 7) Redissolve dried product in HFE7500 at 3 mL / g of expected product. Transfer to Separatory funnel, using minimal additional HFE7500 to finish transfer.

[0137] 8) Add 50% volume EtOH (ethanol) relative to HFE7500. 9) Cap and vigorously shake. Allow the mixture to fully separate and become clear. Collect the lower, fluorinated layer.

[0138] 10) Rotovap product until weight stabilizes (40°C, 15mbar -> 60°C 15 mb ar).

[0139] 11) Upon cooling, a clear gel or viscous liquid is obtained depending on PEG / PFPE length ratios. Larger PEG to PFPE results in a gel-like product. In some embodiments, the final product is also a white wax.

[0140] EXAMPLE 2 - PERFORMANCE OF EXEMPLARY SURFACTANT RELATIVE TO CONTROL SURFACTANTS

[0141] This Example provides results of experiments characterizing an exemplary surfactant provided by this disclosure. The exemplary surfactant has the formula:

[0142] - 15.88

[0143] Figures 5 A and 5B provide NMR spectra for the exemplary surfactant. 1H NMR: Two amides are shown at 8.38 and 7.59 ppm. The weak signal at 6.02 ppm shows ~1% decarbonylation (Fig. 5 A). Fig. 5B: 19F NMR: fluorine NMR shows low decarbonylation at -146.8 and -85.6 ppm.

[0144] Droplets made using this exemplary surfactant at different weight % solutions in HFE 7500 were visualized both before and after thermal cycling using a standard PCR protocol. Droplets showed stability visually and were comparable to two different control surfactants made using different chemistries (see Figure 6). When used in PCR protocols, the exemplary surfactant showed copy counts comparable to both control surfactants (see Figure 7). The exemplary surfactant also showed comparable event counts (number of droplets detected in a digital PCR instrument) compared to both control surfactants, across the tested weight concentrations of 0.5-3 wt% (see Figure 8). It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and the scope of the appended claims. In addition, any elements or limitations of any invention or embodiment thereof disclosed herein can be combined with any and / or all other elements or limitations (individually or in any combination) or any other invention or embodiment thereof disclosed herein, and all such combinations are contemplated within the scope of the invention without limitation thereto.

Claims

CLAIMSWe claim:

1. A surfactant comprising a perfluorinated polyether (PFPE) block or a PFPAE block coupled to a linker molecule (L) via a first amide bond and the linker molecule (L) being coupled via a second amide bond to a hydrophilic polymer block, said hydrophilic polymer block being optionally alkylated.

2. The surfactant of claim 1, wherein the hydrophilic polymer block comprises a polyethylene glycol (PEG) block, the PEG block being optionally alkylated.

3. The surfactant of claim 1 or claim 2, wherein the PFPAE block or PFPE block comprises: a) the formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCO-, wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60, including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; c) the formula CF3O(CF2CF2O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values within each of the recited ranges; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values within each of the recited ranges.

4. The surfactant of claim 3, wherein the PEG block comprises a formula of -(CnEkn O)y-H or -(CnH2nO)y-alkyl, wherein the alkyl is a Ci-Cio alkyl, n is an integer selected from 1, 2, 3, 4, 5, or 6, preferably 1, 2, 3 or 4, more preferably 2, and y is an integer selected from 2-75 or is an integer selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, preferably 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, more preferably 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or y is an average repeat value between 2 and 75, including fractional values thereof, between 2 and 30, including fractional values thereof, between 5 and 25, including fractional values thereof, or between 8 and 20, including fractional values thereof.

5. The surfactant of claim 4, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula - NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH -, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5 (preferably, independently 0, 1, 2 or 3, or e and f are selected such that e + f = 0, 1, or 2); a is an integer selected from 1, 2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); ore) the formula H(CH2) ()(CH2)sO(CH2) I I-, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably q and s are, independently, 1, 2 or 3 and can be the same or different and r is 1, 2, 3, or 4); or f) L forms an amide bond with the PFPAE block or PFPE block to which it is coupled and an amide bond with the hydrophilic polymer block and L is 2-(2- Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO), 1,1 l-diamino-3,6,9- trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9-dioxa-l,12- dodecanediamine.

6. The surfactant of claim 5, wherein the hydrophilic polymer block is alkylated with a methyl or ethyl group.

7. The surfactant of claim 3, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH-, wherein y is an integer selected from 1, 2, 3, 4, and 5, and z is an integer selected from 1, 2, or 3, or y is 2 or 3 and z is 1, 2, or 3, or y is 2 and z is 2; or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)tNH-, wherein: e is 0, 1, or 2, f is 0, 1, 2, or 3, or e and f are selected such that e + f = 0, 1, or 2; a is an integer selected from1, 2, 3, 4, 5, or 6; b is an integer selected from 0 or 1; c is an integer selected from 1 or 2, wherein b+c=2a; g is 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g, h, I, j, k, and m can be the same or different; -g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; I is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3; or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH-, wherein g is an integer selected from 1,2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3.

8. A compound comprising a perfluorinated polyether (PFPE) block or a PFPAE block coupled to a linker molecule (L) via a first amide bond and the linker molecule (L) comprising a second amine group, wherein L comprises: a) the formula -NH(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 (preferably 1, 2, 3, 4, 5, 6, 7, 8, or 9, or more preferably 2) and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2, or 3, or more preferably 2); or b) the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)iNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1,2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2 and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, and k can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula -NH(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or f) L forms a single amide bond with the PFPE bock or the PFPAE block and L is 2-(2-Aminoethoxy)ethylamine, l,8-Diamino-3,6-dioxaoctane (DADOO), 1,1 l-diamino-3,6,9-tri oxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9-dioxa-l,12- dodecanediamine.

9. The compound of claim 8, wherein the PFPAE block or PFPE block comprises: a) the formula of F(CF(CF3)CF2O)XCF(CF3)CO-, wherein x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)yCO-, wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60, including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2CO-, wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values.

10. The compound of claim 8 or claim 9, said compound being selected from the group consisting of:wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein i = 1-12 and wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is an average value between 5 and 50, preferably between 8 and 40;wherein n is an average value between 5 and 50, preferably between 8 and 40, including fractional values;1-12 and m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values;1-12 and m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values;wherein n is a value between 5 and 40, preferably between 5 and 35, including fractional values;wherein n is a value between 5 and 40, preferably between 5 and 35, including fractional values; andwherein n is a value between 5 and 40, preferably between 5 and 35, including fractional values.

11. The compound of claim 8 or claim 9, wherein L has the formula -NH(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from 1, 2, 3, 4, and 5 and z is an integer selected from 1, 2, or 3, y is 2 or 3 and z is 1, 2, or 3, or y is 2 and z is 2.

12. The compound of claim 8 or claim 9, wherein L has the formula -NH(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 1, 2, or 3; a is an integer selected from 1 or 2; b is selected from 0 or 1; c isselected from 1 or 2, wherein b+c=2a; g is 0,1, 2, or 3; and d is an integer selected from 1, 2, 3, or 4.

13. The compound of claim 8 or claim 9, wherein L has the formula -NH((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2, or 3.

14. The compound of claim 8 or claim 9, wherein L has the formula -NH((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2 and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g is an integer selected from 1, 2, or 3; h is an integer selected from 1, 2, or 3; i is an integer selected from 1, 2, or 3; j is an integer selected from 1, 2, or 3; k is an integer selected from 1, 2, or 3; and m is an integer selected from 1, 2 or 3.

15. The compound of claim 8 or claim 9, wherein L has the formula -NH(CH2)qO(CH2)rO(CH2)sNH2, wherein q is an integer selected from 1, 2, 3, or 4; r is an integer selected from 1, 2, 3, or 4; and s is an integer selected from 1, 2, 3, or 4.

16. A composition comprising the surfactant of any one of claims 4-7.

17. The composition of claim 16, further comprising a hydrophobic liquid, optionally wherein the hydrophobic liquid is a fluorinated oil or a silicone oil, or a combination thereof.

18. A method of forming aqueous droplets, comprising: providing a microfluidic device; providing an aqueous liquid to the microfluidic device; providing a fluorinated liquid to the microfluidic device; providing a surfactant of any one of claims 4-7; and forming aqueous droplets in the fluorinated liquid in the presence of the surfactant, said droplets comprising the surfactant, optionally wherein the fluorinated liquid is a fluorinated oil.

19. A composition comprising the compound of any one of claims 8-15.

20. A method of forming an emulsion comprising a plurality of droplets, the method comprising: (a) providing a composition comprising a fluid immiscible or substantially immiscible with water and the surfactant of any one of claims 4-7; (b) providing an aqueous fluid, optionally wherein the aqueous fluid comprises target nucleic acids or biological molecules; and (c) contacting said composition with the aqueous fluid, thereby generating an emulsion of a plurality of droplets of the aqueous fluid dispersed in the fluid immiscible or substantially immiscible with water.

21. An emulsion comprising: a) an aqueous liquid and a surfactant according to any one of claims 4-7 and, optionally, a fluid immiscible or substantially immiscible with the aqueous liquid; or b) a fluid immiscible or substantially immiscible with water and a surfactant according to any one of claims 4-7 and, optionally, an aqueous liquid.

22. An emulsion comprising: (a) a plurality of droplets of an aqueous liquid dispersed in a fluid immiscible or substantially immiscible with the aqueous liquid, and (b) a surfactant according to any one of claims 4-7.

23. A method of making a compound, comprising reacting a PFPAE with a linker molecule (L) comprising at least a first and a second amine group, and forming an amide bond between the PFPAE and the linker molecule (L) via the first amine group to form a compound represented by the formula PFPAE block-L, wherein represents the amide bond.

24. The method of claim 23, wherein the PFPAE comprises: a) the formula of F(CF(CF3)CF2O)xCF(CF3)COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and x is an average repeat number selected from 5 to 50, or 5 to 45, inclusive of fractional values; or b) the formula (CF3CF2CF2(OCF(CF3)CF2)y COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein y is an average repeat number selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54,55, 56, 57, 58, 59, or 60 including fractional values thereof, or y is a value between 5 and 60, or 5 and 50, or 5 and 40, including fractional values within each of the recited ranges; or c) the formula CF3O(CF2CF2O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values; or d) the formula CF3O(CF2CF(CF3)O)m(CF2O)nCF2COO-alkyl, wherein alkyl is a methyl, ethyl, propyl, butyl, or pentyl group and wherein m and n are independently selected such that m+n = a value between 5 and 50, preferably between 8 and 40, including fractional values.

25. The method of claim 24, wherein L comprises: a) the formula NH2(CH2CH2O)y(CH2)zNH2, wherein y is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, or an integer selected from1, 2, 3, 4, 5, 6, 7, 8, or 9, or is 2, and z is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or an integer selected from 1, 2, or 3, or is 2; or b) the formula NH2(CH2)e(CaHbOHc(CH2)g)d(CH2)fNH2, wherein e and f can be the same or different and are, independently, 0, 1, 2, 3, 4, or 5; a is an integer selected from 1,2, 3, 4, 5, or 6; b is selected from 0 or 1; c is selected from 1 or 2, wherein b+c=2a; g is an integer selected from 0, 1, 2, or 3; and d is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; or c) formula NH2((CH2)gO)m(CH2)hCHXiX2, wherein Xi and X2 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or d) the formula NH2((CH2)gO)m(CH2)hCXiX2X3, wherein Xi, X2, and X3 can be the same or different and are -(CH2)iO(CH2)jO(CH2)kNH2, wherein g, h, i, j, k, and m can be the same or different; g is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); h is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); i is an integerselected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); j is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); k is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); and m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (preferably 1, 2 or 3); or e) the formula NH2(CH2)qO(CH2)rO(CH2)sNH2, wherein q, r, and s can be the same or different and are an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or f) L is 2-(2-Aminoethoxy)ethylamine, l,8-Diamino-3,6-di oxaoctane (DADOO), l,l l-diamino-3,6,9-trioxaundecane, and 3,6,9, 12-Tetraoxatetradecane-l,14-diamine, or 4,9- dioxa- 1 , 12-dodecanediamine.

26. A method of making a compound, comprising reacting the compound of any one of claims 8-15 with an activated hydrophilic polymer block that is monodisperse or polydisperse.

27. The method of claim 26, wherein the hydrophilic polymer block is a functionalized polyethylene oxide (PEO), polyethyleneglycol (PEG), poly(N- isopropyl acrylamide) (PNIPAM), polyvinyl caprolactam (PVCL), polyvinyl pyrrolidone (PVP), or polyvinyl alcohol (PVA), or any combination thereof.

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