Covalent surface functionalization of one-dimensional lepidocrocite titanium oxide

Abstract

A one-dimensional lepidocrocite titanium oxide material, the material having a surface functionality covalently bound thereto. Also provided is a method of functionalizing a one-dimensional lepidocrocite titanium oxide material (1DL), comprising: contacting the 1DL material with a hydrocarbon halide or a hydrocarbon alcohol under such conditions that the hydrocarbon halide or hydrocarbon alcohol reacts with the 1DL material so as to give rise to a reaction product, the reaction product being covalently bound to the 1DL material.

Description

COVALENT SURFACE FUNCTIONALIZATION OF ONE-DIMENSIONAL LEPIDOCROCITE TITANIUM OXIDERELATED APPLICATIONS

[0001] The present application claims priority to and the benefit of United States patent application no. 63 / 600,086, “Covalent Surface Functionalization Of One-Dimensional Lepidocrocite Titanium Oxide,” filed November 17, 2023. All foregoing applications are incorporated herein by reference in their entireties for any and all purposes.TECHNICAL FIELD

[0002] The present disclosure relates to the field of materials science, in particular the field of nanofilaments.BACKGROUND

[0003] One-dimensional lepidocrocite titanium oxide materials (IDLs) are an important material with a range of industrial applicability. Accordingly, there is a need in the art for further expanding the capabilities of such materials.SUMMARY

[0004] In meeting the described long-felt needs, the present disclosure provides a one-dimensional lepidocrocite titanium oxide material, the material having a surface functionality covalently bound thereto. Also provided is a method of functionalizing a onedimensional lepidocrocite titanium oxide material (1DL), comprising: contacting the 1DL material with a hydrocarbon halide or a hydrocarbon alcohol under such conditions that the hydrocarbon halide or hydrocarbon alcohol reacts with the 1DL material so as to give rise to a reaction product, the reaction product being covalently bound to the 1DL material.

[0005] Provided here are, inter alia, methods to functionalize the surface of onedimensional lepidocrocite titanium oxide material (1DL). Also provided are functionalized 1DL materials.BRIEF DESCRIPTION OF THE DRAWINGS

[0006] In the drawings, which are not necessarily drawn to scale, like numerals may describe similar components in different views. Like numerals having different letter suffixes may represent different instances of similar components. The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed in the present document. In the drawings:

[0007] FIG. 1 : FTIR spectra of both untreated 1DL (black line) and 1 -iodooctane treated 1DL (red line). Note the peaks in red line around 2900 cm’1, indicative of C-H stretches present in the octane. Also, the region around 1,000 cm’1corresponding to a Ti-O-C vibration.

[0008] FIG. 2: Raman spectra (left) of 1DL (black) and 1 -iodooctane treated 1DL (red) showing the similarity between the two. The peaks are those of lepidocrocite titania. XRD profiles (right) of 1DL (black) and 1 -iodooctane treated 1DL (red). Note overall reduction in peak intensity throughout, indicating partial reduction in crystallinity.

[0009] FIG. 3: Schematic of functionalization process. Upon reaction, iodine is released as an anionic species into solution. Note the atom colors are as follows: Hydrogen (White), Carbon (Grey), Iodine (Pink), Oxygen (Red), Titanium (Blue). Any non-backbone atom of 1DL has been removed for ease of viewing.

[0010] FIG. 4. (left) X-ray diffraction of 1DL and Dop-IDL. Shift in the d-spacing (left figure). FTIR (right) of 1DL and Dop-IDL notice in red the peaks around 1000 cm-1

[0011] FIG. 5: Proposed, non-limiting schematic for functionalization process for dopamine.DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0012] The present disclosure may be understood more readily by reference to the following detailed description of desired embodiments and the examples included therein.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety.The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0014] The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

[0015] As used in the specification and in the claims, the term "comprising" can include the embodiments "consisting of' and "consisting essentially of.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients / steps and permit the presence of other ingredients / steps. However, such description should be construed as also describing compositions or processes as "consisting of and "consisting essentially of' the enumerated ingredients / steps, which allows the presence of only the named ingredients / steps, along with any impurities that might result therefrom, and excludes other ingredients / steps.

[0016] As used herein, the terms “about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ±10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0017] Unless indicated to the contrary, the numerical values should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.

[0018] All ranges disclosed herein are inclusive of the recited endpoint and independently of the endpoints. The endpoints of the ranges and any values disclosed hereinare not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and / or values.

[0019] As used herein, approximating language can be applied to modify any quantitative representation that can vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language can correspond to the precision of an instrument for measuring the value. The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” can refer to plus or minus 10% of the indicated number. For example, “about 10%” can indicate a range of 9% to 11%, and “about 1” can mean from 0.9-1.1. Other meanings of “about” can be apparent from the context, such as rounding off, so, for example “about 1” can also mean from 0.5 to 1.4.

[0020] Further, the term “comprising” should be understood as having its open- ended meaning of “including,” but the term also includes the closed meaning of the term “consisting.” For example, a composition that comprises components A and B can be a composition that includes A, B, and other components, but can also be a composition made of A and B only. Any documents cited herein are incorporated by reference in their entireties for any and all purposes.

[0021] Any embodiment or aspect provided herein is illustrative only and does not limit the scope of the present disclosure or the appended claims. Any part or parts of any one or more embodiments or aspects can be combined with any part or parts of any one or more other embodiments or aspects.

[0022] Provided here are, inter alia, methods to functionalize the surface of onedimensional lepidocrocite titanium oxide material (1DL). IDLs can, in some embodiments, have a 5A x 7A cross section and exist as essentially all surface. Leveraging the chemistry of the terminations allows us to covalently attach groups to surface functionalize the material. One method of functionalization utilizes a long chain alkyl halide, e.g., 1 -iodooctane. The second method utilizes dopamine hydrochloride, a molecule from the catechol group. Exemplary, non-limiting disclosure of IDLs is found in PCT / US2022 / 070644 and inPCT / US2023 / 072374, both of which are incorporated herein in their entireties for any and all purposes.

[0023] As an example, we demonstrated that functionalization is achievable with a long chain alkyl halide (1 -iodooctane). In this approach, we took completely untreated 1DL material and mixed that material with the functionalizing compound and allowed for the reaction to occur. We have also introduced co-solvents such as, but not limited to, alcohols to improve miscibility between the 1DL and the compound. Heat can be supplied to improve the reaction kinetics.

[0024] Analysis was performed by Fourier Transform Infrared Spectroscopy (FTIR) shown in FIG. 1. To remove any physically absorbed 1 -iodooctane from the surface of the IDLs, the material was heavily washed with a miscible solvent (ethanol in this test). The presence of C-H peaks in the FTIR (around 2,900 cm’1) demonstrates the presence of octane ligands on the surface of the IDLs. Up to this point, there has been no documented FTIR signal in any 1DL sample tested. Further, the presence of peaks in the 1,000 cm’1range is indicative of Ti-O-C bonding, a feature not previously seen in 1DL samples. Finally, the shift in the very broad peak in the 3,000-4,000 cm’1range indicates a change in the -OH chemistry in the surface of the IDLs.

[0025] In terms of structure, the 1DL maintains its lepidocrocite backbone as shown in FIG. 2 left, along with at least some of its overall crystallinity, as seen in FIG. 2, right image.

[0026] A schematic illustrating the compounds before and after a first proof is presented in FIG. 3.

[0027] A second example method to functionalize the surface of the 1DL used dopamine hydrochloride. A molecule from the family of catechol group. Catechol is a benzenediol comprising a benzene core carrying two hydroxy substituents ortho to each other. Dopamine here is a catechol with the hydrogen on position 4 substituted with 2- aminoethyl group. As dopamine binds to 1DL surface with its hydroxy groups, one can switch the 2-aminoethyl groups with other chains, which in turn allows one to tailor the 1DL surface functionalization as desired. Thus, one can, for example, covalently bind a

[0028] In a similar fashion to 1 -iodooctane functionalization, we added a solution of dopamine hydrochloride in deionized water to an aqueous suspension of IDLs. This addition is associated with an instantaneous color change indicating a reaction has occurred.

[0029] The initial proof of the dopamine surface functionalization came from the d- spacing shift highlighted in FIG. 4. The peak shift seen in the far left of left figure. Additionally, highlighted in FIG. 4 on the right is the FTIR profile of the dopamine and 1DL. To remove dopamine not attached to the 1DL the sample is washed with a miscible solvent (e.g., water) until the solvent does not register any trace of dopamine contaminants using FTIR. Like the 1-iodocotane, the emergence of peaks in the 1,000 cm'1range is indicative of Ti-O-C bonding. The diminishing of the 3000-4000 cm'1broad peak indicates a reduction in - OH sites on the surface of the 1DL.

[0030] Aspects

[0031] The following Aspects are illustrative only and do not limit the scope of the present disclosure or the appended claims. Any part or parts of any one or more Aspects can be combined with any part or parts of any one or more other Aspects.

[0032] Aspect 1. A one-dimensional lepidocrocite titanium oxide material, the material having a surface functionality covalently bound thereto. The surface functionality can be, for example, a hydrocarbon. Such hydrocarbons can include, without limitation, alkanes, alkenes, and alkynes.

[0033] The surface functionality can be the reaction product of at least one of a hydrocarbon halide - for example, an alkyl halide - or a hydrocarbon alcohol with the 1DL.

[0034] The covalent binding between the 1DL and the functionality can be a covalent bond between an oxygen of the 1DL and a carbon of the functionality. The surface functionality can include, for example, a cyclic portion, including an aromatic portion. An aromatic portion of the surface functionality can be covalently bound to the 1DL.

[0035] Aspect 2. The material of Aspect 1, wherein the surface functionality comprises a hydrocarbon. The hydrocarbon can be, for example, a Cl, C2, C3, C4, C5, C6, C7, C8, C9, or CIO carbon chain. Such a chain can also include one or more substituents; example substituents include without limitation, alkyl groups (e.g., methyl, ethyl, propyl), halogens (e.g., fluoro, chloro, bromo, iodo), a hydroxyl group (-OH), an amino group (- NFL), a nitro group (-NO2), a carboxyl group (-COOH), an aldehyde group (-CHO), a ketone group (-C=O), an ester group (-COOR), an ether group (-OR), an amide group (- CONH2), a sulfonic acid group (-SO3H), a thiol group (-SH), a phenyl group (-CeHs), or even a cyanide group (-CN).

[0036] Aspect 3. The material of Aspect 2, wherein the hydrocarbon comprises an alkyl chain. The hydrocarbon can also include an alkene or alkyne chain.

[0037] Example hydrocarbon halides include, without limitation, chloromethane (Methyl chloride): CEEC1, bromomethane (Methyl bromide): CEFBr, iodomethane (Methyl iodide): CEEI, chloroethane (Ethyl chloride): C2H5CI, bromoethane (Ethyl bromide): C^HsBr, 1 -Chloropropane: C3H7CI, 2-Bromopropane: CriHvBr, 1,2-Dichloroethane (Ethylene di chloride): C2H4Q2, 1,1,1 -Tri chloroethane: C2H3Q3, Tetrachloromethane (Carbon tetrachloride): CCE, and the like.

[0038] Aspect 4. The material of Aspect 2, wherein the hydrocarbon comprises an aromatic molecule. Example aromatic molecules include, without limitation, benzene (CeHe), toluene (CMC), aniline (CeHsNBL), phenol (CeHsOH), naphthalene (CwHs), anthracene (CMHW), biphenyl (C12H10), styrene (CeEECE^CEE), xylene (CsHw), and benzoic acid (CeHsCOOH), as but some examples.

[0039] Aspect 5. A method of functionalizing a one-dimensional lepidocrocite titanium oxide material (1DL), comprising: contacting the 1DL material with a hydrocarbon halide or a hydrocarbon alcohol under such conditions that the hydrocarbon halide or hydrocarbon alcohol reacts with the 1DL material so as to give rise to a reaction product, the reaction product being covalently bound to the 1DL material.

[0040] A hydrocarbon halide can include a hydrocarbon portion. A hydrocarbon alcohol can include a hydrocarbon portion. Non-limiting examples are provided in FIGs. 3 and 5, which show (respectively) the functionalization of a 1DL by reaction with 1- iodooctane (FIG. 3) and by reaction with dopamine (FIG. 5).

[0041] Example hydrocarbon halides include, without limitation, alkyl halides, alkene halides, and even alkyne halides. A hydrocarbon can include, for example, a Cl, C2, C3, C4, C5, C6, C7, C8, C9, or CIO carbon chain. Such a chain can also include one or more substituents; example substituents include without limitation, alkyl groups (e.g., methyl, ethyl, propyl), halogens (e.g., fluoro, chloro, bromo, iodo), a hydroxyl group (-OH), an amino group (-NEL>), a nitro group (-NO2), a carboxyl group (-COOH), an aldehyde group (- CHO), a ketone group (-C=O), an ester group (-COOR), an ether group (-OR), an amide group (-CONH2), a sulfonic acid group (-SO3H), a thiol group (-SH), a phenyl group (- Cells), or even a cyanide group (-CN).

[0042] The contacting can be performed, for example, in the presence of any one or more of an alcohol, a base, or an acid. Contacting in the presence of an alcohol is considered particularly suitable, but is not a requirement.

[0043] A variety of alkyl halides can be used. For example, alkyl iodides can be used. Alkyl chlorides can be used, as can alkyl bromides and / or alkyl fluorides.

[0044] Aspect 6. The method of Aspect 5, wherein the hydrocarbon alcohol is a diol. Example such hydrocarbon alcohols include, without limitation, ethylene glycol (1,2- ethanediol), propylene glycol (1,2-propanediol), 1,2-butanediol, 1,2-pentanediol, 1,2- hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2- dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, 1,2-eicosanediol, 1,2-cyclohexanediol, and the like.

[0045] Aspect 7. The method of Aspect 5, wherein the hydrocarbon alcohol is a catechol and / or a catechol derivative. Example include, without limitation, catechol (1,2- dihydroxybenzene), dopamine (3,4-dihydroxyphenethylamine), adrenaline (epinephrine) (4- (l-hydroxy-2-(methylamino)ethyl)benzene-l,2-diol), noradrenaline (norepinephrine) (4-(2- amino- 1 -hydroxy ethyl)benzene- 1 ,2-diol), L-DOP A (3 ,4-dihydroxy-L-phenylalanine), hydroxytyrosol (3,4-dihydroxyphenylethanol), catechin (3,3',4',5,7-pentahydroxyflavan), quercetin (3,3',4',5,7-pentahydroxyflavone), piceatannol (3,4,3',5'-tetrahydroxy-trans- stilbene), urushiol, and the like.

[0046] Aspect 8. The method of any one of Aspects 5-7, wherein the reaction product is bound to the material via a Ti-O-C bond. Example such bonds are shown in FIG. 3 and FIG. 5 of the present disclosure.

[0047] Aspect 9. The method of any one of Aspects 5-8, wherein the material is contacted with a hydrocarbon alcohol, and wherein the reaction product is characterized as the hydrocarbon portion of the hydrocarbon alcohol. Such an example is provided in FIG. 5, in which a dopamine contacts a 1DL and forms a Ti-O-C bond between the dopamine and the 1DL.

[0048] Aspect 10. The method of any one of Aspects 5-8, wherein the material is contacted with a hydrocarbon halide, and wherein the reaction product is characterized as the hydrocarbon portion of the hydrocarbon halide. As an example, if the hydrocarbon halide is an alkyl halide, the reaction product can be the alkyl portion of the alkyl halide. Such an example is provided in FIG. 3.

[0049] The disclosed methods can also include further modifying the reaction product covalently bound to the material. As but one example, one can effect binding of dopamine to the 1DL, after which one can then exchange the 2-aminoethyl group of the dopamine with a different functional group and / or modify the 2-aminoethyl group of the dopamine. This in turn allows one to further tailor the surface functionalization of the 1DL materials. Thus, one can covalently associate a reaction product with the 1DL material and then further modify the side chains of the associated reaction product. The disclosed technology thus allows one to construct materials having a broad range of functionalities, with the materials including a 1DL as their base.

Claims

What is Claimed:

1. A one-dimensional lepidocrocite titanium oxide material, the material having a surface functionality covalently bound thereto.

2. The material of claim 1, wherein the surface functionality comprises a hydrocarbon.

3. The material of claim 2, wherein the hydrocarbon comprises an alkyl chain.

4. The material of claim 2, wherein the hydrocarbon comprises an aromatic molecule.

5. A method of functionalizing a one-dimensional lepidocrocite titanium oxide material, comprising: contacting the material with a hydrocarbon halide or a hydrocarbon alcohol under such conditions that the hydrocarbon halide or hydrocarbon alcohol with the material so as to give rise to a reaction product, the reaction product being covalently bound to the material.

6. The method of claim 5, wherein the alcohol is a diol.

7. The method of claim 5, wherein the alcohol is at least one of a catechol or a catechol derivative.

8. The method of any one of claims 5-7, wherein the reaction product is bound to the material via a Ti-O-C bond.

9. The method of any one of claims 5-7, wherein the material is contacted with a hydrocarbon alcohol and wherein the reaction product is characterized as the hydrocarbon portion of the hydrocarbon alcohol.

10. The method of any one of claims 5-7, wherein material is contacted with a hydrocarbon halide and wherein the reaction product is characterized as the hydrocarbon portion of the hydrocarbon halide.

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