Polymer strand and process for producing polymer strand

Abstract

To provide a pressed strand composition for producing a polymer strand.SOLUTION: There is provided a pressed strand composition for forming a multifilament strand, wherein the pressed strand composition comprises: (a) a poly(ethylene oxide) having a weight average molecular weight (Mw) of 100 kDa or greater, and the poly(ethylene oxide) is dissolved in an aqueous solvent at a poly(ethylene oxide) concentration greater than an entanglement concentration (ce) of the poly(ethylene oxide) in the composition; and (b) one or more other polymeric chemicals.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 066,154, filed August 14, 2021, the entire contents of which are incorporated herein by reference.

[0002] Field FIELD OF THE INVENTION This application relates to polymer strands, as well as processes and pressed strand compositions for making polymer strands, and uses of and articles made from polymer strands. [Background technology]

[0003] Many common techniques for creating bioactive strands for biomaterials are unable to produce strands without damaging the biomolecules incorporated into the strands, while maintaining production rates sufficient for practical applications. For example, electrospinning can produce strands with collagen at length scales similar to those found in the human body, but this method requires highly specialized equipment, uses volatile solvents that can denature the collagen, and exposes the strands to high shear stresses that can damage the collagen molecules. Similar problems to electrospinning exist for other bioactive molecules. Wet extrusion can be used to create self-assembled collagen strands without the use of high shear rates or volatile solvents, but this process is extremely slow and typically produces a single, thick strand at a time. Furthermore, both electrospinning and wet extrusion processes rely on extrusion through small-diameter nozzles or needles that easily clog, limiting their ability to create strands incorporating macromolecules, supramolecular assemblies, and nano / microparticles.

[0004] There remains a need for a process for making polymer strands that offers one or more of improved throughput, longer strand lengths, controllable strand diameters, controllable strand cross-sectional profiles, the ability to incorporate additives within the strands, and the use of simpler equipment that is amenable to automation. Summary of the Invention

[0005] A process for making polymer strands has been developed, the process comprising inserting a nucleating element into a prepared strand composition, the prepared strand composition comprising a polymer mixed with a solvent, the polymer having a concentration in the prepared strand composition that is equal to or greater than an overlap concentration (c*) of the polymer in the prepared strand composition; and withdrawing the nucleating element from the prepared strand composition such that a strand comprising the polymer is pulled from the prepared strand composition by the nucleating element, the nucleating element extending over a pulling time (τ pull ) is the reptation time (τ) required to disentangle the polymer in the pressed strand composition. rep ) thereby inducing a viscoelastic response of the pressed strand composition as the strand is pulled from the pressed strand composition by the nucleating element.

[0006] The process may further include depositing the polymer strands onto a solid substrate.

[0007] In an aspect, a process for making a multifilament strand of polyethylene oxide (PEO) and collagen is provided, the process comprising inserting a nucleating element into a pressed strand composition comprising PEO and collagen mixed with a solvent, and withdrawing the nucleating element from the pressed strand composition such that a multifilament strand comprising PEO and collagen filaments is pulled from the pressed strand composition by the nucleating element.

[0008] The article of manufacture may include polymer strands made by the process.

[0009] In one embodiment, the composition for forming the polymer strands has a weight average molecular weight (M w ), wherein the poly(ethylene oxide) is dissolved in an aqueous solvent at a poly(ethylene oxide) concentration greater than the overlap concentration (c*) of the poly(ethylene oxide) in the composition.

[0010] The polymer strands of the present invention are useful in a variety of applications, including as standalone fibers, in woven and nonwoven materials, and in hydrogels. Some example applications include cell culture extracellular matrix materials (e.g., 2D and 3D cell culture and tissue regeneration support materials), medical devices (e.g., bandages, sutures, surgical meshes, and implants such as tendons), textiles (e.g., face masks, textiles for the fashion industry, and protective clothing), and biocomposites containing high-value additives. Articles such as threads, yarns, multifilament fibers, woven fabrics, knitted fabrics, other nonwoven fabrics (e.g., felt), or blends thereof, can be made from the polymer strands produced by the process. Strand orientation in mesh articles can be parallel (0°), orthogonal (90°), between 0° and 90°, or multidirectional. In one application, polymer fiber network constructs of polymer strands can be formed on or within a solid substrate by incorporating the polymer strands on or within the solid substrate. The solid substrate can include, for example, fabrics formed from other natural or synthetic strands, hydrogel matrices, glass, polydimethylsiloxane (PDMS), polystyrene, thermoplastic polyolefins, thermoplastic polyurethanes, or other thermoplastic elastomers. The hydrogel matrix can include porous or non-porous polyacrylamide hydrogel matrices or agarose hydrogel matrices, which may or may not be activated with 3-(aminopropyl)triethoxysilane, glutaraldehyde, sulfosuccinimidyl 6-(4'-azido-2'-nitrophenylamino)hexanoate (sulpho-SANP AH), other suitable surface functionalizing molecules, or any mixture thereof.

[0011] The process described herein is simpler to implement, can incorporate bioactive molecules while retaining at least some of the bioactivity of the bioactive molecules, and has a production rate sufficient for large-scale manufacturing. The process allows for the design of efficient production processes for a variety of different types of polymer strands with desired lengths, diameters, and / or cross-sectional shapes. Using the process, polymer strands can be produced at a faster throughput than electrospinning and wet spinning.

[0012] Additional features will be described or will become apparent during the course of the following detailed description. It should be understood that each feature described herein may be utilized in any combination with any one or more of the other described features, and that each feature is not necessarily dependent on the presence of another feature, except as would be apparent to one of ordinary skill in the art.

[0013] For a clearer understanding, preferred embodiments will now be described in detail, by way of example, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows a schematic diagram of an apparatus for making polymer strands. [Figure 2A] FIG. 1 shows a schematic diagram of a cross-sectional side view of an apparatus for simultaneously producing multiple polymer strands. [Figure 2B] FIG. 2B shows a front view of a pin brush containing multiple nucleating elements of the device of FIG. 2A. [Figure 3] Figure 1 shows a graph of bulk viscosity η (cP x 10) of solutions of 500 kDa dextran and water as a function of concentration. Bulk viscosity values ​​were extrapolated from an exponential fit (dashed lines) for the various wt% used in the contact stretching experiments. [Figure 4]A graph of failure rate as a function of τpull is shown for 500 kDa dextran in water at four different concentrations. Each data set was fitted using a Weibull cumulative distribution function, all yielding r2 > 0.9. Every concentration shows a sharp transition from 0% to 100% failure rate over a narrow range of τpull. The error in τpull was less than 1%, and failure rates were taken as the percentage of failures from at least 15 trials. [Figure 5A] A graph showing the experimentally determined τ as a function of concentration for four different dextrans of increasing molecular weight is shown in Figure 4. Each data set was fitted with an exponential function (all r > 0.9). [Figure 5B] Figure 5B shows a semi-log plot of the data from Figure 5A rescaled as τrep × Mw-3, which reduces the data to a single exponential trend (r2 = 0.998). Although error bars are not visible, the maximum mean error in τrep is 0.4 s at 500 kDa, and the error in concentration is less than 1 wt%. [Figure 6] Figure 6A is a graph of strand diameter as a function of pulling duration for various concentrations of 500 kDa dextran in water. Figure 6B is a graph of strand diameter as a function of concentration of various Mw dextran. All strands shown in Figure 6B were pulled at 40 cm / s for a pulling duration of 0.25 s. Each data point is the average of three measurements for five strands pulled under the same conditions. Error bars represent the standard deviation of the mean. [Figure 7] Figure 7A shows a graph depicting η / %wt7 / 3 for 500 kDa dextran. Figure 7B shows a graph depicting strand diameter at various Mw as a function of pulling duration (τpull). The viscosity data in Figure 7A was interpolated from Figure 3, and the linear fit has r2 > 0.9. The data points in Figure 7B are the same as those in Figure 6B, and the linear fit has r2 = 0.9. [Figure 8A]Figure 1 shows a graph of polyethylene oxide (PEO) concentration (wt%) versus viscosity (Pa·s) for a press-stranded composition of 1 M Da PEO in 10 mM aqueous HCl solvent, demonstrating a logarithmic increase in viscosity as PEO concentration increases. [Figure 8B] 8B shows a graph of viscosity (Pa·s) of the pressed strand composition versus the average length (m) of PEO strands pulled from the pressed strand composition of FIG. 8A, demonstrating the ability to pull PEO strands to lengths of over 15 m. [Figure 8C] 1 shows a graph of PEO concentration (wt%) versus average length (m) of pressed strand compositions. [Figure 9] Figure 1 shows a graph of the hydration % mass fraction of collagen and PEO in solution as a function of the % dry mass fraction of collagen in solution at the point of successful strand formation during the dehydration process. The linear relationship between increasing collagen content and the hydration mass fraction of collagen and PEO allows for the reproducible creation of PEO-collagen strands of desired collagen composition. [Figure 10] SEM images of PEO-collagen strands prepared from solutions with the % dry mass fraction of collagen indicated in the upper left corner of each image are shown. The average strand diameters, along with the standard deviation, are shown in the table below the images (n=25). [Figure 11] Figure 1 shows an SEM image of strands formed with an initial composition of 90 wt% collagen and 10 wt% PEO in their dry form. After removing the polymer by washing in PBS for 1 hour at 37°C followed by rinsing with water, the collagen was critical point dried for SEM analysis. The resulting collagen strands contain subfibrillar structures similar to those found in native collagen. Arrows indicate fibril-sized collagen subcomponents of the strands. [Figure 12]SEM images of PEO-collagen strands subjected to a 1-hour PBS wash, three successive water washes, and drying under airflow are shown. The % dry mass fraction of collagen in the strand-forming solution for each strand is shown in the upper left of the image. Low-collagen content strands have a ribbon-like appearance, while high-collagen content strands retain a more rounded cross-sectional structure. The average strand diameter, along with the standard deviation, is shown in the table on the lower right (n=25). [Figure 13] The summed Raman spectra (top) of strands formed from viscous PEO solutions and solutions with % dry mass fractions of collagen ranging from 0 to 90% are shown. The integrals of the spectra from 1100 to 1150 cm-1 (bottom left) and 1550 to 1740 cm-1 (bottom right) represent the PEO and collagen content, respectively. [Figure 14] A graph of the relative content of PEO total and Raman peak integrals from the Raman total spectrum is shown in Figure 13. The presence of the collagen peak relative to the PEO peak increases or decreases linearly with the % dry mass fraction of collagen in each strand-forming solution. This demonstrates control of the collagen content of the strands based on the collagen content in the strand-forming solution. [Figure 15] Immunofluorescence images of native conformation ColI (α1) stained PEO-collagen strands are shown. The % dry mass fraction of collagen in the strand-forming solution for each image strand is indicated in the top left of the image. [Figure 16] A graph of second harmonic generation (SHG) anisotropy peaks of dried and PBS-washed PEO-collagen strands is shown, demonstrating the alignment of collagen within the strands along their longitudinal axis. [Figure 17] 1 shows a graph of pulling speed (spinning speed) (m / s) versus average length of PEO / collagen multifilament strands pulled from a pressed strand composition containing 8.5 wt% 1 MDa PEO and 0.6 wt% collagen in a 10 mM aqueous HCl solvent in top-down and bottom-up orientation. [Figure 18]1 shows a graph of wetted surface area (mm2) versus average strand length (m) showing the effect of varying pin diameter on the average strand length of PEO / collagen multifilament strands. [Figure 19A] 1 shows a graph of PEO concentration (wt%) versus average strand length (m) illustrating the effect of varying PEO concentration in the pressed strand composition on the average strand length of PEO / collagen multifilament strands. [Figure 19B] 1 shows a graph of collagen concentration (wt%) versus average strand length (m) showing the effect of varying collagen concentration in the pressed strand composition on the average strand length of collagen / PEO multifilament strands. [Figure 19C] 1 shows a graph of PEO concentration (wt%) versus pressed composition viscosity (Pa·s) illustrating the effect of increasing PEO concentration on pressed composition viscosity in the presence of a constant collagen concentration of 0.6 wt%. [Figure 19D] 1 shows a graph of collagen concentration (wt%) versus pressed composition viscosity (Pa·s) illustrating the effect of increasing collagen concentration on pressed composition viscosity in the presence of a constant PEO concentration of 8.5 wt%. [Figure 19E] 1 shows a graph of pressed strand composition viscosity (Pa·s) versus average strand length (m) illustrating optimization of fiber length by varying pressed strand composition viscosity. [Figure 20] 1 shows a graph comparing the average strand length (m) of multifilament PEO / collagen strands pulled from 20 mM acetic acid and 10 mM HCl. [Figure 21A] 1 shows a graph of initial filtration efficiency (%) versus particle size (nm) for nonwoven fabrics made with PEO strands made according to the present process. [Figure 21B] FIG. 21B shows a graph of total filtration efficiency (%) versus particle size (nm) for the nonwoven fabric of FIG. 21A. [Figure 22]Figure 1 shows the combined Raman spectra of strands formed from a viscous PEO solution and a solution containing equal amounts of PEO and gelatin. The PEO-gelatin spectrum has a broad peak in the amide I region that is not seen in the spectrum of pure PEO strands. [Figure 23]

[0023] Figure 1 shows a graph illustrating the extent of citric acid incorporation into PEO strands. The pH of pressed strand compositions of 90 wt% pure water, 0.1 M citric acid, and 10 wt% PEO with 1 M citric acid was measured prior to strand formation (Before). Approximately 200,000 strands, 30 cm in length, were pulled from the pressed strand solution and rehydrated in 10 ml of pure water, at which point the pH of the resulting solution was again measured (After). [Figure 24A] Transmission electron microscope images of 1 MDa PEO strands with 2 nm silver nanoparticles (seen as clusters in the left panel and indicated by arrows in the right panel) incorporated into the strands. The press strand composition consisted of 10 wt% 1 MDa PEO in water and a silver nanoparticle concentration of 2000 ppm. [Figure 24B] 1 shows a transmission electron microscope image of a 1 MDa PEO strand with a diameter of less than 200 nm and with 2 nm silver nanoparticles incorporated into the strand. DETAILED DESCRIPTION OF THE INVENTION

[0015] The process involves contact drawing of polymer strands from a press-strand composition (i.e., spin dope) containing a polymer mixed with a solvent. The polymer in the press-strand composition nucleates on a nucleating element inserted into the press-strand composition, and as the nucleating element is withdrawn from the press-strand composition, the polymer molecules become entangled, resulting in the formation of liquid bridges at the interface between the surface of the press-strand composition and the atmosphere outside the surface of the press-strand composition. By continuing to draw the strands at an appropriate rate, more of the polymer in the press-strand composition is pulled by the strands from the press-strand composition, thereby lengthening the strands being pulled. With a continuous supply of press-strand composition, the process can draw strands of infinite length.

[0016] The pressed strand composition comprises a polymer mixed with a solvent. Preferably, the polymer is dissolved in a solvent to form a solution or mixed with a solvent to form a paste.

[0017] The solvent preferably comprises a polar solvent, such as water, an alcohol (e.g., a primary alcohol such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, etc., a secondary alcohol such as 2-propanol, or a tertiary alcohol such as tert-butanol), and a mixture thereof. An aqueous solvent is preferred. The pH of the aqueous solvent is adjusted by adding an acid or a base. Examples of bases include hydroxides, carbonates, bicarbonates, etc., and mixtures thereof. Examples of acids include mineral acids (e.g., HCl, H2SO4, HNO3, H3PO4, etc.), or organic acids (e.g., acetic acid, citric acid, succinic acid, trifluoroacetic acid / 2,2,2-trifluoroethanol, etc., and mixtures thereof). The aqueous solvent may further comprise salts or other additives, particularly salts or other additives commonly used in biochemistry, e.g., cell culture. Salts or other additives may include, for example, saline (e.g., normal saline), buffer solutions (e.g., Tris buffer, Tris-buffered saline, phosphate buffer, phosphate-buffered saline), plasma, lactated Ringer's solution, acetated Ringer's solution, tissue culture medium, or mixtures thereof. In some embodiments, the pH of the solvent may be adjusted to be acidic, neutral, or basic depending on the polymer.

[0018] The polymer can be any polymer with suitable solubility in the solvent and a molecular weight that can be withdrawn from the solvent by the nucleating element under process conditions. The strands can be formed from synthetic or natural polymers. Some polymers include polysaccharides (e.g., dextran, chitosan, carrageenan, cellulose, etc.), polypeptides (e.g., collagen, spider silk, silkworm silk, other insect silk, etc.), poly(ethylene oxide) (PEO), polyvinyl alcohol (PVA), polyethylene glycol (PEG), hydroxypropyl cellulose, poly(2-ethyl-2-oxazoline) (P2E2O), poly(4-styrenesulfonic acid-co-maleic acid), poly(acrylic acid), poly(diallyldimethylammonium chloride), poly(methacrylic acid), poly(methyl vinyl ether-alt-maleic acid), poly(vinylpyrrolidone) (PVP), crosslinked polymers thereof, and copolymers thereof.

[0019] A particularly useful group of polymers are those that can act as scaffolds for other chemicals that cannot be pulled as strands or are difficult to pull as strands. Some examples of scaffold polymers include dextran, PEO, PVA, PEG, hydroxypropyl cellulose, poly(2-ethyl-2-oxazoline), poly(4-styrenesulfonic acid-co-maleic acid), poly(acrylic acid), poly(diallyldimethylammonium chloride), poly(methacrylic acid), poly(methyl vinyl ether-alt-maleic acid), poly(vinylpyrrolidone) (PVP), low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), nylon, polytetrafluoroethylene, thermoplastic polyurethanes, crosslinked polymers thereof, and copolymers thereof.

[0020] One or more other chemicals may be present in the pressed strand composition. During the strand formation process, other chemicals are incorporated or doped into or onto the polymer strands as they are formed. Some examples of other chemicals that may be loaded onto the scaffold polymer include collagen, gelatin, enzymes, actin, tubulin, keratin, amino acids, spider silk, silkworm silk, elastin, laminin, fibronectin, resilin, abductans, fibrin, integrin receptor ligands, fibulin, globulin, thrombin, glycoproteins, proteoglycans, DNA, RNA, nucleotides, carrageenan, chitin, chitosan, cellulose, sugars, growth factors, hormones, cysteine, cellulose, cellulose acetate ... Examples of suitable anti-inflammatory agents include steroids, chemokines, antibodies, lipids, hyaluronic acid, metal ions, non-metal ions, nanoparticles (e.g., carbon nanotubes, metal nanoparticles), colorants, surfactants, detergents, vitamins, bases, mineral and organic acids (e.g., citric acid), other natural health products, other small molecule pharmaceuticals (e.g., minocycline, riluzole, dalfampridine, escitalopram, deoxygedunin, 7,8-dihydroxyflavone, quercetin, dexamethasone, tacrolimus), and combinations thereof.

[0021] In the case of other chemicals that are also polymeric substances and capable of forming strands, the resulting polymer strands can include multifilament strands of two or more polymers, in which strands of the scaffold polymer carry polymer strands of the other polymer chemical(s). In this way, long strands of various polymers can be formed that were previously impossible or more difficult to form. Multifilament strands enable the deployment of commercially available spin-draw-wind, braiding, loom, and knitting machines, as well as machines used to manufacture medical devices such as sutures, fabrics, braided small-diameter vascular grafts, or tendons. In some embodiments, the other chemicals can include monomers that polymerize before, during, or after strand formation to provide polymer strands comprising the polymer carried by the scaffold polymer. In some embodiments, the scaffold polymer can be separated, for example, mechanically or by application of a wash solvent that dissolves the scaffold polymer but not the other polymers, leaving behind thin strands of the other polymers.

[0022] The one or more other chemicals are present in the pressed strand composition in an amount suitable for the other chemicals in the polymer strand. Preferably, the one or more other chemicals are present in the pressed strand composition at a concentration ranging from 0.1 to 50 wt%, based on the total weight of the pressed strand composition. In some embodiments, the concentration of the one or more other chemicals in the pressed strand composition is 0.1 to 30 wt%, or 0.2 to 30 wt%, or 0.2 to 5 wt%, or 0.2 to 9 wt%, or 0.3 to 20 wt%, or 0.3 to 10 wt%, or 0.3 to 9 wt%, or 0.3 to 8 wt%, or 0.3 to 5 wt%, or 0.3 to 3 wt%, or 0.4 to 10 wt%, or 0.5 to 9 wt%, or 0.5 to 8 wt%, or 0.5 to 5 wt%, or 0.5 to 3 wt%.

[0023] The press-strand composition may further comprise a stabilizing compound for the polymer strand. The stabilizing compound is preferably a cross-linking agent for the polymer strand. Some examples of the stabilizing compound include glyoxal, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), aldehydes (e.g., formaldehyde, glutaraldehyde), cross-linking agents that generate free radicals, or mixtures thereof.

[0024] The overlap concentration (c*) of the polymer in the pressed strand composition is the minimum concentration of polymer in the pressed strand composition at which the conformations of individual polymer chains begin to overlap each other. This is the point at which the concentration in a given filled volume is equal to the concentration of polymer in the pressed strand composition. The concentration of polymer in the pressed strand composition is equal to or greater than the overlap concentration.

[0025] The entanglement concentration (c e ) is the concentration of polymer in the pressed strand composition at which individual polymer chains begin to entangle with each other. The entanglement concentration is always at least as high as the overlap concentration, but can be up to 1000 times higher than the overlap concentration. The entanglement concentration is often at least 10 times higher than the overlap concentration. The concentration of polymer in the pressed strand composition is preferably equal to or greater than the entanglement concentration. Preferably, the concentration of polymer in the pressed strand composition is high enough so that the entire pressed strand composition is entangled.

[0026] The concentration of the polymer is preferably at least 0.01 wt%, more preferably in the range of 0.01 wt% to 99 wt%, based on the total weight of the prepared composition. In some embodiments, the polymer is present in the prepared composition in an amount of at least 7 wt%, preferably 7 to 14 wt%, more preferably 8 to 14 wt% or 7 to 10 wt%, based on the total weight of the prepared composition. In some embodiments, such as type I collagen, the concentration of the polymer in the prepared composition is 40 wt% or more, e.g., 40 to 95 wt% or 40 to 65 wt%. In other embodiments, such as PEO, the concentration of the polymer in the prepared composition is 0.5 wt% or more, e.g., 0.5 to 70 wt%. The required polymer concentration depends on the molecular weight (M w ) Generally, higher molecular weight polymers require lower concentrations.

[0027] The polymer preferably has a molecular weight (M) of 1 kDa or more, or 5 kDa or more, or 10 kDa or more, or 35 kDa or more, or 40 kDa or more, or 50 kDa or more, or 70 kDa or more, or 100 kDa or more, or 1,000 kDa or more, or 8,000 kDa or more. w In some embodiments, the polymer has a molecular weight (M) of 20,000 kDa or less. w ) Generally, higher molecular weight polymers provide the ability to make longer polymer strands.

[0028] The reptation time (τ) of the polymer in the press-stranded composition rep ) is the time required to disentangle the polymer chains in the pressed stranded composition. The reptation time should be as long as possible to allow for increased tension time, but less than the desired tension time. The reptation time is preferably at least 0.01 seconds, more preferably at least 0.1 seconds.

[0029] The pulling time (τ) of the nucleating element from the pressed strand composition pull ) is τpull = path length / pulling rate, where path length is the set distance that the nucleating element pulls the polymer strand and pulling rate is the rate at which the nucleating element pulls the strand over the set distance. pull ) can instead be defined in terms of the strand rather than the nucleating element, in which case the pull time (τ pull ) is τ pull = strand length / pulling speed, where strand length is the set length that the polymer strand is pulled over and pull speed is the speed at which the strand is pulled over that length. pull ) is the τ of the nucleation element when the strand is connected to the nucleation element. pull is the same as τ pull Defining {overscore (R)} in relation to strands is useful when the strands are transferred from the nucleation element to a strand take-up mechanism, which is preferred in a continuous strand formation process.

[0030] In the process, the pulling time of the nucleation element (or the strand, if the strand is not connected to the nucleation element) is equal to the reptation time of the polymer (τ rep The reptation time (τ repHaving a tension time less than the reptation time induces a viscoelastic response in the pressed strand composition when the polymer strand is pulled from the pressed strand composition. Thus, at tension times shorter than the reptation time, the entanglements act as temporary crosslinks, resulting in a viscoelastic response, allowing the polymer strand to be pulled from the pressed strand composition without breaking. However, if the interaction time between the nucleating element or pre-formed strands and the entangled polymer in the pressed strand composition is longer than the reptation time, the entanglement will be lost and the strand will break. The tension time is preferably selected to maximize the length of the strand for the desired tension speed. The tension speed is preferably in the range of 0.1 to 4 m / s, or 0.5 to 4 m / s, or 0.5 to 3 m / s, or 0.5 to 2 m / s.

[0031] The polymer strands may be pulled in any direction relative to the direction of gravity, for example, up, down, or sideways. Pulling the polymer strands downward is preferred because the effect of gravity on the pressed strand composition helps maintain a stable spin cone during the pulling process, thereby allowing for the formation of longer polymer strands. The spin cone is the volume of the pressed strand composition that faces outward from the surface of the pressed strand composition during pulling (spinning).

[0032] Using this process, virtually unlimited polymer strand lengths can be achieved by continuously replenishing the stretched strand composition. Strand lengths of 10 meters or more, or even up to 100 meters or more, can be achieved. In some embodiments, the strand length ranges from 0.01 to 100 meters. In some embodiments, the strand length ranges from 0.01 to 15 meters or from 0.01 to 10 meters. In some embodiments, the strand length can be 10 cm or more, or 50 cm or more, or 1 m or more, or 10 m or more.

[0033] The bulk viscosity of the press-formed composition can be adjusted to control strand diameter, as a lower bulk viscosity results in thinner strands. As the bulk viscosity of the press-formed composition increases, thicker strands can be formed. However, if the viscosity of the press-formed composition is too low, the spin cone will collapse and the growing strands will break; if the viscosity is too high, the spin cone will not contain enough fluid in volume to allow strand formation. Therefore, it is important to properly set the viscosity of the press-formed composition. In some embodiments, the bulk viscosity of the press-formed composition is preferably in the range of 8 to 100 Pa·s (8,000 cP to 100,000 cP) as measured by the vertical falling ball method. In another embodiment, the bulk viscosity of the pressed resin solution is preferably in the range of 100 to 5,000 Pa·s (100,000 to 5,000,000 cp), more preferably 100 to 1,000 Pa·s (100,000 to 1,000,000 cp), even more preferably 100 to 400 Pa·s, even more preferably 150 to 300 Pa·s, even more preferably 175 to 250 Pa·s, such as 200 Pa·s, as measured with a StressTech™ HR rheometer. When the polymer comprises PEO, the bulk viscosity is preferably 100 to 400 Pa·s, more preferably 150 to 300 Pa·s, even more preferably 175 to 250 Pa·s, or 150 to 200 Pa·s, such as 200 Pa·s.

[0034] The bulk viscosity of the press-formed composition is affected by the concentration of polymer in the press-formed composition. Increasing the concentration of polymer in the press-formed composition increases the bulk viscosity, while decreasing the concentration decreases it. Adjusting the concentration of polymer in the press-formed composition therefore adjusts the diameter of the strands produced. Average strand diameters in the range of 20 to 20,000 nm can be achieved by appropriately adjusting the viscosity of the press-formed composition. A major benefit of the process is the ability to produce ultrafine strands with average strand diameters of 200 nm or less, e.g., 20 to 200 nm. Furthermore, the strand diameter remains relatively constant over the length of the strand.

[0035] Different cross-sectional shapes of the strands can be obtained in the process. For example, the strands can have a circular or oval cross-section. The entire strand can have one cross-sectional shape, or different portions of the strand can have different cross-sectional shapes. Thus, ribbons and other architectures of strands can be produced.

[0036] The nucleation element can be any object capable of nucleating a strand when the element is inserted into the prepared strand composition. Strand nucleation results in the deposition of a portion of the prepared strand composition, e.g., in the form of a droplet, at one or more nucleation sites on the nucleation element. When the nucleation element is withdrawn from the prepared strand composition, a liquid bridge forms between the prepared strand composition on the nucleation element and the prepared strand composition remaining in the reservoir. When the nucleation element is further pulled away from the reservoir, a polymer strand forms between the nucleation element and the reservoir. The nucleation element provides non-random nucleation of the polymer. Non-random nucleation allows one or more nucleation sites to be predetermined for better control of strand growth and other process steps. The nucleation element has a size and shape such that when the nucleation element is withdrawn from the prepared strand composition, the polymer forms a strand. The aspect ratio (height to maximum width) of the nucleation element is preferably in the range of 1:100 to 1000:1. In some embodiments, the aspect ratio preferably ranges from 1:1 to 1000:1. The nucleating elements preferably have a cap width small enough to allow for initial deposition of thin polymer strands onto the cap when the cap is inserted into the pressed strand composition. The width of the nucleating element to which the polymer strands are attached is preferably 0.5 to 4 mm, more preferably 2 to 4 mm. In some embodiments, the width of the nucleating element can be 1 mm or less, or 0.75 mm or less, for example 0.5 mm. The cap preferably has a flat, conical, pyramidal, or elliptical geometry.

[0037] The nucleating element has a surface, and the nucleating element preferably has a surface that is at least 11 mm 2 , preferably at least 50 mm 2 The pressed strand composition is inserted into the pressed strand composition so that the surface area of ​​the pressed strand is wetted with the liquid. Preferably, the wetted surface area is 400 mm 2 up to, preferably 200 mm 2 up to, and even more preferably, 110 mm 2Preferably, the liquid contact surface area is 11 to 400 mm 2 , more preferably 11 to 200 mm 2 , and even more preferably 11 to 110 mm 2 , and even more preferably 50 to 110 mm 2 , and even more preferably 60 to 90 mm 2 The range is.

[0038] A single nucleating element can be used to pull one polymer strand. However, multiple strands can be pulled simultaneously from the same press-stranded composition by using multiple discrete nucleating elements. The multiple nucleating elements can be provided in either a regular or irregular array with regular or random spacing. When multiple nucleating elements are used, the multiple nucleating elements preferably have a minimum center-to-center spacing between nucleating elements that is at least 1.5 times, preferably at least 2 times, and more preferably at least 2.5 times the diameter of the thickest adjacent nucleating element. In some embodiments, the spacing is at least 0.2 mm, preferably at least 0.5 mm, and more preferably at least 1 mm. The lower limit is primarily due to the resolution of the 3D printer and the tolerances achievable by machining. The desired strand thickness also dictates the minimum spacing and width of the nucleating elements. Larger pin spacing and / or wider nucleating elements may be necessary for thicker strands. The nucleating elements can be manufactured by any suitable method, such as 3D printing or machining. The nucleation elements may have any suitable geometry, e.g., polygonal or elliptical cross-section. Some examples of nucleation elements include pins, needles, rods, and protrusions (e.g., pillars, ridges, nodules, granules, etc.) on a surface. In some embodiments, a plurality of such nucleation elements, one or more types, are attached to a base and used to simultaneously tension multiple strands. Thus, pin brushes, sandpaper, textured gloves, rough surfaces, etc. may be used to simultaneously tension multiple strands.

[0039] The nucleation elements may be embodied in a device that contains features for attaching or tethering the nucleation elements, containing the prepared strand composition, and translating the nucleation elements into and out of the prepared strand composition. In some embodiments, the nucleation elements are attached to and protrude from a flat plate. In some embodiments, the prepared strand composition is contained in a shallow pool on the flat plate. During strand formation, the flat plates may be oriented such that the plates face each other and stand vertically, thereby extending the nucleation elements horizontally, or may be oriented horizontally, extending the nucleation elements vertically. In a horizontal orientation, the flat plate containing the prepared strand composition is preferably below the flat plate holding the nucleation elements. The flat plate is preferably 1 cm thick. 2 While the minimum footprint is 0.01 mm, the maximum footprint is limited only by the operational requirements for creating strands. Thus, the maximum footprint can reach several square meters or more. Other mounting and containment arrangements can be envisioned by those skilled in the art. Features for translating the nucleation element can include motorized or manual stages. Automated devices are preferred.

[0040] After strand nucleation on the nucleation element, the strand can be transferred from the nucleation element to a strand take-up mechanism (e.g., a continuous spinning device such as a godet) that can continuously pull and collect the strand. In this way, strands of indefinite length can be produced.

[0041] In one embodiment, as shown in FIG. 1 , an apparatus 1 for fabricating polymer strands from a pressed strand composition includes a 3D-printed solution reservoir 3 containing the pressed strand composition, a microneedle 5 having a tip 6 for pulling strands from the pressed strand composition, and a translation stage 8 to which the microneedle 5 is attached using a 3D-printed mount 9. The solution reservoir is attached to a stand 2, and the translation stage 8 is mounted such that the tip 6 of the microneedle 5 translates along a horizontal vector to insert into the pressed strand composition in the solution reservoir 3 and then withdraw from the solution reservoir 3 to pull a polymer strand from the pressed strand composition in the opposite direction along the same horizontal vector. The movement of the translation stage 8 is controlled by a variable speed motor (not shown). At least the tip 6 of the microneedle 5 is preferably made of stainless steel.

[0042] In another embodiment, as shown in FIGS. 2A and 2B , an apparatus 20 for simultaneously producing multiple polymer strands from a pressed strand composition includes a 3D-printed solution support 21 for containing the pressed strand composition and a pin brush 27 including a 70×35 array of pins 25 (single-labeled) protruding from the front surface of a brush plate 28. The solution support 21 includes a support plate 23 having a gap 24 between the front and rear surfaces of the support plate 23 for containing the pressed strand composition, and a 70×35 array of openings 22 (single-labeled) in the front surface of the support plate 23 that can align with the array of pins 25. Once the pins 25 and openings 22 are aligned, the pins 25 can be inserted through the openings 22 and into the pressed strand composition in the gaps 24 and then withdrawn to pull polymer strands from the pressed strand composition. While the apparatus 20 is shown as a handheld apparatus, the solution support 21 can be mounted on a stand and the brush plate 28 can be mounted on a translation stage and operated in a manner similar to the apparatus of FIG. 1 . The apparatus 20 has a high density of strand nucleation sites for high-throughput strand formation. Instead of a support plate with gaps for containing the prepared strand composition and openings for accessing the gaps, the support plate can have a flat surface capable of holding the prepared strand composition in a shallow pool. Such an arrangement eliminates the need for aligning pins and openings.

[0043] After the polymer strands are made, they can be transferred to a collector, such as a spool or circular frame, where they can be subsequently assembled into threads, yarns, fabrics, knits, felts, etc. The entire manufacturing process can be done by hand, or to improve production efficiency and better control strand size, the process can be automated using simple robotic systems.

[0044] Example Example 1: Process optimization for polymer strand fabrication material and method: The following dextran molecular weights (Mw Dextran of 70, 150, 250, and 500 kDa was investigated. The 70, 150, and 500 kDa dextran was purchased from Dextran Products Limited, while the 250 kDa dextran was purchased from Pharmacosmos™. w Various solutions with dextran concentrations ranging from 40 wt% (wt / wt) to 63 wt% (wt / wt) were made for each M. Deionized (DI) water was the solvent used for analyzing the strand pulling process. Type I collagen (rat tail collagen I from Corning) in DI water and 0.02 N acetic acid was used as the solvent for strand diameter analysis. w For dextran, homogeneous polymer solutions with the desired concentration were obtained by adding the dry polymer to the appropriate mass of solvent in a plastic weighing dish and manually stirring with a pipette tip until the polymer was completely dissolved. The resulting solution was then transferred to a 1 mL syringe to prevent solvent loss due to evaporation during storage and to control the volume of solution added to the contact stretching device.

[0045] Viscosity measurement All experiments were performed at 22.5–24.0°C and a relative humidity of less than 20%. Dextran solution viscosity (η) was measured using the falling-ball method. A spherical stainless steel ball bearing with a diameter of 0.399 ± 0.002 cm and a mass of 0.2611 ± 0.0001 g was dropped into the solution in a polystyrene conical tube. Aqueous solutions of 500 kDa dextran were prepared at 35, 40, 45, 50, and 55 wt% and centrifuged at 3000 rcf for 15 minutes to remove any floating air bubbles. Using a digital timer accurate to the nearest 0.001 s and a ruler accurate to the nearest 0.5 mm, the distance traveled by the falling ball was measured over time, from which velocity was calculated. 0.001 g / cm 3 The density of each solution was measured using an Anton Parr DMA 35 handheld density meter, accurate to the nearest 1000. The viscosity was calculated as follows:

number

[0046] Contact stretching device An apparatus, as shown in Figure 1, was constructed to create polymer strands. The apparatus included a 0.5 mm shank diameter steel microneedle (product #13601C) purchased from Ted Pella™ to pull the strands. The microneedle was attached to a 100 mm linear translation stage (Thorlabs™ DDSM100 / M) using a 3D-printed coupling. Using this mounting configuration, the translation stage was capable of reaching speeds of up to 400 mm / s. The translation stage was operated using Kinesis software from Thorlabs, which set the translation speed and stop positions. The stage speed was calibrated by recording video at set speeds of 60 mm / s using an Edgertronic™ high-speed camera equipped with a Nikon™ Nikkor™ 50 mm lens. A solution reservoir was 3D printed to hold the solution from which the microneedle would pull the strands. The solution reservoir was designed to hold 50 μL in a 2 × 5 × 5 mm rectangular reservoir with an open lid and a syringe-fillable front face. The microneedle could reach a depth of approximately 4 mm within the reservoir at the position limit of the translation stage.

[0047] For analysis of the strand pulling process, the 3D-printed solution reservoir was filled with 50 μL of dextran solution. The dextran solution was replaced every 10 min to mitigate the effects of evaporation and ensure that the microneedle penetrated a consistent depth relative to the surface of the dextran solution. The stage was moved so that the microneedle penetrated the filled solution reservoir to a depth of approximately 4 mm at a speed of 29 mm / s, paused for 0.5 s, and then retracted at a set speed for the desired pulling duration (τ ), calculated as follows: pull ) is programmed to obtain:

number

[0048] A trial was assigned a success if it resulted in a strand of the set path length; otherwise, a failure was recorded and the failure mode was recorded. Two failure modes were observed: Mode I was a relaxation failure, which occurred when the strand separated from one or both ends before the pull was complete; Mode II was a strand drop failure, in which a drop was trapped along the strand, causing the strand to sag. At least 15 trials were performed for each τ pull The failure rate was calculated as follows:

number

[0049] τ that results in a 0% failure rate pull Starting from τ, we reduce the stage translation speed until the failure rate reaches 100%. pull The microneedle was wiped clean between trials using an ethanol-soaked Kimwipe™. High-speed videos of several trials were recorded using an Edgertronic™ camera for qualitative analysis of the pulling process.

[0050] τ pullThe failure rate data as a function of was fitted with a Weibull cumulative distribution function, a statistical model widely used in failure analysis over time. Using Matlab™ curve fitting tools, the data was fitted to the following:

number

[0051] Strand diameter measurement To characterize the strand diameter, at least five strands were collected at a given pulling duration onto a 25.4 × 76.2 × 1 mm glass slide (Ultident™ 170-7107A) and then covered with a 24 × 50 × 0.15 mm glass coverslip (Deckglaser™ 470819) using double-sided tape. All concentrations and M of dextran were analyzed. w For the tensile tests, the pulling duration was set to 0.25 s unless otherwise noted. To measure the diameter, strands were imaged using a 40x objective on a Nikon Eclipse™ Ti optical microscope. Each strand was imaged at three points approximately 1 cm apart along the strand length. After importing into ImageJ™, the images were converted to binary and processed using ImageJ™'s smoothing function, which simplifies edge detection by averaging pixels in a 3 x 3 matrix. The diameter of the strand was then measured between the two outer edges using a rectangular region of interest with a width of 200 pixels. This allowed each diameter measurement to be averaged over the 17 μm strand length and reduced measurement error by ensuring that the measured diameter was perpendicular to the strand length.

[0052] Results and Discussion: Dextran was used as a model polymer, and the results obtained with dextran can be broadly applied to other polymers. τ is used to understand the contact drawing process and to identify the key parameters controlling strand formation. pull The strand formation process was observed using a high-speed camera at various times during successful pulling. pull At τ (which results in a 0% failure rate), the strand remains connected to both the microneedle and the solution reservoir until the pulling is complete, exemplifying a successful attempt. pull As τ increases, the rate of Mode I failure increases, where an incomplete strand separates from at least one contact point before tension is complete. Mode I failure is more frequent and more predictable (as explained below) than Mode II failure. In Mode II failure, a droplet becomes trapped along the strand, causing it to sag. Mode II failure accounts for less than 2% of all failures. For 500 kDa dextran in four different concentrations of water, τ pull The failure rate as a function of τ is shown in Figure 4. For each concentration, the failure rate is pull There is an abrupt transition from 0% to 100% over a very narrow range of values. This abrupt transition in the cumulative distribution of failures indicates the characteristic time scale of the contact stretching process.

[0053] Dextran molecules are known to form random coils in water, meaning that water is a θ-solvent for dextran. 70 and 500 kDa dextrans have entanglement concentrations (c*) of 10.6 and 5.1 g / dL, or approximately 9.6 and 4.8 wt%, respectively. For a given solution, the entanglement concentration (c e ) is much higher than c*. As an example, for polystyrene (a neutral polymer) in toluene, c e ≈10c*. Here, concentrations approximately 6 and 10 times higher than c* were used for 70 and 500 kDa dextrans, respectively, so that all dextran solutions were in an entangled state. Within the entangled solution, the reptation time (τ rep) is the characteristic time required for the polymer to become entangled and flow freely. Therefore, the interaction time with the entangled solution is τ rep For longer lengths, entanglement disappears and a viscous response is observed, while τ rep On shorter time scales, entanglements act as temporary crosslinks, resulting in a viscoelastic response. Because all dextran concentrations are much higher than the overlap concentration c*, the sharp transition from 0 to 100% failure rate in Figure 4 suggests that entanglements are the primary mechanism for strand formation. Therefore, by fitting the curves in Figure 4 and extracting the inflection points (representing time scales), we can estimate the τ for a given solution. rep It is possible to extract

[0054] To further investigate the role of strand entanglement in the strand formation process, the failure rate curves were fitted with a Weibull cumulative distribution function, a statistical model widely used to analyze systems with failure rates proportional to time. For 24 data sets, 19 fits yielded r 2 >0.90. The lowest calculated r 2 The value is 0.76. Each fit has a shape parameter k>1, which represents an increasing failure rate with time, as would be expected from a system where increasing strain duration leads to an increasing likelihood of a viscous response. In theory, with known concentrations and well-defined M w A solution with a single distinct τ rep The transition from viscoelastic to viscous response should be instantaneous, since the polymer used here is polydisperse (PDI=9.1 for 500 kDa dextran), and the solution may have local heterogeneity in concentration. Both factors are captured by the parameter k, τ rep This results in a distribution of

[0055] From each fit, the scale parameter a is determined experimentally for the particular solution by τ rep Figure 5A shows various M w As a function of the concentration of the value of τ repPlot these data for a given M w For τ rep increases or decreases exponentially with concentration. rep The increase in M ​​can be understood as an increase in entanglement number density resulting from increasing concentration. As the entanglement density increases, the time required for the polymer to become entangled and flow freely increases. Figure 5A shows that at a constant concentration, M w With increasing τ rep This is most clearly observed with 250 and 500 kDa dextrans. At a given concentration, M w Doubling τ is equivalent to joining two polymer chains together end-to-end, while the entanglement density remains the same. rep The increase in does not come from an increase in entanglement density, but rather from each polymer having to disentangle twice as many entanglements.

[0056] The reptation model for entangled solutions is given by τ rep M w 3 According to this model, τ rep Rescaling the data allows the data to be reduced to a single exponential trend (Figure 5B). This is because all dextran solutions analyzed in this study exhibited a c e This shows that the strands have a higher concentration, supporting the contention that polymer entanglement is the primary mechanism for strand formation.

[0057] The data were well fitted with an exponential function (r 2 =0.998), but the reptation model is rep / M w 3predicts that τ scales as a power law with concentration. However, while this model is based on monodisperse linear polymers, the dextran used in these experiments is known to be somewhat polydisperse and branched at high molecular weights. Both of these experimental conditions significantly complicate the interpretation of the entanglement model, as polydispersity is known to increase the relaxation time of polymer networks by more than three-fold, and the presence of branches can suppress reptation and increase relaxation time proportionally to branch length. Despite this discrepancy, the experimentally determined τ rep / M w 3 The data are reduced to general trends, which validate polymer entanglement as a mechanism for strand formation and allow prediction of the processing conditions necessary to produce strands over a wide range of molecular weights and solution concentrations.

[0058] In contact stretching, τ rep Pulling over shorter timescales produces solid strands that can be collected and stored without strain for months. These strands do not unravel or viscously flow over these extended periods, indicating that water evaporates from the pulled strands. Because the strand diameters are on the order of microns but lengths are at least several centimeters, water evaporation occurs rapidly due to the large surface area to volume ratio. Further insight into the strand production process can be gained by analyzing the effects of contact drawing conditions and initial solution properties on the final strand diameter.

[0059] Figure 6A shows the τ at various concentrations of 500 kDa dextran in water. pull Figure 1 shows the dry strand diameter as a function of τ. For a given concentration, the strand diameter varies within experimental error. pull According to these data, τ pull is τ rep For shorter strands, the final strand diameter is independent of how fast the strands are pulled. However, the strand diameter increases with increasing concentration. This trend continues for all Mw It is shown by the value. w It can be seen that for , the strand diameter increases exponentially with concentration. For a given concentration, the strand diameter is generally M w The diameter of the strands increases with increasing pH. This trend is observed for dextrans ranging from 70 to 250 kDa, but not for dextrans ranging from 250 to 500 kDa. The open circles in Figure 6B show the diameter of strands from 500 kDa dextran dissolved in an 8.70 mg / ml collagen acidic solution. These data overlap very well with the data for 500 kDa in water, indicating that the incorporation of small amounts of biological material into the dextran solution does not affect strand formation. Therefore, the formation of collagen / dextran strands and other polymer strands can be predicted using the trends in Figure 6B.

[0060] The trend of increasing strand diameter with increasing concentration can be qualitatively understood by analyzing the contact drawing process. As the strand is pulled and the microneedle stops moving, there is a secondary flow of liquid bridges that attach to the strand at its end. Numerous previous studies of liquid bridges in entangled solutions have characterized the recoverable elastic strain stored within the viscoelastic solution. In the absence of applied strain, this stored elastic energy causes secondary flow. For 45 wt% and 50 wt% solutions of 500 kDa dextran and water, secondary flow begins with liquid bridges with diameters approximately 200 times larger than the final strand. Over time, the liquid flows back into the solution reservoir, shortening the liquid bridge until all the liquid returns to the solution reservoir and the final strand is released. Relatively large variations in diameter measurements can result from variations in the time elapsed between pulling the strand and collecting the strand. Because the strands were collected manually, strands collected before all the liquid had drained appear larger than strands collected at later time points. This effect may be the main source of experimental error in Figure 6A.

[0061] Interestingly, this secondary flow occurs significantly faster in the 45 wt% solution than in the 50 wt% solution, and both stretches occur over the same duration. The 45 wt% solution, with a bulk viscosity of approximately 8000 cP, has an average flow velocity of 3.1 mm / s, while the 50 wt% solution, with a bulk viscosity of approximately 85,000 cP, has an average flow velocity of 1.1 mm / s (see Figure 3 for bulk viscosity values). Therefore, the increase in strand diameter with increasing concentration can be qualitatively understood by analyzing the tip of this necking region. At this tip, the concentrated solid strand meets the liquid bridge, and this intersection recedes at a constant flow rate over time. Similarly, assuming a constant evaporation rate, a higher flow rate results in more polymer flowing with the liquid back to the solution reservoir, resulting in smaller strands. A lower flow rate results in a larger weight fraction of polymer remaining in the strand as the solution dries, resulting in larger final strands. In other words, the bulk viscosity controls the secondary flow velocity, which in turn controls the strand diameter.

[0062] Furthermore, according to the reptation model, τ rep and viscosity are directly related through:

number

[0063] τ rep Figure 7B shows all M values ​​for dextran, with the understanding that M can be used as a surrogate for viscosity. w For τ rep 1 shows a plot of strand diameter as a function of τ. repIt increases and decreases linearly with (r 2 =0.90), which means that the final strand diameter is w This means that η increases or decreases linearly with the value of η. Therefore, the increase or decrease in strand diameter with concentration seen in Figure 6B can also be explained by the fact that increasing concentration leads to an increase in viscosity. This demonstrates that the final strand diameter is primarily determined by the concentration and viscosity of the solution.

[0064] Analysis of 10 cm-long stable liquid bridges formed from highly viscous dextran solutions using this process identified key parameters controlling the contact stretching process. Failure analysis demonstrated that the formation of stable crosslinks depends on the relaxation time of entanglements within the polymer solution. If the strand is pulled for a time shorter than this critical time scale, the liquid bridges stabilize and form polymer strands of the desired length. While the pulling rate has no significant effect on strand diameter, the viscosity of the initial solution does. As viscosity increases, the secondary flow rate decreases, resulting in larger final strand diameters. This dependence of strand diameter on solution properties persists with the addition of type I collagen, which is important for the use of these strands as biomaterials.

[0065] Example 2: Preparation of Poly(ethylene oxide) Strands material and method: Polyethylene oxide (PEO) (1 MDa, lot # MKCM5188 and MKCF6841) was obtained from Sigma Aldrich. Hydrochloric acid (HCl) was purchased from ACP chemicals and diluted to 10 mM with reverse osmosis water.

[0066] Fifteen grams of 10 mM HCl solution was weighed into a 50 mL VWR falcon tube using a CL Series OHAUS scale. The desired amount of PEO was weighed using a VWR analytical balance. The PEO powder was gradually added to the 10 mM HCl solvent, and the solution was mixed for 5 minutes using a glass stir rod. The solution was then left to homogenize at ambient temperature for 3-5 days to form the PEO-prepared strand composition. The prepared strand composition was degassed using an Eppendorf™ Centrifuge 5702 RH.

[0067] The PEO strands were pulled from the pressed strand composition using a pulling speed ranging from 0.5 to 4 m / s. Optionally, 1 to 2 m / s is the range in which the spin cone is most stable. As the pulling speed increased, the length of the multifilament strand gradually increased and then decreased. When the pulling speed increased beyond the optimal range, the spin cone became long and unstable, resulting in a decrease in strand length. The ambient conditions in the room were recorded with a TP49 Thermo Pro™ hygrometer. The ambient relative humidity ranged from 25 to 27%, and the ambient temperature ranged from 27 to 29°C.

[0068] Results and Discussion: PEO is a linear, unbranched homopolymer of ethylene oxide. The rheology of PEO-containing pressed strand compositions is important to understand in detail, especially when PEO is used to create long, strong strands, with the aim of using PEO as a scaffolding polymer for the formation of strands of other polymeric materials, such as collagen.

[0069] In various industrial fields, water-soluble polymers are commonly used as thickeners to control the viscosity of aqueous solutions. Controlling the viscosity of polymer solutions requires understanding the complex relationship between chemical composition, polymer molecular weight, and polymer concentration. Understanding the flow properties of PEO solutions applied to the fabrication of continuous strands is important, especially when PEO is used as a scaffold polymer for nanoscale multifilament strands.

[0070] The properties of the pressed strand composition should allow for the formation of a spin cone containing the polymer strand and promote its stability. The spin cone should remain stable for as long as possible. When manually or mechanically pulling short lengths of strand (<1 m), the strand is pulled for <4 seconds, so spin cone instability is not an issue and results in either a good or bad strand. When pulling long strands, especially long multifilament strands, it is necessary to manage spin cone stability for minutes rather than seconds.

[0071] It has now been discovered that controlling the viscosity of the press-formed composition results in improved spin cone stability. If the press-formed viscosity is too low, an unstable spin cone results, which collapses rapidly (<5 seconds), resulting in no strands or short strands. If the press-formed composition viscosity is too high, shorter fibers are produced. Figure 8A (from Ebagninin K et al., Journal of Colloid and Interface Science 336 (2009) 360-367) shows that the press-formed composition viscosity is logarithmically related to the polymer concentration, and adjusting the viscosity in this way benefits from precision. Long PEO strands, typically >40 meters, can only be formed if the press-formed composition viscosity is stable enough to persist but not so viscous as to prevent the recruitment of new PEO molecules to the spin cone, resulting in the spin cone being pulled into nascent strands. From Figure 8B, it is clear that a press-form composition viscosity range of 300 to 5,000 Pa·s, preferably 300 to 1,000 Pa·s, e.g., 650 Pa·s, is optimal. In Figure 8B, each point represents the average of at least seven replicates. The average strand lengths from viscosities of 300, 650, and 1,000 Pa·s are significantly higher (P<0.05) than strands formed from press-form compositions with viscosities of 5,000 Pa·s or higher. Press-form compositions with viscosities below 150 Pa·s do not support strand formation due to spin cone instability. Press-form composition viscosities above 5,000 Pa·s produce shorter PEO-based strand lengths.

[0072] For 1 MDa PEO, c* is 1.5 wt% based on the total weight of the pressed strand composition, and c eThe PEO concentration is 5 wt% based on the total weight of the press-on strands (Ebagninin 2009). As is evident from Figure 8C, at these PEO concentrations, strands are not formed. Strands are formed when the PEO concentration is about 7 wt% or higher based on the total weight of the press-on strands. Furthermore, long strands are formed only when the PEO concentration in the press-on strands is within a relatively narrow range of 7-14 wt%, preferably 7-10 wt%. e At these higher concentrations, the pulling of the strands is therefore accompanied by a viscoelastic response.

[0073] Example 3: Fabrication of collagen strands using an 8 MDa poly(ethylene oxide) scaffold polymer material and method: A 0.1 wt% aqueous stock solution of 8 MDa poly(ethylene oxide) (PEO) (Sigma-Aldrich) and nano-pure water was prepared from PEO powder and equilibrated for 48 hours. The aqueous PEO solution was mixed with a collagen stock solution of 9.29 mg / ml rat tail collagen (Corning) in 20 mM acetic acid. The two solutions were mixed so that the dry mass fractions of collagen and PEO represented the desired collagen percentage in the final strand. The PEO-collagen solution was placed on a shaking table at 4 °C for 48 hours to dissolve and form a homogeneous solution. A solution for forming pure PEO strands was made following the same protocol as the 0.1 wt% PEO stock solution, but with a 1% PEO mass fraction.

[0074] The prepared polymer-collagen solution was poured onto a smooth plastic surface. Water was removed by evaporation under ambient conditions (25°C, 30% humidity) until the concentration of PEO and collagen in the solution was high enough to form strands. Strand formation was tested every 10 minutes by applying the pipette tip to the surface and withdrawing the pipette. This was repeated until a usable strand was formed, one that was dry upon formation and retained its shape after formation, at which point the final mass of the solution was measured and the total mass fraction of PEO and collagen was recorded (Figure 9).

[0075] contact stretching Strands were formed by pressing two substrates together and then separating them. One substrate was a plastic surface covered with the prepared PEO-collagen solution, and the other was a customized 3D-printed pin brush, as described in connection with Figure 2B. Contact stretching resulted in the formation of dry PEO-collagen strands. Each pin of the pin brush served as a nucleation point for the strands, allowing control of strand spacing and the number of strands formed. The process could be repeated multiple times without disturbing the PEO-collagen solution or either substrate. Strands were collected on microscope slides, glass coverslips, and SEM stubs for characterization. All strands were unidirectionally aligned.

[0076] Strand characterization Strands prepared from solutions with dry mass fractions of collagen of 0%, 30%, 50%, 70%, 80%, and 90% were characterized with emphasis on strand structure, collagen content, and collagen organization before and after hydration. Strands from solutions with a mass fraction of 95% were also formed but were not fully analyzed.

[0077] scanning electron microscope Scanning electron microscopy (SEM) was performed on all strand compositions after initial strand formation and after the rehydration drying process. Strands were first collected by pulling them onto SEM stubs. At this point, several SEM stubs were set aside for dried strand analysis, while others were hydrated in PBS for 1 hour at room temperature, rinsed three times with nanopure water, and dried under laboratory airflow. Samples were then sputter-coated with gold / palladium to a thickness of 3.18 nm and imaged using magnifications up to 145,000x on a JEOL 840 SEM (JEOL Ltd.) operating in the 2-5 kV range. Strand diameters (n = 25) and architectures from the resulting images were analyzed using the line tool in ImageJ™.

[0078] Raman spectroscopy Raman spectroscopy was performed on dry PEO-collagen strands and rehydrated, rinsed 90% PEO-collagen strands (n=5). The Raman system included an inverted microscope (1X71; Olympus, Center Valley, PA), an IHR550 Raman spectrometer (Horiba Jobin Yvon, Edison, NJ), and a 532 nm solid-state laser for sample excitation. All spectra were acquired using a 1.3 NA 100x oil immersion objective, a 1 μm laser spot, a 200 μm pinhole size, and 3 mW laser power. The glass coverslip with the attached strands was placed on the inverted microscope with the strands oriented parallel to the laser polarization. The spectrum of each strand was recorded at 800 cm. -1 ~1800cm -1 The analysis consisted of ten 10-second acquisitions in the spectral range of 1000 cm. Individual spectra were background subtracted and linear baseline corrected before summing the spectra for each collagen % of the strand. The summed spectra were then smoothed using a 25-wavenumber moving average filter and re-baselined before analysis. The spectra for each collagen % were analyzed using a 25-wavenumber moving average filter and re-baselined before analysis. -1 ~1150cm -1 (CO stretching vibration and CH rocking vibration specific to PEO), and 1550-1740 cm -1 (the collagen-specific amide I peak). These integrals were then normalized to their respective wavenumber ranges and then summed. The contribution to this sum associated with the collagen-specific amide peak was then calculated from each group.

[0079] Collagen immunofluorescence PEO-collagen strands were collected on microscope slides and rinsed in PBS for 2 hours. The PBS was then removed and replaced with 5% bovine serum albumin (BSA) (Sigma-Aldrich) in PBS for 20 minutes. After 20 minutes, the solution was replaced with fresh 5% BSA PBS and left on a shaking table for 16 hours. A 1% wt / wt BSA PBS solution was prepared and left on a shaking table for 16 hours at 4°C. After 16 hours in the 5% BSA PBS bath, the samples were rinsed 3 times in PBS for 15 minutes each time and placed in a pre-prepared 1% BSA PBS bath with mouse anti-collagen I α1 antibody (Novus Biologics, Oakville, ON, Canada) at a ratio of 1:10,000 relative to native collagen and left on a shaking table for 24 hours at 4°C. The samples were then rinsed in PBS for 3 x 15 minutes, at which point a solution of 1% BSA in PBS and 1:20000 Fluoro 549 goat anti-mouse IgG (Novus Biologics, Oakville, ON, Canada) was added to the samples and incubated in the dark on a shaking platform for 20 hours at 4°C, followed by 3 x 15 minute PBS washes, and then the samples were left in PBS to hydrate and imaged.

[0080] Immunofluorescence imaging Immunofluorescence images were acquired on a Nikon™ Eclipse™ Ti epifluorescence microscope using a 20x objective with a 4-second exposure. Slides containing stained strands were imaged while hydrated in PBS. All images were acquired with a pixel size of 170 nm. Images were processed with ImageJ™ software. Strand diameter was measured at three positions along each strand using the line tool. The average of these measurements was used as a normalization factor for the mean integrated intensity of each strand selected using the box tool.

[0081] Second Harmonic Generation Second harmonic generation (SHG) imaging of PEO-collagen strands before and after PBS washing was performed using a home-built system. An ultrafast pulsed laser (Femtolux™ 3, Ekspla) at 1030 nm wavelength, set at a pulse width of 250 fs and a repetition rate of 5 MHz, was raster-scanned across the sample using a pair of galvanometer-scanned mirrors (ScannerMAX™, Pangolin™ Laser Systems Inc.) with a pixel dwell time of 6 μs. The SHG signal was collected in forward scattering geometry using custom 0.8 NA objectives (87-789 and 48-637, Edmund Optics Inc.) and filtered, and detected with a photon-counting photomultiplier tube (H10682-210, Hamamatsu Photonics KK). The laser was focused onto the sample using an air-immersion microscope objective (20x, 0.8 NA, Zeiss™) immediately after passing through a liquid crystal polarization retarder (LCC1223-C, Thorlabs, Inc.) and a quarter-wave plate (WPMP4-22-BB-1030, Karl Lambrecht Corp.) used to change the polarization of the laser. Eight SHG signal images were acquired per strand sample, with the laser polarization rotated by 22.5° between each image.

[0082] Results and Discussion: PEO-collagen strands containing 0% to 90% collagen, based on the total weight of the strand, were successfully fabricated using contact stretching of a viscous PEO-collagen melt. Scanning electron microscope (SEM) images of the strands (Figure 10) revealed a constant strand diameter (600 ± 200 nm) independent of collagen content, similar to previous work using a collagen-dextran melt (International Patent Application WO 2018 / 137041, published August 2, 2018). A gradual change in surface topography was observed depending on the collagen content, transforming from pronounced peaks and valleys at 0% and 30% collagen content (Figure 10) to a smooth configuration at 50% and 70% collagen content (Figure 10), and finally to a rough, ridged surface at 80% and 90% collagen content (Figure 10). High-resolution SEM images of critical-point dehydrated collagen strands containing more than 90% collagen (FIG. 11) show a longitudinal subfibrillar structure.

[0083] Upon hydration for 1 hour in a fiber-forming buffer (FFB), e.g., PBS or its variants, followed by drying, the swelling of the strands was inversely proportional to the collagen content (Figure 12). After rehydration and subsequent dehydration, strands with lower collagen content appeared as flat ribbons on the SEM stub, while higher concentrations retained their rounder architecture (Figure 12). In both the dehydrated and critical-point dehydrated samples, the fibrillar substructure of the strands persisted (Figure 11), suggesting that collagen strand diameter is preserved rather than the ordered lateral molecular packing, and that the two are not codependent.

[0084] Collagen content and organization were measured using Raman spectroscopy, immunofluorescence imaging, and second harmonic generation (SHG). The Raman spectra of dried PEO-collagen strands show a clear transition from a PEO-dominated spectrum for 0% strands to a collagen-dominated spectrum for 90% collagen strands. This is due to the increase in the peak at 1100–1150 cm with increasing collagen content. -1The decrease in the peaks characteristic of PEO (lower left of Figure 13) and the peaks at 1550–1740 cm -1 This is clearly shown by the corresponding increase in amide I, a peak characteristic of collagen (Figure 13, bottom right). The corresponding linear relationship between collagen content and amide peak occurrence indicates that the strands have the same dry mass fraction of collagen and PEO as the viscous solution from which they are pulled (Figure 14). Furthermore, after a 1-hour wash in PBS at room temperature and three subsequent water washes, the 90% collagen strands showed an increase in collagen versus PEO signal occurrence corresponding to the predicted value from the linear relationship fitted from unhydrated PEO-collagen strands. This indicates that upon rinsing, PEO is solubilized from the strands, leaving the 100% collagen strands in place.

[0085] After hydration, all PEO-collagen strands were bound by mouse anti-collagen I α1 antibodies against native collagen, demonstrating that the native molecular structure of collagen is preserved after the strand formation process (Figure 15). Successful preparation of immunofluorescence samples highlights the insolubility of the strands, as the process requires more than 60 hours in a hydrated state before imaging. This degree of hydration stability has not been demonstrated by electrospinning in the absence of a nonaqueous solvent or the addition of a crosslinker.

[0086] SHG anisotropy distributions of strands containing 70%, 80%, and 90% collagen were acquired both before and after washing with PBS. No significant differences were observed between sample groups (Figure 16), but the average anisotropy distribution demonstrates molecular alignment within the strands. SHG signals were not obtained for strands with less than 70% collagen, because PEO has an absorption band that overlaps with the output of the incident laser of the SHG system.

[0087] Contact stretching of long PEO-collagen strands was successfully achieved from a viscous aqueous solution compressed between two substrates. Ranging from pure PEO to 90% collagen, the strands formed by contact stretching can be submicron in diameter and up to several meters in length, demonstrating anisotropic native collagen structure and insoluble, undenatured collagen molecules, as confirmed by SEM, immunofluorescence imaging, Raman spectroscopy, and second-harmonic generation. High throughput (13 km / s) and control of strand alignment make these strands useful for fabricating nonwoven and woven fabrics for a variety of applications, such as cell culture and regenerative medicine, while recreating a nontoxic extracellular matrix (ECM) environment.

[0088] Example 4: Fabrication of collagen strands using a 1 MDa poly(ethylene oxide) scaffold polymer In one experiment, PEO / collagen multifilament strands were pulled from a press-stranded composition containing 8.5 wt% 1 MDa PEO and 0.6 wt% collagen. The strands were pulled in top-down and bottom-up multifilament strand production configurations at five different spinning speeds: 0.5 m / s, 1 m / s, 2 m / s, 3 m / s, and 4 m / s, with five replicates of each. Figure 17 shows the results. It is clear from Figure 17 that the spin cone is directly affected by gravity. The placement of the press-stranded composition reservoir and the method by which the multifilament strand is produced are important. At a pull speed of 1 m / s using the top-down orientation, the spin cone appears to be most stable and produces the longest strand length. However, at higher speeds, gravity overstretches the spin cone, resulting in the absence of a spin cone and shorter fiber lengths. When the pressed strand composition reservoir is positioned such that the strands are pulled upward against gravity, the spin cone collapses and "unwinds" back into the bulk pressed strand composition, and the nascent strands break.

[0089] In another experiment, collagen / PEO multifilament strands were pulled from a press-strand composition containing 8.5 wt% 1 MDa PEO and 0.6 wt% collagen. The effects of pin diameter and pin immersion depth into the press-strand composition on spin cone stability and strand length were investigated. Pin arrays were designed with Onshape™ software and printed using a B9 Creator V1.2 3D printer. Pin diameters ranging from 0.5 mm to 4 mm were tested, and the strands were immersed 7.4 mm into the press-strand composition. Figure 18 shows the linear relationship between wetted surface area and average strand length, with each point representing the average of 10 replicates. When expressed as wetted surface area, the longest strand was 105.6 mm. 3 (2.4 mm pin diameter and 7.4 mm immersion in the press-strand composition). The pin diameter, pin height, and reservoir depth can be modified depending on the wetted surface area required for the desired strand length calculated based on the equation: y = 0.4768x + 7.8893, where y is the average strand length in meters and x is mm. 2 The optimal pin architecture also involves setting the distance between each pin. If the pins are placed too close together, the strands will intermingle, disrupting the spinning process. To avoid intermingling, the center-to-center distance should be at least twice the pin diameter.

[0090] In a separate experiment, PEO / collagen multifilament strands were pulled from a press-strand composition containing various concentrations of 1 MDa PEO and a constant 0.6 wt% collagen. The pulling speed and pin architecture were the same for each concentration. Therefore, the effect of PEO concentration in the press-strand composition on spin cone stability, as defined by average strand length, was investigated. The amount of PEO was varied between 6 and 12 wt% as follows: 6 wt%, 7 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, and 12 wt%. The results are shown in Figure 19A, where each point represents the average of at least seven individual strands. Error bars represent one standard error. It is clear from Figure 19A that the addition of collagen to the PEO scaffold polymer also results in an optimization curve in which strand length peaks between specific high and low values ​​of PEO concentration. Similarly, an improvement in strand length with increasing PEO concentration, followed by a decrease in strand length at higher PEO concentrations, is observed with PEO alone (see Figure 8C).

[0091] In a separate experiment, PEO / collagen multifilament strands were pulled from a press-strand composition containing 8.5 wt% 1 MDa PEO and various concentrations of collagen. The pulling speed and pin architecture were the same for each concentration. Therefore, the effect of collagen concentration in the press-strand composition on spin cone stability, as defined by average strand length, was investigated. The amount of collagen was varied between 0.2 and 5 wt% as follows: 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 3 wt%, and 5 wt%. The results are shown in Figure 19B, where each point represents the average of at least seven individual strands. Error bars represent one standard error. It is clear from Figure 19B that the effect of collagen concentration on average strand length is biphasic over the concentration range investigated. Referring to Figure 19D, it is clear that the viscosity of the pressed stranded composition does not increase linearly with increasing collagen concentration. At viscosities between 150 and 250 Pa·s, e.g., at collagen concentrations of 0.4 wt%, 0.8 wt%, 2 wt%, and 3 wt%, longer fibers are formed. At viscosities above 250 Pa·s, e.g., at collagen concentrations of 1 wt%, 1.2 wt%, and 5 wt%, the average fiber length decreases. At very low collagen concentrations, e.g., 0.2 wt%, this response is not observed.

[0092] Both Figures 19A and 19B show that to produce the longest strands, the concentration of all polymeric materials, including PEO and collagen, is preferably 8-13 wt% based on the total weight of the pressed strand composition.

[0093] In a separate experiment, the viscosity of the above-mentioned pressed resin compositions was measured using a StressTech™ HR rheometer (ATS RheoSystems™) in a parallel plate configuration with 40 mm diameter plates and a 0.5 mm gap. The sample was loaded using a spatula, and once the plate gap was reached, excess pressed resin composition was removed. The sample was held for 30 seconds before measurement, then 0.1 s-1 The samples were subjected to pre-shearing at 20°C for 30 seconds. -1 The shear rate sweeps were repeated twice with new samples and expressed as averages. All samples exhibited non-Newtonian shear-thinning behavior. Figure 19C shows how the viscosity of the pressed strand composition changes with increasing PEO concentration when the collagen concentration is held constant at 0.6 wt%. Figure 19D shows how the viscosity of the pressed strand composition changes with increasing collagen concentration when the PEO concentration is held constant at 8.5 wt%. Figure 19E shows the relationship between the viscosity of the pressed strand composition and the average fiber length. Polynomial regression: q=-6E-09p 4 +1E-05p 3 -0.0059p 2 +1.2831p-57.525 (where q is the average strand length in meters and p is the viscosity of the pressed lay composition in Pa s) mathematically represents this relationship, and fiber length can be predicted or "tuned" by adjusting the viscosity of the pressed lay composition. For example, the longest fibers are produced when the viscosity of the pressed lay composition is set at 178 Pa s.

[0094] In another experiment, the effect of acid solvent selection on average strand length was investigated. Two pressed strand compositions were prepared containing 8.5 wt% 1 MDa PEO and 0.6 wt% collagen in 20 mM acetic acid or 10 mM HCl solvents. These are common collagen solvents used in industry. Fibers were produced from each pressed strand composition using a variable-speed winder at a pulling speed of 1 m / s, and average lengths were measured based on 10 replicates. The pin architecture was the same for each pressed strand composition. The effect of solvent selection was significant, as can be seen in Figure 20. Under the conditions tested, hydrochloric acid was the superior solvent, producing strands with average strand lengths more than two times longer than those produced from acetic acid.

[0095] For the experiments in Example 4, the ambient room conditions were recorded with a TP49 Thermo Pro™ hygrometer. The ambient relative humidity ranged from 25-30% and the ambient temperature ranged from 26-32°C.

[0096] Example 5: Preparation of nonwoven fabric from poly(ethylene oxide) strands Poly(ethylene oxide) (PEO) strands were produced by pulling strands from an aqueous solution of PEO in water using an apparatus such as that described in connection with Figure 2 and utilizing process conditions determined by the methodology described in Example 1. The strands were formed into a nonwoven fabric by layering continuous pulled fibers produced using a multi-pin nucleating element, although other conventional techniques can be used. The fabric was evaluated for potential usefulness in the manufacture of NIOSH respirator-approved "N95" filter masks.

[0097] Figure 21A shows a graph of the initial filtration efficiency (%) of the nonwoven fabrics versus particle size (nm). Polymer + Polymer represents a nonwoven fabric made solely from PEO. As can be seen in Figure 21A, the initial filtration efficiency of the nonwoven fabric is greater than 98% across the entire particle size range from 1 nm to 500 nm. Such efficiency exceeds the 95% efficiency mark (dashed line) required for N95 masks and is better than fabrics utilizing dry felt and polymer (dry felt + polymer). Dry felt + polymer is a single polymer layer plus felt composed of 60% wt wool and 40% wt linen. As can be seen in Figure 21B, the filtration efficiency (%) of the nonwoven fabric is not lost after a particulate load equivalent to the N95 mask testing protocol.

[0098] Example 6: Preparation of poly(ethylene oxide)-gelatin strands Gelatin is composed of low molecular weight hydrolyzed collagen peptides of 3-5 kDa (Leon-Lopez A et al., Molecules. 2019, 24, 4031, p. 16). This example demonstrates the application of contact stretching strand formation using small peptides with random coil secondary structure. Poly(ethylene oxide)-bovine skin-derived type B gelatin (PEO-gelatin) strands were produced by a process similar to that used for the PEO-collagen strands in Example 2. The strands were prepared by adding 5 wt% PEO (M w = 1,000 kDa) and 5 wt% gelatin in an acetic acid solution. For comparison, strands were also formed from a viscous PEO aqueous solution.

[0099] Figure 22 shows the summed Raman spectrum of the PEO-gelatin strands. The PEO-gelatin spectrum has a broad peak in the amide I region, which is not seen in the spectrum of the pure PEO strands, thereby indicating the successful formation of gelatin strands supported on PEO strands.

[0100] Example 7: Preparation of citric acid-loaded poly(ethylene oxide) strands Poly(ethylene oxide) (PEO) strands were made by a process similar to that of the PEO-collagen strands of Example 3, except that citric acid was incorporated into the PEO strands instead of collagen. The strands were prepared by dissolving 10 wt% PEO (M citric acid) in pure water, 0.1 M citric acid in water, and 1 M citric acid in water. w = 1,000 kDa solution. The pH of the pressed strand composition was measured before strand formation (before). Approximately 200,000 strands, 30 cm in length, were pulled from each pressed strand solution and rehydrated in 10 ml of purified water, at which point the pH of the resulting solution was again measured (after).

[0101] As can be seen in Figure 23, for PEO strands pulled from a solution in pure water, the pH of the press-strand solution (before) and the rehydrated strand solution (after) remained unchanged at pH 8. In contrast, for strands pulled from a press-strand solution containing citric acid, the pH of the rehydrated strand solution was less than 6 in both cases, indicating that in both cases at least some of the citric acid was incorporated into the PEO strands during the strand formation process. Furthermore, in the case of 1 M citric acid, the pH of the rehydrated strand solution was lower than in the case of 0.1 M citric acid, indicating that greater loading of citric acid into the PEO is due to the press-strand solution having a higher citric acid concentration.

[0102] Example 8: Preparation of silver nanoparticle-loaded poly(ethylene oxide) strands Poly(ethylene oxide) (PEO) strands were made by a process similar to that of the PEO-collagen strands in Example 3, except that silver nanoparticles were incorporated into the PEO strands instead of collagen. The strands were prepared by dissolving 10 wt% PEO (M w = 1,000 kDa) and 2,000 ppm silver nanoparticles (diameter = 2 nm) from a pressed solution.

[0103] As can be seen in Figure 24, PEO strands incorporate both clusters of silver nanoparticles (left panel) and unclustered silver nanoparticles (right panel). As can be seen in Figure 24B, silver nanoparticles are also incorporated into PEO strands with strand diameters less than 200 nm.

[0104] The novel features will become apparent to those skilled in the art upon examination of the description. However, it should be understood that the scope of the claims should not be limited by the embodiments, but should be accorded the broadest interpretation consistent with the language of the claims and the specification as a whole.

Claims

1. 1. A press-strand composition for forming a multifilament strand, said press-strand composition comprising: (a) a weight average molecular weight (M ｗ ) in an aqueous solvent, the entanglement concentration (c ｅ ), and (b) one or more other polymeric chemicals A pressed composition comprising:

2. 10. The pressed composition of claim 1, wherein the one or more other polymeric chemicals comprise one or more of an enzyme, keratin, an integrin receptor ligand, a glycoprotein, a proteoglycan, DNA, RNA, a polysaccharide, an antibody, and a lipid.

3. 2. The pressed composition of claim 1, wherein the one or more other polymeric chemicals comprise one or more of collagen, gelatin, actin, tubulin, spider silk, silkworm silk, elastin, laminin, fibronectin, resilin, abductan, fibrin, fibulin, globulin, thrombin, carrageenan, chitin, chitosan, cellulose, and hyaluronic acid.

4. 10. The pressed strand composition of claim 1, wherein the one or more other polymeric chemicals include collagen, chitosan, and spider silk.

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