Hydrogen-Bonded, Mechanically Strong Nanofibers with Tunable Antioxidant

Activity

Adwait Gaikwad1, Hanna Hlushko1, Parvin Karimineghlani, Victor Selin, and Svetlana A.

Sukhishvili*

Department of Materials Science & Engineering, Texas A&M University, College Station,
Texas 77843, USA
Abstract

We report on mechanically strong, water-insoluble hydrogen-bonded nanofiber mats

composed of a hydrophilic polymer and a natural polyphenol that exhibit prolonged antioxidant

activity. The high performance of fibrous mats resulted from the formation of a network of

hydrogen bonds between a low-molecular-weight polyphenol (tannic acid, TA) and a water-

soluble polymer (polyvinylpyrrolidone, PVP), and could be precisely controlled by the TA-to-PVP

ratio. Dramatic enhancement (5 to 10-fold) in tensile strength, toughness and Young’s moduli of

the PVP/TA fiber mats (as compared to those of pristine PVP fibers) was achieved at the maximum

density of hydrogen bonds, which occurred at ~0.2-0.4 molar fractions of TA. The formation of

hydrogen bonds was confirmed by an increase in the glass transition temperature of the polymer

after binding with TA. When exposed to water, the fibers exhibited composition- and pH-

dependent stability, with the TA-enriched fibers fully preserving their integrity in acidic and

neutral media. Importantly, the fiber mats exhibited strong antioxidant activity with dual (burst

and prolonged) activity profiles, which could be controlled via fiber composition – a feature useful

for controlling radical scavenging rates in environmental and biological applications.

Keywords: Hydrogen bonding, Polyvinylpyrrolidone, Tannic acid, Electrospinning, Nanofibers,

pH-dependent stability, Antioxidant.

1
These authors contributed equally to this work.

1
INTRODUCTION

Electrospinning is a versatile technique to fabricate fibers with nano-to-microscale

diameters using polymers, ceramics, or nanocomposite materials,1,2 and arrange them within

fibrous mats. Because of the high specific surface area and the open, porous structure, engineered

electrospun fibrous materials are finding applications in tissue engineering,3 drug delivery,4,5 water

purification,6,7 and energy storage.8,9 For many biomedical and environmental applications, several

properties of the fiber materials should be simultaneously achieved. Specifically, the fibers should

be (a) stable in water at environmental pH values, (b) demonstrate robust mechanical performance,

comparable or exceeding those of biological fibers, and (c) capable of controllably

retaining/releasing small molecules for programmed materials functionality. While attaining one

or two of these properties with electrospun fiber mats was partially successful,10-12 none of the

previously reported materials have simultaneously addressed all three of the above challenges.

Enhancing material functionality by using low-molecular weight drugs, proteins, binding

agents, or antioxidants has long been an important goal in engineering electrospun fibers. While

inclusion of functional molecules was often achieved by simple blending of small functional

molecules with polymers,13 this approach does not rely on optimized molecular interactions of

small molecules with a polymer matrix, and often results in phase separation, low payloads, and/or

poor control of small molecule functionality.14 On the other hand, in polymer-polymer systems,

good compatibility can be achieved by employing non-covalent electrostatic or hydrogen-bonding

interactions. For example, polyelectrolyte complexes (PECs) composed of ionically associated

polymers have been successfully electrospun into chemically stable robust nanofiber mats.10,11,15,16

Electrostatic assembly cannot be used, however, with neutral, nontoxic and environmentally

benign polymers, such as polyethylene oxide (PEO) or polyvinylpyrrolidone (PVP). Yet these

2
polymers can be assembled by means of hydrogen bonding,17 which also enables facile inclusion

of efficient radical scavengers, such as polyphenols.18 Moreover, the physical crosslinking

resulting from hydrogen bonding was demonstrated to improve both toughness and tensile strength

of polymer materials.19,20

This work aims to explore the effect of incorporation of a hydrogen-bonding, natural

polyphenol – tannic acid (TA) – on thermo-mechanical properties of polymer fibers and leverage

the antioxidant capability of TA. The main challenge was to simultaneously achieve robust

structural stability and high radical-scavenging performance of the fibrous mats in an aqueous

environment. TA is a biocompatible, water-soluble polyphenol with anticarcinogenic and

antioxidant properties. 21-23 The hydrogen-donating property of its phenolic groups enables binding

of TA within complexes and multilayers with a variety of hydrogen-accepting neutral polymers,24

including polyvinylpyrrolidone (PVP).18,25-28 Because of the low acidity of TA (pKa ~8.9),

hydrogen bonding between TA and PVP persists until pH ~8.5,18 making this hydrogen-bonding

pair highly suitable for use in common environmental and biomedical conditions. In contrast, the

use of another common partner – polycarboxylic acids – for hydrogen-bonding assembly with PVP

results in materials which dissociate in neutral and basic aqueous environments.17,29-32 This

limitation is also applicable to the extruded complexes of hydrogen-bonded polymers based on

polycarboxylic acids, which are stable exclusively in acidic environment.33

Prior approaches to incorporate antioxidant functionality in fibrous mats explored a

blending strategy of other natural antioxidants (such as curcumin or fenugreek) within the fibers

to achieve enhanced wound healing,34,13 rather than relying on direct hydrogen bonding. For

example, incorporation of an antioxidant polyphenol molecule whose chemistry is close to that of

TA, i.e. gallic acid, within the biomedical fiber mats required formation of an inclusion complex

3
with cyclodextrin.35 Additionally, Whittaker et al.36 attempted to use hydrogen bonding to

incorporate TA within poly(N-vinylcaprolactam) nanofibers. However, due to an inhomogeneity

of solution viscosity, the fiber’s morphology was largely dominated by the bead formation, and

antioxidant properties of the beaded fiber mats were not explored.36 In contrast, in our work, the

effect of TA/PVP hydrogen-bonding interactions on fiber morphology and diameters were both

well-controlled to obtain bead-free, uniform nanofibers with maximized specific surface area

desirable for leveraging the functionality of TA. In PVP/TA electrospun fibers, the polymeric

component provided mechanical integrity, TA contributed the radical-scavenging capability, and

the hydrogen bonding between PVP and TA served to increase the strength and toughness of the

fibers. Importantly, composition of the fibers could be designed to achieve tensile properties

superior to those previously reported for antioxidant-containing fibers,37 and exceeding those

reported for collagen in ambient air.38 At the same time, programming the composition of the fibers

was critical for optimizing the fiber performance against two important parameters, i.e.

preservation of fiber integrity upon exposure to aqueous environment at varied acidity and

achieving efficient and controlled antiradical performance.

EXPERIMENTAL SECTION

Materials

Polyvinylpyrrolidone (PVP) (Mw 1,300,000 g/mol), potassium peroxydisulfate, and

dimethyl sulfoxide (DMSO) were purchased from Alfa Aesar. Tannic acid (TA) and N, N-

dimethylformamide (DMF) were purchased from Sigma Aldrich. 200 proof ethanol and 2,2'-azino-

bis(3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) were received from

VWR. Ultrapure Milli-Q water (DI) (Millipore) with a resistivity of 18.2 MΩ/cm was used in all

experiments. All materials were used as received with no further purification.

4
Fiber Fabrication via Electrospinning

Two separate sets of the fibers were prepared and used for studies of the effect of PVP/TA

total concentration on the fiber diameter, or for investigation of mechanical, antioxidant, and pH-

stability properties of the fiber mats. In the first case, solutions of PVP/TA were prepared in a

75/25 DMF/DMSO (v/v) solvent at an equimolar ratio of PVP and TA hydrogen-bonding units

but varied total concentration (10.5-15 wt.%). For easier dissolution, the solutions were gently

stirred at ambient temperature overnight. For preparation of the second set of fibers, PVP and TA

were dissolved in 75/25 DMF/DMSO (v/v) at 13.5 wt.% total concentration but varied mole

fractions of TA to PVP. In all cases, the solutions were used for electrospinning immediately after

preparation.

In a typical electrospinning procedure, 3.5 mL of solution was placed in a syringe with a

0.4 mm inner-diameter tip. A standard home-built single-needle electrospinning setup equipped

with a rotary collector covered with conductive aluminum foil was used to obtain mats of

uniaxially aligned fibers. The high voltage power supply (ES 30-0.1P, Gamma High Voltage

Research) was connected to the tip of the syringe needle (size 21G) and to the collector to complete

the circuit. The flow rate was controlled by a syringe pump (NE-1000, New Era Systems, Inc.)

and kept constant at 0.43 mL/hr. The fibers were spun for 8 hours at an applied voltage of 12 kV.

The fibers were collected on a rotatory collector which was placed at a distance of 35 cm from the

spinneret, at a rotational speed of 1000 rpm. For control fibers, electrospinning was performed

with a 12.5 wt.% solution of PVP at a flow rate of 0.5 mL/hr and 13 kV, when the collector was

placed at a distance of 25 cm from the spinneret. All electrospinning experiments were performed

in ambient conditions (24 oC and 50-60% relative humidity). After deposition, mats of aligned

fibers could be easily detached from the surface of the collector.

5
Fiber Characterization

Scanning Electron Microscopy. The fiber mat morphology was studied by scanning electron

microscopy (SEM) using a JSM-7500F (JEOL) instrument equipped with a cold cathode UHV

field emission conical anode gun. The images were taken at an accelerating voltage of 3 kV and a

working distance of 15 mm. The surface of the samples was sputtered with 2 nm Pt/Pd coating to

avoid charging. A systematic investigation of the fiber diameter was carried out by the ImageJ®

software.39 Each average fiber diameter was obtained from more than 100 fiber diameter

measurements collected from multiple SEM images.

Mechanical Analysis. Tensile testing of uniaxially aligned fiber mats was performed with a tensile

tester (Gatan MT10365, Deben UK Ltd.) using the procedure described elsewhere.3,40,41 The

rectangular fiber mats with dimensions 17 mm x 9 mm were attached to a C-shaped 25 mm x 15

mm cardboard holder using a 5-minute-curing epoxy adhesive (Flow-mix, 5-minute epoxy,

Devcon home) as shown in Scheme 1. The specimen was then fixed by the jaws of the tensile

Scheme 1. Schematic representation of mechanical testing setup of a fiber mat, including C-

sectioned cardboard scaffold (a), a fiber mat is placed between glass coverslips and thickness
is measured using a micrometer (b), a cardboard scaffold with a fiber mat attached using a
5-min-curing epoxy adhesive (c), a Gatan tensile tester with a fiber mat attached and the
middle of the C-section is cut (d), and a tested specimen (e).

6
tester, and the middle of the C-shape holder was cut as shown in Scheme 1, to separate the upper

and lower sections of the scaffold. A strain rate of 0.5 mm/min and a gauge length of 15 mm were

used for all of the specimens tested.

Prior to the attachment of the fiber mat to the holder, the fiber mat thickness was

determined using a digital micrometer with a precision of 1 μm. Subsequently, the fiber mat was

placed between two glass coverslips to increase the contact area and reduce the compression of the

fiber mat, and the thickness of the sandwich construct was recorded as shown in Scheme 1. The

thickness of the fiber mat was determined after subtraction of the thickness of the glass coverslips.

While the same amounts of solutions were spun, some mass losses occurred during spinning and

sample collection, resulting in a ~30% variation in thickness of the collected samples. Specifically,

the sample thicknesses varied between 50 and 90 m, with a much smaller variation of the fiber

mat densities of 0.27±0.02 g/cm3. Values of stress, tensile strength, and elastic moduli were

determined in the tensile test experiments for the free-standing fibrous material.

Thermal Analysis. Thermogravimetric analysis (TGA) and differential scanning calorimetry

(DSC) studies with the fiber mats were performed using TGA 5500 and Q2500 equipment (TA

Instruments, USA), respectively. All experiments were carried out using 10°C/min heating and

cooling rates. The samples were prepared by placing 10 to 12 mg of fiber mats into a platinum pan

for TGA analysis or into a hermetically sealed aluminum pan for DSC. The glass transition

temperature (Tg) for the fibers was determined as the middle of the transition in the DSC profile

using the thermal analysis software provided by TA Instruments.

Fiber Stability at Various pH. Stability of the fiber mats in solutions at different pH ranging from

4 to 11 was studied using a combination of visual inspection of the fiber mats, UV-Vis studies of

the supernatant solutions, and SEM studies of the fiber mats. To determine the concentration of

7
TA released in solution, the fiber mats with different PVP-to-TA ratios were cut into small

rectangular pieces with masses of 1.2 to 4 mg, weighed, and placed into vials containing 20 mL of

DI water at pH 6. Periodically, 1-mL aliquots of the supernatant solutions were collected, diluted

with 2 mL of DI water, and measured using a UV 2600 spectrophotometer (Shimadzu Inc.). The

absorbances were measured for a characteristic TA absorption band at 260 nm using DI water as

a reference and converted to the amounts of TA released to solution. The extinction coefficient of

TA solutions was determined from a calibration curve obtained in a separate experiment using TA

solutions of known concentrations. The percent of released TA was calculated using the following

equation:

3𝐴 1701
% 𝑇𝐴 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 = × × 100
𝜀𝑙 𝑚(𝑓𝑖𝑏𝑒𝑟 𝑚𝑎𝑡) × 𝜔(𝑇𝐴 𝑖𝑛 𝑓𝑖𝑏𝑒𝑟 𝑚𝑎𝑡)
(1)

where A is absorbance, ε = 6.0 ∙ 104 L mol-1 cm-1 is the extinction coefficient of TA at 260 nm,

l = 1 cm, 1701 is the molecular weight of TA in g/mol, m is the mass of an immersed fiber mat in

grams, and ω is the mass fraction of TA in the fiber mat.

Antioxidant Activity. Antioxidant activity of the fiber mats was assessed by their capability to

reduce the concentration of ABTS radical cation, ABTS•+. A solution of ABTS•+ was prepared by

mixing equal volumes of 7 mM solutions of ABTS precursor and 2.45 mM solutions of potassium

peroxydisulfate in DI water (all solutions were purged with nitrogen prior to use), followed by 24-

hour incubation in the dark to complete the formation of ABTS•+.42 The ABTS•+ stock solution was

prepared by diluting the original ABTS•+ solution with nitrogen-purged DI water to achieve an

absorbance value A of 1.7 or 3 at 732 nm. For comparing antiradical performance of PVP-TA0.67

bulk complexes and nanofiber mats, 20 mL of stock solutions with A of 1.17 and 18 mg samples

were used. For quantitative assessment of burst versus prolonged antiradical performance, pieces

8
of fiber mats with different PVP/TA compositions weighing 1.2 to 1.4 mg were used for immersion

in 50 mL of ABTS•+ stock solutions with an initial absorbance value of 3. Periodically, 1-mL

aliquots were collected from the containers containing pieces of PVP/TA fibers, diluted with 2 mL

of DI water, and analyzed using UV-Vis spectrometry. To account for the contribution of TA

released from the fibers to solution, a separate set of experiments was conducted in which the fiber

mats were not continuously exposed to ABTS•+, but instead were kept in contact with DI water. In

this set of experiments, fiber mats with masses of 2 to 2.6 mg were placed in 20 mL of DI water

at pH ~ 6.5. Aliquots of these solutions were added to 3 mL of ABTS•+ stock solution and

incubated in the dark for the same amount of time as the exposure of the original fibers to water to

assure completion of the reaction. In both experiments, antioxidant activity was calculated from a

decrease in the intensity of the ABTS•+ solutions at 732 nm (ε = 25400 M-1cm-1),43 calculated as

(𝐴0 − 𝐴)⁄𝜀 , where A0 is absorbance of the control ABTS•+ solution (which was incubated for the

same time period, but without the fiber mats or supernatant solutions), and A is absorbance of

ABTS•+ solutions exposed to nanofibers or fiber supernatant solutions. The antioxidant activities

of the fiber mats and the supernatant solutions were quantified as the moles of ABTS•+ reduced by

1 mg of the fiber mats.

9
RESULTS AND DISCUSSION

To achieve simultaneous control of the fiber mechanical properties, stability in aqueous

environment, and antioxidant activity, a wide range of PVP/TA ratios was explored. Scheme 2

schematically illustrates the electrospinning procedure of uniaxially aligned hydrogen-bonded

fibers. To assure processability of the fibers, we pursued a strategy of dissociating PVP/TA

hydrogen bonding in organic solvents, such as DMF or DMSO, which are capable of modulating

intermolecular binding via competitive hydrogen bonding.44-46 This strategy was pursued because

in contrast to electrostatically associated polyelectrolyte complexes, which can be ‘soften’ by

disruption of ionic pairing by inorganic salts,10 hydrogen-bonded complexes are not significantly

affected by the addition of small ions.44 PVP/TA solutions in DMF/DMSO 75/25 (v/v) were easily

processable, clear viscous liquids in which intermolecular binding was suppressed. However,

hydrogen bonds between PVP and TA were formed as solvent evaporated during the spinning

process. The fiber compositions, controlled by the ratio of the components in the spinning

Scheme 2. Schematic representation of electrospinning of PVP-TA fibers from DMF/DMSO

solutions. The SEM image shows a representative image of as-spun free-standing fibers prepared
using a 13.5 wt.% PVP-TA solution containing equimolar amounts of hydrogen-binding units.

10
solutions, are abbreviated as PVP-TAX, where X is the molar fraction of TA hydrogen-bonding

units, calculated as the ratio of moles of hydroxyl groups of TA to the sum of moles of PVP

repeating units and hydroxyl groups of TA. In this abbreviation system, the fibers abbreviated as

PVP-TA0.5 are composed of PVP and TA with equal number hydrogen-bonding units.

Figure 1 shows that bead-free, aligned fibers with good uniformity were produced from

solutions with a broad range of PVP-to-TA ratios. Progressively thinner fibers are formed from

solutions with increased content of TA, with the average fiber diameter decreasing from 708  65

nm to 395  82 nm for PVP-TA0.33 to PVP-TA0.67 systems, respectively. In addition, Figure S1

illustrates an increase in the fiber diameters obtained from solutions with an increased total

concentration but fixed PVP-to-TA ratio. Both results are consistent with previous literature and

reflect the commonly observed trend associated with the slower flow of more viscous higher-

polymer-containing solutions through the metallic needle tip during the electrospinning process.
47-49

(a) PVP (b) PVP-TA0.33 (e)

3!m 3!m

(c) (d)
PVP-TA0.50 PVP-TA0.67
(f)

3!m 3!m

Figure 1. The dependence of the fiber diameter on the mole fraction of TA in PVP-TA solution
with the total concentration of 13.5 wt.%. SEM micrographs and insets illustrate the fiber diameter
distributions for PVP (a), PVP-TA0.33 (b), PVP-TA0.5 (c), and PVP-TA0.67 (d), change in average
diameter of a fiber with a change in mole fraction of TA (e) and a fiber mat of PVP-TA0.5 (f).

11
(a) (b)

(c)
PVP-TA0.25 PVP-TA0.50 PVP-TA0.67
PVP o o o o

o o o o o
o o o OH
o OH OH

o o o o o HO OH o HO OH HO OH

o o o OH OH OH OH
o o o OH OH
o HO OH HO OH
HO OH o
o o o o o
HO HO
HO HO
o o HO
HO

o
o o o o
OH
o HO OH o OH OH o
OH OH OH OH
OH OH OH OH
o
OH OH
OH OH
OH
o OH
o
OH
OH
o
OH
OH
HO OH o o o o o o o
o o
TA o o o o o o
o o
HO
HO
o o o
o o o o o o
o o o o o o
o
OH OH o
OH OH OH o OH o HO OH HO OH
HO OH o o o o
o OH
OH
OH OH
o HO OH o o OH OH OH
OH o o o o OH
OH HO OH o
OH o o o o OH OH
o HO
HO OH o o HO OH o HO
HO
o
HO
HO
o o HO
HO
o
o o o
HO
HO o o
o o
o o o OH OH
o
OH
o
OH
o o o o OH o OH OH
OH
OH
OH OH
o
OH OH
OH
OH o o OH OH
o o
OH
OH
OH
o o o
OH
OH
OH OH
o o o
o o o
o o

Figure 2. Tensile strength, toughness (a), as well as elongation at break and elastic moduli (b) of
the uniaxially aligned free-standing PVP-TA fiber mats as a function of molar fraction of TA,
along with schematic representation of PVP-TA binding at increased molar fractions of TA (c).

Mechanical properties of as-electrospun fibers prepared at various PVP-to-TA ratios

were then determined under longitudinal tension. These experiments yielded the stress-strain

curves shown in Figure S2, which were used to determine the dependencies of tensile strength,

toughness, elastic modulus, and elongation at break on the fiber composition. Note that these

results were obtained with the uniaxially oriented free-standing fiber mats, and the data shown in

Figure 2a and Figure S2 were calculated from the dimensions of the fiber mats.

12
 As shown in Figure 2a, the tensile strength and toughness of pristine PVP fibers (2.6 MPa

and 0.344 MJ/m3, respectively) was greatly increased after the addition of small fractions of TA,

and achieved their maximum values of tensile strength (~16 MPa) and toughness (~1.12 MJ/m3)

at 0.25 to 0.30 TA mole fraction. The ~6-fold enhancement in tensile properties of PVP-TA

nanofibers is the result of establishment of a network of hydrogen bonds between PVP and TA.

This observation is in agreement with previous reports of the effect of hydrogen bonding on

mechanical properties of self-assembled polymer materials for other systems.19 Further increase

in TA concentration deteriorated the fiber mechanical properties, resulting in materials with only

2-fold higher tensile strength as compared to that of pristine PVP fibers. Note that single-

component TA fibers could not be prepared because of the low-molecular weight of TA and the

resulting lack of intermolecular interactions and entanglement network. The occurrence of the

maxima in tensile strength and toughness most likely results from the formation of the densest

network of hydrogen bonds at intermediate PVP-TA compositions (see schematic representation

in Figure 2c). Fewer PVP-TA hydrogen bonds are formed in a large excess of either PVP or TA

because hydrogen bonds in this system are formed exclusively between hydrogen-donating groups

of TA and hydrogen-accepting carbonyl moieties of PVP.

Unlike tensile strength and toughness, elongation at break was the largest for pristine PVP

fibers, and decreased with increasing TA content, because small, non-polymeric TA molecules

could not support large fiber extension (Figure 2b). On the other hand, addition of TA caused an

increase in Young’s moduli of the fibers of pristine PVP fiber mats from ~35 MPa to ~293 MPa.

Comparing our results with a study on similar system, the modulus of the PVP-TA0.33 fibers was

nearly 24 times higher than that of randomly oriented electrospun fibers of hydrogen bonded

complexes with similar fiber diameters.50 Note that the fiber mats with the largest content of TA

13
studied here (PVP-TA0.67) retained their structural flexibility and could be handled without

breaking individual fibers.

For the solution-processed materials, including electrospun fibers, the remnant solvent

and/or the hydrating water can significantly affect materials’ mechanical and thermal properties.
51,52,53
The fiber mats in Figure 2 and Figure S2 were studied immediately after electrospinning

without any heat pre-treatment, when mats were also exposed to the ambient environment. A

question then arose of the role of the co-solvent and water on the fiber’s mechanical properties.

The data in Figure 2b and Figure S2 show the high elongation at break for the fibers of pristine

PVP (Tg of 180 oC)54 at room temperature, suggesting the occurrence of plasticization. Therefore,

it was important to quantify the fraction of solvents present in the fibers. Figure 3a shows the

TGA data of pristine PVP fibers along with PVP-TA fibers with different component ratios in the

temperature range between 50 and 250 oC. The complete TGA scans are shown in Figure S3,

(a) (b)

Figure 3. TGA analysis of individual fiber components and PVP-TA fibers: TGA data for
the fibers of different compositions during heating between 50 and 250 oC and inset image
shows the method of calculating solvent content for PVP-TA0.60 (a), as well as quantified
contents of water and DMF/DMSO as a function of mole fraction of TA in PVP-TA fibers
(b).

14
which illustrates decomposition of individual TA and PVP components above 225 oC, and 400 oC,

respectively.55 Decomposition of PVP-TA fibers occurred within the 250-450 oC temperature

range, with specific decomposition profile dependent on the PVP-to-TA ratio (Figure S3). Figure

3a shows that at temperatures below 250 oC, where PVP and TA remained thermally stable, two-

step mass loss occurred, which is attributed to sequential loss of water at ~100 oC and DMF/DMSO

between 150 and 250 oC (boiling points of DMF and DMSO 153 oC and 189 oC, respectively).56

Figure 3b shows quantification of the content of water and organic solvents in the PVP-TA fibers.

Interestingly, the uptake of water versus organic solvents was highly dependent on the fiber

composition. TGA results show that pristine PVP fibers with the largest water loss of ~20% were

the most hydrated. On the other hand, as the fibers became enriched with TA, the amount of water

in the fibers decreased, while more DMF/DMSO was retained within the fibers. These trends

occurred because of the hydrophilic nature of PVP, which is soluble in water54, and hydrophobicity

of PVP-TA complexes, which phase-separate from aqueous solutions.18

The occurrence of hydrogen bonding between the fiber components was then studied in a

series of differential scanning calorimetry (DSC) experiments which aimed to explore the effect

of PVP-TA binding on the fiber glass transition temperature, Tg. During the first heating cycle,

solvent loss dominated the loss of water, as indicated by an endothermic peak between 90 oC and

125 oC observed in all samples (Figure S4a). In good agreement with the data in Figure 3,

however, the magnitude of this peak was largest for pristine PVP fibers and decreased for the fibers

with higher TA content. In the second heating cycle, shown in Figure 4a, solvent evaporation was

complete, and distinct glass transitions for fibers of all compositions were observed. The fiber Tg

increased from ~177 oC for pristine PVP (in good agreement with the previously reported of 180
o
C)54 to ~234 oC for the fibers with the equimolar ratio of PVP-to-TA units. This increase reflects

15
loss of segmental mobility of PVP due to hydrogen bonding with TA. Note that the glass transition

temperature could not be determined for the fibers with the mole fraction of TA larger than 0.5

because of the onset of degradation of excess TA, which was not bound within PVP-TA complex

(Figure S4b).

(a) (b)

Figure 4. DSC thermograms of pristine PVP and PVP-TA fibers with varied ratios of the
components collected during the second heating cycle at a heating rate of 10 oC/min (a), and the
glass transition temperature, Tg, as a function of molar fraction of TA in the electrospun fibers (b).
The total concentration of PVP and TA in the electrospinning solutions was 13.5 wt.%.

We then explored functionality of PVP-TA fiber mats in an aqueous environment, which

is required for leveraging the antioxidant properties of the fiber mats for potential biomedical and

environmental applications. Figure 5 shows the stability/solubility diagram of the fibers as a

function of fiber composition and solution pH. To identify specific solubility regimes (stability,

gelation, and dissolution), the fiber mats were immersed in solutions at different pH for 10 days

and studied using visual inspection. The fibers were considered stable if they fully preserved their

morphology.

16
Figure 5. Stability diagram of PVP-TA fiber mats of different compositions in aqueous solutions
at various pH after 10 days of immersion.

Figure 5 illustrates that the fiber mats of all compositions were more stable in solutions at

acidic, neutral and slightly basic pH, and dissolved in strongly basic solutions. This observation is

consistent with previous reports on PVP-TA layer-by-layer films and reflects dissociation of PVP-

TA complexes at high pH’s when TA becomes ionized (pKa of 8.5).18 The pH of

stability/dissolution transitions was strongly dependent on the fiber composition. The fibers with

high percentage of PVP (such as PVP-TA0.33) were not structurally stable in the entire range of pH

because of the high hydrophilicity of PVP which was present in excess in these fibers. These fiber

mats fully lost their morphology by turning into continuous hydrogels at pH 4 to 8 and dissolving

at pH > 8. In contrast, fibers with higher content of TA were stable within a wider pH range because

all hydrophilic PVP was bound with TA within hydrophobic PVP-TA complexes. Specifically,

PVP-TA0.5 fiber mats were stable up to pH 8, swelled at pH 9, and dissolved at higher pHs. The

fiber pH stability region further expanded to more basic pH (pH =10 for PVP-TA0.67 fibers) as the

content of TA increased. More detailed studies were performed for pH 6 to correlate stability of

the fibers and retention of their morphology with release of TA to the solution. Fibers of different

17
Figure 6. SEM images of PVP-TA0.33, PVP-TA0.5, and PVP-TA0.67 fibers before (a) and after
(b) 50 days of immersion in aqueous solution at pH 6. The scale bar is 4 μm. Release profile of
TA from the fibers of various compositions a pH 6 (c), along with the analysis of the average
fiber diameters before and after the immersion (d).

18
compositions were immersed at pH 6 for 50 days, the morphology of fibers was explored with

SEM, and the release of the TA was measured with UV-Vis spectroscopy, as shown in Figure 6.

Consistent with the morphological stability (Figure 6a and 6b) was compositional stability

of the fibers, monitored as release of TA to the surrounding solution. Figure 6c illustrates the

strong effect of the fiber composition on release of TA in solution at pH 6. Consistent with our

previous report on solubilization of PVP-TA hydrogen-bonded complexes18 with excess of

hydrophilic PVP, PVP-rich PVP-TA0.33 fibers released almost half of assembled TA as they lost

their morphology and turned to hydrogels. At the same time, fibers with higher content of TA

retained at least 92% of TA when exposed to aqueous solutions for as long as 50 days. These

results show that controlling the composition of electrospun fibers allows one to engineer the fiber

stability and the dose of TA released to solution in response to pH triggers.

The capability of the fiber mats to scavenge free radicals was then explored using the

morphologically stable PVP-TA samples. The advantage of using the nanofiber mats compared to

bulk complexes is illustrated in Figure 7a. While a solution-cast solid sample of PVP-TA0.67

complex was fragile and rigid, electrospun fibers were flexible and easy to handle. Because of high

specific surface area of the fibrous mats, they demonstrated orders of magnitude higher overall

antioxidant performance (Figure 7a).

We then hypothesized that assembly of TA within the fibers can restrict immediate

availability of the antioxidant as compared to solution and result in its prolonged action. Testing

this hypothesis required experiments at much longer time scales than those used in antioxidant

studies of polyphenols dissolved in solutions,42 or included within ultrathin adsorbed layers.57

The antioxidant activity of the fiber mats was assessed by the standard ABTS•+ radical

scavenging assay. To quantify the capability of the fiber mats to reduce ABTS•+, small coupons of

19
 Figure 7. Comparison of the antioxidant efficiency of a continuous film and a fiber mat of
PVP-TA0.67 composition to reduce ABTS•+ radicals at short time (a), and quantification of the
antioxidant activity of the fiber mats and the corresponding solution extracts as a function of
immersion time (b).

the fiber mats were exposed to ABTS•+ solutions of which absorbance was monitored during 22

days of the immersion experiment. Additionally, to determine relative contributions of released

and assembled TA to the overall antioxidant activity, parallel ABTS•+ antioxidant tests were

performed in which the fiber mats were exposed to water rather than ABTS•+ solutions, and

aqueous extracts were collected and analyzed for antioxidant activity after certain periods of time.

Figure 7b demonstrates that unlike TA present in solution, PVP-TA0.5 and PVP-TA0.67 fiber mats

demonstrated a long-term antioxidant performance. The fiber mats with lower content of TA

(PVP-TA0.33) were not used in these experiments because they fully lost their fibrous morphology

as a result of exposure to ABTS•+ solutions (Figure S5), similarly to their exposure to water

(Figure 7b).

During the first 2 days, the amount of ABTS•+ reduced by the immersed fiber mats closely

matched the amount of ABTS•+ radical reduced by fiber supernatant solutions (Figure 7b),

20
suggesting that at the initial stage, antiradical activity of the fibers is brought mostly by TA

released to solution. At the same time, after 2 days of immersion, the amount of reduced ABTS•+

continued increasing for the fibers and stayed relatively the same for the fiber supernatant

solutions. This suggests that at the longer times of immersion, antioxidant activity was

supplied/occurred not by TA released from fibers to solution, but by TA assembled within the

fibrous mats. The antioxidant capacity of the fiber mats continued to slowly rise between 5 and 15

days and reached its plateau value after ~15 days.

To estimate the fraction of TA assembled within the fiber mats that was available for

reacting with ABTS•+, the overall maximum antioxidant capacity of the fibers was determined by

measuring the activity of free TA in solution. The maximum amount of ABTS•+ that can be reduced

by all TA in the fibers was 24.2 ± 1.3 mmol of the radical per 1 g of TA (Figure S6). From a

comparison of the amounts of ABTS•+ radical reduced by the immersed fiber mats after 22 days

with the total amount of TA in the fibers, and assuming a sharp boundary between ABTS•+-

penetrated and ABTS•+-unaffected fiber material, the penetration depth of ABTS•+ within PVP-

TA0.5 and PVP-TA0.67 fibers was estimated as ~43 nm and ~13 nm, respectively. These values

correspond to 21% and 12% of the outer circular cross-sectional area of the fibers, respectively.

Oxidation of TA within ABTS•+ penetration zone was also evident visually from the yellow color

of the fiber mats characteristic of oxidized TA (Figure S7). More efficient penetration of ABTS•+

within PVP-TA0.5 fibers (as compared to PVP-TA0.67 fibers) agrees with softened and flattened

morphology and a wider diameter distribution for the dry PVP-TA0.5 fiber mats (Figure 8), all

suggesting a significant water uptake occurring during exposure of these fibers to ABTS•+

solutions. Free volume acquired due to solvent uptake facilitated ABTS•+ diffusion within the

fibers and increased availability of TA for oxidation, ultimately boosting antioxidant performance

21
of the fibers. In contrast, the fibers with a higher content of TA (PVP-TA0.67) demonstrated no

changes in the fiber diameters or morphology (Figure 8). It is likely that the low degree of swelling

of PVP-TA0.67 fibers restricted penetration of ABTS•+ and resulted in lower antioxidant activity of

these fibers as compared to that of the more swellable PVP-TA0.5 fibers.

Figure 8. The average fiber diameters and SEM images of PVP-TA0.5 and PVP-TA0.67 fiber
mats before and after 22-day exposure to ABTS•+ solutions. The scale bar is 4 μm.

CONCLUSION

In summary, we report on robust polymeric electrospun fibers whose mechanical properties

in their dry state, stability in aqueous environments at different pH values, and antioxidant

properties can be efficiently tuned by the ratio of hydrogen-bonding components. Addition of

hydrogen-bonding, antioxidant small molecules to a water-soluble polymer enabled almost an

order of magnitude enhancement in the fiber tensile strength, toughness, and Young’s modulus as

a result of formation of a network of hydrogen bonds. At the same time, simultaneous control of

the solubility properties of the fiber mats in aqueous environments along with their functionality

(antioxidant activity) was achieved. This work demonstrates a unique capability of the fibers to

22
prolong antioxidant activity, supplied by fiber-assembled antioxidant small molecules. We believe

that this class of new antioxidant materials with high surface area, robust mechanical properties,

controlled stability in aqueous environment, and capability for long-term antioxidant protection

can find applications in environmental and biomedical engineering constructs which benefit from

the long-term antioxidant properties of these materials. One example of such application is tissue

engineering constructs which can impart controlled levels of scavenging of reactive oxidant

species across the span of weeks often required for successful tissue regeneration.

Supporting Information

The supporting information file consists of seven figures which present SEM micrographs of PVP-

TA0.5 fibers electrospun from solutions of varying concentrations; tensile stress-strain curves for

the PVP-TA fiber mats of different compositions; full TGA thermograms of pristine PVP, TA and

PVP-TA fibers; DSC thermograms for PVP, TA and PVP-TA fibers during the first heating cycle;

as well as SEM images and the visual appearance of PVP-TA fiber mats after reacting with ABTS•+

solutions.

Corresponding Author

*E-mail: svetlana@[Link].

Notes

The authors declare no competing financial interest.

Acknowledgment

This work was supported in part by the National Science Foundation under Award DMR-1610725,

DMR-1905535, and the Texas A&M University Experiment Station. The authors acknowledge

Materials Characterization Facility at Texas A&M University for enabling optical and scanning

electron microscopy measurements.

23
References

(1) Thenmozhi, S.; Dharmaraj, N.; Kadirvelu, K.; Kim, H. Y. Electrospun Nanofibers:

New Generation Materials for Advanced Applications. Materials Science and Engineering: B

2017, 217, 36-48.

(2) Xue, J.; Xie, J.; Liu, W.; Xia, Y. Electrospun nanofibers: New Concepts, Materials,

and Applications. Accounts of Chemical Research 2017, 50, 1976-1987.

(3) Dahlin, R. L.; Kasper, F. K.; Mikos, A. G. Polymeric Nanofibers in Tissue

Engineering. Tissue Engineering Part B: Reviews 2011, 17, 349-364.

(4) Sill, T. J.; von Recum, H. A. Electrospinning: Applications in Drug Delivery and

Tissue Engineering. Biomaterials 2008, 29, 1989-2006.

(5) Jiang, T.; Carbone, E. J.; Lo, K. W. H.; Laurencin, C. T. Electrospinning of Polymer

Nanofibers for Tissue Regeneration. Progress in Polymer Science 2015, 46, 1-24.

(6) Ma, Z.; Kotaki, M.; Ramakrishna, S. Electrospun Cellulose Nanofiber as Affinity

Membrane. Journal of Membrane Science 2005, 265, 115-123.

(7) Ma, H.; Burger, C.; Hsiao, B. S.; Chu, B. Ultra-fine Cellulose Nanofibers: New

Nano-Scale Materials for Water Purification. Journal of Materials Chemistry 2011, 21, 7507-

7510.

(8) Lee, J. S.; Jun, J.; Cho, S.; Kim, W.; Jang, J. Electrospun Three-Layered Polymer

Nanofiber-Based Porous Carbon Nanotubes for High-Capacity Energy Storage. RSC Advances

2017, 7, 201-207.

(9) Chinnappan, A.; Baskar, C.; Baskar, S.; Ratheesh, G.; Ramakrishna, S. An

Overview of Electrospun Nanofibers and Their Application in Energy Storage, Sensors and

Wearable/Flexible Electronics. Journal of Materials Chemistry C 2017, 5, 12657-12673.

24
 (10) Meng, X.; Perry, S. L.; Schiffman, J. D. Complex coacervation: Chemically Stable

Fibers Electrospun from Aqueous Polyelectrolyte Solutions. ACS Macro Letters 2017, 6, 505-511.

(11) Boas, M.; Gradys, A.; Vasilyev, G.; Burman, M.; Zussman, E. Electrospinning

Polyelectrolyte Complexes: pH-Responsive Fibers. Soft Matter 2015, 11, 1739-1747.

(12) Celebioglu, A.; Kayaci-Senirmak, F.; İpek, S.; Durgun, E.; Uyar, T. Polymer-Free

Nanofibers from Vanillin/Cyclodextrin Inclusion Complexes: High Thermal Stability, Enhanced

Solubility and Antioxidant Property. Food & function 2016, 7, 3141-3153.

(13) Mei, L.; Fan, R.; Li, X.; Wang, Y.; Han, B.; Gu, Y.; Zhou, L.; Zheng, Y.; Tong, A.;

Guo, G. Nanofibers for Improving the Wound Repair Process: The Combination of a Grafted

Chitosan and an Antioxidant Agent. Polymer Chemistry 2017, 8, 1664-1671.

(14) Xu, F.; Weng, B.; Gilkerson, R.; Materon, L. A.; Lozano, K. Development of

Tannic acid/Chitosan/Pullulan Composite Nanofibers from Aqueous Solution for Potential

Applications as Wound Dressing. Carbohydrate Polymers 2015, 115, 16-24.

(15) Ma, G.; Liu, Y.; Fang, D.; Chen, J.; Peng, C.; Fei, X.; Nie, J. Hyaluronic

acid/Chitosan Polyelectrolyte Complexes Nanofibers Prepared by Electrospinning. Materials

Letters 2012, 74, 78-80.

(16) Penchev, H.; Paneva, D.; Manolova, N.; Rashkov, I. Novel Electrospun Nanofibers

Composed of Polyelectrolyte Complexes. Macromol Rapid Comm 2008, 29, 677-681.

(17) Sukhishvili, S. A.; Granick, S. Layered, Erasable Polymer Multilayers Formed by

Hydrogen-Bonded Sequential Self-Assembly. Macromolecules 2002, 35, 301-310.

(18) Erel-Unal, I.; Sukhishvili, S. A. Hydrogen-Bonded Multilayers of a Neutral

Polymer and a Polyphenol. Macromolecules 2008, 41, 3962-3970.

25
 (19) Song, P. a.; Xu, Z.; Guo, Q. Bioinspired Strategy to Reinforce PVA with Improved

Toughness and Thermal Properties via Hydrogen-Bond Self-Assembly. ACS Macro Letters 2013,

2, 1100-1104.

(20) Lv, Z.; Qiao, J.-N.; Song, Y.-N.; Ji, X.; Tang, J.-H.; Yan, D.-X.; Lei, J.; Li, Z.-M.

Baroplastics with Robust Mechanical Properties and Reserved Processability Through Hydrogen-

Bonded Interactions. ACS Applied Materials & Interfaces 2019, 11, 12008-12016.

(21) Sakagami, H.; Jiang, Y.; Kusama, K.; Atsumi, T.; Ueha, T.; Toguchi, M.; Iwakura,

I.; Satoh, K.; Ito, H.; Hatano, T. Cytotoxic Activity of Hydrolyzable Tannins Against Human Oral

Tumor Cell Lines: A Possible Mechanism. Phytomedicine 2000, 7, 39-47.

(22) Chen, K.-S.; Hsiao, Y.-C.; Kuo, D.-Y.; Chou, M.-C.; Chu, S.-C.; Hsieh, Y.-S.; Lin,

T.-H. Tannic Acid-Induced Apoptosis and Enhanced Sensitivity to Arsenic Trioxide in Human

Leukemia HL - 60 Cells. Leukemia Research 2009, 33, 297-307.

(23) Tikoo, K.; Sane, M. S.; Gupta, C. Tannic Acid Ameliorates Doxorubicin-Induced

Cardiotoxicity and Potentiates its Anti-Cancer Activity: Potential Role of Tannins in Cancer

Chemotherapy. Toxicology and Applied Pharmacology 2011, 251, 191-200.

(24) Costa, E.; Coelho, M.; Ilharco, L. M.; Aguiar-Ricardo, A.; Hammond, P. T. Tannic

Acid Cediated Suppression of PNIPAAM Microgels Thermoresponsive Behavior.

Macromolecules 2011, 44, 612-621.

(25) Schmidt, D. J.; Hammond, P. T. Electrochemically Erasable Hydrogen-Bonded

Thin Films. Chemical Communications 2010, 46, 7358-7360.

(26) Kozlovskaya, V.; Xue, B.; Lei, W.; Padgett, L. E.; Tse, H. M.; Kharlampieva, E.

Hydrogen-Bonded Multilayers of Tannic Acid as Mediators of T-cell Immunity. Advanced

Healthcare Materials 2015, 4, 686-694.

26
 (27) Le, Z.; Chen, Y.; Han, H.; Tian, H.; Zhao, P.; Yang, C.; He, Z.; Liu, L.; Leong, K.

W.; Mao, H.-Q.; Liu, Z.; Chen, Y. Hydrogen-Bonded Tannic Acid-Based Anticancer Nanoparticle

for Enhancement of Oral Chemotherapy. ACS Applied Materials & Interfaces 2018, 10, 42186-

42197.

(28) Kozlovskaya, V.; Zavgorodnya, O.; Chen, Y.; Ellis, K.; Tse, H. M.; Cui, W.;

Thompson, J. A.; Kharlampieva, E. Ultrathin Polymeric Coatings Based on Hydrogen‐bonded

Polyphenol for Protection of Pancreatic Islet Cells. Advanced Functional Materials 2012, 22,

3389-3398.

(29) Yang, S. Y.; Rubner, M. F. Micropatterning of Polymer Thin Films with pH-

sensitive and Cross-linkable Hydrogen-bonded Polyelectrolyte Multilayers. Journal of the

American Chemical Society 2002, 124, 2100-2101.

(30) Kharlampieva, E.; Sukhishvili, S. A. Hydrogen‐bonded Layer‐by‐Layer Polymer

Films. Journal of Macromolecular Science, Part C: Polymer Reviews 2006, 46, 377-395.

(31) Khutoryanskiy, V. V. Hydrogen-bonded Interpolymer Complexes as Materials for

Pharmaceutical Applications. International Journal of Pharmaceutics 2007, 334, 15-26.

(32) Sukhishvili, S. A.; Granick, S. Layered, Erasable, Ultrathin Polymer Films. Journal

of the American Chemical Society 2000, 122, 9550-9551.

(33) Li, J.; Wang, Z.; Wen, L.; Nie, J.; Yang, S.; Xu, J.; Cheng, S. Z. D. Highly Elastic

Fibers Made from Hydrogen-bonded Polymer Complex. ACS Macro Letters 2016, 5, 814-818.

(34) Selvaraj, S.; Fathima, N. N. Fenugreek Incorporated Silk Fibroin Nanofibers: A

Potential Antioxidant Scaffold for Enhanced Wound Healing. ACS Applied Materials & Interfaces

2017, 9, 5916-5926.

27
 (35) Aytac, Z.; Kusku, S. I.; Durgun, E.; Uyar, T. Encapsulation of Gallic

acid/Cyclodextrin Inclusion Complex in Electrospun Polylactic Acid Nanofibers: Release

Behavior and Antioxidant Activity of Gallic Acid. Materials Science and Engineering: C 2016,

63, 231-239.

(36) Whittaker, J. L.; Subianto, S.; Dutta, N. K.; Choudhury, N. R. Induced Insolubility

of Electrospun Poly(n-vinylcaprolactam) Fibres Through Hydrogen-bonding with Tannic Acid.

Polymer 2016, 87, 194-201.

(37) Yang, W.; Sousa, A.; Thomas-Gahring, A.; Fan, X.; Jin, T.; Li, X.; Tomasula, P.;

Liu, L. Electrospun Polymer Nanofibers Reinforced by Tannic acid/Fe+++ Complexes. Materials

2016, 9, 757.

(38) Naik, N.; Caves, J.; Chaikof, E. L.; Allen, M. G. Generation of Spatially Aligned

Collagen Fiber Networks Through Microtransfer Molding. Advanced Healthcare Materials 2014,

3, 367-374.

(39) Rieger, K. A.; Schiffman, J. D. Electrospinning an essential oil: Cinnamaldehyde

Enhances the Antimicrobial Efficacy of Chitosan/Poly (ethylene oxide) Nanofibers. Carbohydrate

Polymers 2014, 113, 561-568.

(40) Huang, Z.-M.; Zhang, Y.; Ramakrishna, S.; Lim, C. Electrospinning and

Mechanical Characterization of Gelatin Nanofibers. Polymer 2004, 45, 5361-5368.

(41) Asvar, Z.; Mirzaei, E.; Azarpira, N.; Geramizadeh, B.; Fadaie, M. Evaluation of

Electrospinning Parameters on the Tensile Strength and Structure Retention Strength of

Polycaprolactone Nanofibrous Scaffolds Through Surface Response Methodology. Journal of the

Mechanical Behavior of Biomedical Materials 2017, 75, 369-378.

28
 (42) Huang, D.; Ou, B.; Prior, R. L. The Chemistry Behind Antioxidant Capacity

Assays. Journal of Agricultural and Food Chemistry 2005, 53, 1841-1856.

(43) Cai, H.; Liu, X.; Zou, J.; Xiao, J.; Yuan, B.; Li, F.; Cheng, Q. Multi-wavelength

Spectrophotometric Determination of Hydrogen Peroxide in Water with Peroxidase-catalyzed

Oxidation of ABTS. Chemosphere 2018, 193, 833-839.

(44) Selin, V.; Aliakseyeu, A.; Ankner, J. F.; Sukhishvili, S. A. Effect of a Competitive

Solvent on Binding Enthalpy and Chain Intermixing in Hydrogen-bonded Layer-by-layer Films.

Macromolecules 2019, 52, 4432-4440.

(45) Wang, Y. H.; He, J.; Aktas, S.; Sukhishvili, S. A.; Kalyon, D. M. Rheological

Behavior and Self-healing of Hydrogen-bonded Complexes of a Triblock Pluronic((r)) Copolymer

with a Weak Polyacid. J Rheol 2017, 61, 1103-1119.

(46) Ma, S.; Yuan, Q.; Zhang, X.; Yang, S.; Xu, J. Solvent Effect on Hydrogen-bonded

Thin Film of Poly(vinylpyrrolidone) and Poly(acrylic acid) Prepared by Layer-by-layer Assembly.

Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015, 471, 11-18.

(47) Deitzel, J. M.; Kleinmeyer, J.; Harris, D.; Tan, N. B. The Effect of Processing

Variables on The Morphology of Electrospun Nanofibers and Textiles. Polymer 2001, 42, 261-

272.

(48) Thompson, C.; Chase, G. G.; Yarin, A.; Reneker, D. Effects of Parameters on

Nanofiber Diameter Determined From Electrospinning Model. Polymer 2007, 48, 6913-6922.

(49) Zong, X.; Kim, K.; Fang, D.; Ran, S.; Hsiao, B. S.; Chu, B. Structure and Process

Relationship of Electrospun Bioabsorbable Nanofiber Membranes. Polymer 2002, 43, 4403-4412.

29
 (50) Heiny, M.; Shastri, V. P. Nanofibers of Elastin and Hydrophilic Segmented

Polyurethane Solution Blends Show Enhanced Mechanical Properties Through Intermolecular

Protein–Polymer Hydrogen-bonding. Biomacromolecules 2016, 17, 1312-1320.

(51) Gupta, D.; Jassal, M.; Agrawal, A. K. The Electrospinning Behavior of Poly (vinyl

alcohol) in DMSO-Water Binary Solvent Mixtures. RSC Advances 2016, 6, 102947-102955.

(52) Hassan, A.; Rahman, N. A.; Yahya, R. Moisture Absorption Effect on Thermal,

Dynamic Mechanical and Mechanical Properties of Injection-Molded Short Glass-

Fiber/Polyamide 6, 6 Composites. Fibers and Polymers 2012, 13, 899-906.

(53) Yin, F.; Tang, C.; Li, X.; Wang, X. Effect of Moisture on Mechanical Properties

and Thermal Stability of Meta-Aramid Fiber Used in Insulating Paper. Polymers 2017, 9, 537.

(54) Turner, D.; Schwartz, A. The Glass Transition Temperature of Poly (n-vinyl

pyrrolidone) by Differential Scanning Calorimetry. Polymer 1985, 26, 757-762.

(55) Mallakpour, S.; Naghdi, M. Fabrication and Characterization of Novel

Polyvinylpyrrolidone Nanocomposites Having SiO2 Nanoparticles Modified With Citric Acid and

Ascorbic Acid. Polymer 2016, 90, 295-301.

(56) Vinci, D.; Donaldson, M.; Hallett, J.; John, E.; Pollet, P.; Thomas, C.; Grilly, J.;

Jessop, P.; Liotta, C.; Eckert, C. Piperylene sulfone: A Labile and Recyclable DMSO Substitute.

Chemical Communications 2007, 1427-1429.

(57) Zhang, W.; Yang, Z.-Y.; Cheng, X.-W.; Tang, R.-C.; Qiao, Y.-F. Adsorption,

Antibacterial and Antioxidant Properties of Tannic Acid on Silk Fiber. Polymers 2019, 11, 970.

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Table of Content

31