A Polyvinyl Alcohol/Acrylamide Hydrogel with Enhanced Mechanical Properties Promotes Full-Thickness Skin Defect Healing by Regulating Immunomodulation and Angiogenesis Through Paracrine Secretion

Hydrogel-based tissue-engineered skin has attracted increased attention due to its potential to restore the structural integrity and functionality of skin.However,the mechanical properties of hydrogel scaffolds and natural skin are substantially different.Here,we developed a polyvinyl alcohol(PVA)/acrylamide based interpenetrating network(IPN)hydrogel that was surface modified with polydopamine(PDA)and termed Dopa-gel.The Dopa-gel exhibited mechanical properties similar to native skin tissue and a superior ability to modulate paracrine functions.Furthermore,a tough scaffold with tensile resistance was fabricated using this hydrogel by three-dimensional printing.The results showed that the interpenetration of PVA,alginate,and polyacrylamide networks notably enhanced the mechanical properties of the hydrogel.Surface modification with PDA endowed the hydrogels with increased secretion of immunomodulatory and proangiogenic factors.In an in vivo model,Dopa-gel treatment accelerated wound closure,increased vascularization,and promoted a shift in macrophages from a proinflammatory M1 phenotype to a prohealing and anti-inflammatory M2 phenotype within the wound area.Mechanistically,the focal adhesion kinase(FAK)/extracellular signal-related kinase(ERK)signaling pathway may mediate the promotion of skin defect healing by increasing paracrine secretion via the Dopa-gel.Additionally,proangiogenic factors can be induced through Rho-associated kinase-2(ROCK-2)/vascular endothelial growth factor(VEGF)-mediated paracrine secretion under tensile stress conditions.Taken together,these findings suggest that the multifunctional Dopa-gel,which has good mechanical properties similar to those of native skin tissue and enhanced immunomodulatory and angiogenic properties,is a promising scaffold for skin tissue regeneration.

Enhance of Grafting Reaction of Acrylic Acid and Acrylamide onto Preirradiated Polypropylene Film

Grafting of acrylic acid (AAc) and acrylamide (AAm) onto preirradiated PP film was performed in aqueous solution of AAc and AAm, respectively. Electron beam accelerator was used as irradiation source. The effect of ferrous sulfate, sodium nitrate, methanol and glucose on the degree of grafting was demonstrated. The function of the different additives was compared by the grafting of different monomers (AAc and AAm). The results show that the four of these additives are elective on the grafting of AAc. Only two of these additives, ferrous sulfate and methanol were effective on the grafting of AAm.

Preparation of Hollow Silica Microspheres via Poly（N-isopropylacrylamide）

Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of PNIPAM template at 50 ~C. The PNIPAM template can be easily removed by water at room temperature so that SiO2 hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO2 hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy- drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO2 because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.

Synthesis and Flocculation Property of Chitosan-Acrylamide Graft Copolymer

Chitosan, as a kind of natural polymer, has many advantages, such as abundant sources, biological degradation, no secondary contamination and facile modification. In this work, we prepared modified chitosan flocculants with double electrical behavior via polymerizing chitosan, acrylamide and sodium carboxymethyl cellulose together by using ammonium persulfate as the indicator in water. The product is a comb-type of chitosan copolymer and a polymeric ampholyte. And then we studied the product by FTIR, UV-Vis, TG, DSC spectrometeries and viscometry, etc. We also performed CACM′s water treat experiment. The effects of pH values, reaction time and dose of the new floccalant on treating various of waste water have been investigated, too.

Studies on LCST of poly (N-isopropylacrylamide-co-acrylic acid-co-N-diacetone acrylamide)

Linear copolymers from N-isopropylacrylamide （NIPA）, acrylic acid （AA） and diacetone acrylamide （DAA） have been prepared. The effect of composition, ionic strength and pH on their lower critical solution temperature （LCST） has been investigated.

A Temperature-sensitive Hydrogel Refolding System: Preparation of Poly(N-isopropyl acrylamide) and Its Application in Lysozyme Refolding

Temperature-sensitive hydrogel—poly(N-isopropyl acrylamide) (PNIPA) was prepared and applied to protein refolding. PNIPA gel disks and gel particles were synthesized by the solution polymerization and inverse suspension polymerization respectively. The swelling kinetics of the gels was also studied. With these prepared PNIPA gels, the model protein lysozyme was renatured. Within 24h, PNIPA gel disks improved the yield of lysozyme activity by 49.3% from 3375.2U·mg^-1 to 5038.8U·mg^-1. With the addition of faster response PNIPA gel beads, the total lysozyme activity recovery was about 68.98% in 3h, as compared with 42.03% by simple batch dilution. The novel refolding system with PNIPA enables efficient refolding especially at high protein concentrations. Discussion about the mechanism revealed that when PNIPA gels were added into the refolding buffer, the hydrophobic interactions between denatured proteins and polymer gels could prevent the aggregation of refolding intermediates, thus enhanced the protein renaturation.

PHOTO-INDUCED GRAFT POLYMERIZATION OF ACRYLAMIDE ON POLYPROPYLENE MEMBRANE SURFACE IN THE PRESENCE OF DIBENZYL TRITHIOCARBONATE

Ultraviolet （UV）-induced graft polymerization of acrylamide （AAm） on polypropylene substrates was successfully conducted using dibenzyl trithiocarbonate （DBTTC） as photoinitiator. It was confirmed by chemical analysis and surface morphology observation with attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. A possible mechanism for this graft process was presented, which suggested that, under UV irradiation, the C： S bond in DBTTC could split and abstract a hydrogen from the polypropylene surface and a surface free radical was then formed, and initiated the graft polymerization of AAm.

Poly (Acrylamide-co-Acrylic Acid) Hydrogel Induced by Glow-Discharge Electrolysis Plasma and Its Adsorption Properties for Cationic Dyes

In this paper, poly （acrylamide-co-acrylic acid） （P（AM-co-AA）） hydrogel was pre- pared in an aqueous solution by using glow-discharge electrolysis plasma （GDEP） induced copoly- merization of acrylamide （AM） and acrylic acid （AA）, in which N,N＇-methylenebisacrylamide （MBA） was used as a crosslinker. A mechanism for the synthesis of P（AM-co-AA） hydrogel was proposed. To optimize the synthesis condition, the following parameters were examined in detail： the discharge voltage, discharge time, the content of the crosslinker, and the mass ratio of AM to AA. The results showed that the optimum pH range for cationic dyes removal was found to be 5.0-10.0. The P（AM-co-AA） hydrogel exhibits a very high adsorption potential and the ex- perimental adsorption capacities for Crystal violet （CV） and Methylene blue （MB） were 2974.3 mg/g and 2303.6 mg/g, respectively. The adsorption process follows a pseudo-second-order kinetic model. In addition, the adsorption mechanism of P（AM-co-AA） hydrogel for cationic dyes was also discussed.

Radiation graft of acrylamide onto polyethylene separators for lithium-ion batteries

To improve the affinity between separators and electrolyte in lithium-ion battery,microporous polyethylene(PE) separator was grafted of polyacrylamide(PAAm) by radiation.Chemical structure of the PAAmgrafted PE separators(denoted as PE-g-PAAm) was characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Properties of the pristine PE and PE-g-PAAm were tested by scanning electron microscope,liquid electrolyte uptake and lithium-ion conductivity.Electrochemical performances of the grafted PE separators(up to 0.76 × 10^(-3) S/cm of ionic conductivity at room temperature) were much better than pristine PE,and performance of the battery with the grafted separator behaved better than with the virgin PE separator,under the same condition(assembled in Ar-filled glove box).

Determination of Residual Acrylamide in Medical Polyacrylamide Hydrogel by High Performance Liquid Chromatography tandem Mass Spectroscopy

Objective To determine residual acrylamide in medical polyacrylamide hydrogel by high performance liquid chromatography tandem mass spectroscopy （HPLC-MS）. Methods After 13C3 labeled acrylamide was added, the sample was extracted with water and then cleaned up with ExtrelutTM 20. The polyacrylamide hydrogel sample and 20 clinical cases were analyzed by HPLC-MS/MS and isotope dilution quantifying technique in selected reaction monitoring （SRM） mode. Results Acrylamide was separated from polyacrylamide hydrogel. The concentration of acrylamide in polyacrylamide hydrogel ranged from 3.9×10^-9 to 3.1×10^- 8g/L in the 20 clinical cases. The peak area was favorable linear and the range was up to 3 000 μg/L. The recovery rate was 103.1% with a relative standard deviation （RSD） of 6.20%, when the mark level was 50 lag/L. Conelusion HPLC-MS is a rapid, accurate, and sensitive method for the determination of residual acrylamide in medical polyacrylamide hydrogel.

¹³C NMR and Raman Studies of Fullerene-Based Poly (Acrylamides)

A new classification of the different types of fullerene-containing polymers is presented according to their different properties and applications they exhibit in a variety of fields. 13C NMR and Raman studies of a series of polymeric samples of fullerene-grafted poly (acrylamide), which were prepared by systematic variation of concentration of fullerene and acrylamide, are described. 13C NMR spectral analysis of the polymeric samples showed a peak for fullerene at 143 δppm and for poly (acrylamide) between 170 and 180 δppm and Raman spectral analysis of the poly-meric samples gave the Raman band for fullerene between 1470 cm-1 and poly (acrylamide) at 2800 cm-1. The Tg value, obtained from DSC results, showed a high glass transition temperature at 100.94°C revealing the presence of fullerene in the polymeric matrix. TGA analysis shows that polymer is thermally stable up to 340°C.

Research on the Graft Copolymerization of EH-lignin with acrylamide

Lignin isolated from enzymatic hydrolyzed corn-stalks (EH-lignin) is a renewable natural polymer noted for its versatility and applicability in a vari-ety of uses. Graft copolymerization of EH-lignin with acrylamide (AM) and the application of this copolymer as a flocculant in dye wastewater treatment were studied in this article. The influ-ences of some factors on yield of copolymer and the grafting ratio were investigated and the structure of EH-lignin/AM graft copolymer was characterized by FT-IR. According to the yield and the grafting ratio, the optimum conditions for graft copolymerization were as follows: initiator K2S2O8-Na2S2O3 with a quantity 3 wt% of EH-lignin, mass ratio of AM to EH-lignin was 2~3, reaction time 4h and temperature at 50℃. It was found that the absorption capacity of graft copolymer to two azo-dyes was enhanced with the increase of grafting ratio. Furthermore, the residue concen-tration of EH-lignin/AM graft copolymer remained in the supernatant after flocculation was much lower than that of pure EH-lignin.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

Synthesis and characterization of Ce_(0.8)Sm_(0.2)O_(1.9) nanopowders using an acrylamide polymerization process

Ce0.8Sm0.2O1.9(SDC) nanopowders were synthesized by an acrylamide polymerization process.The XRD results showed that SDC powders prepared at 700 °C possessed a cubic fluorite structure.Transmission electron microscopy(TEM) indicated that the particle sizes of powders were in the range of 10-15 nm.A 98.3% of theoretical density was obtained when the SDC pellets were sintered at 1350 °C for 5 h,indicating that the powders had good sinterability.The conductivity of the sintered SDC ceramics was 0.019 S/cm at 6...

Preparation of Nanocrystalline Tin Dioxide Particles via the Acrylamide Polymerization Process

We report simple acrylamide polymerization process to prepare nanocrystalline tin dioxide(SnO_2) particles.A small amount of the so-called premix solution(monofunctional acrylamide and difunctional N,N'-methylenebisacrylamide) was mixed with the aqueous solution of Sn^(4+) in certain proportion,and a few drops of ammonium persulfate solution were added as initiator.When homogenized by magnetic stirring and heated to about 70℃,the mixed solution became a gel.This hydrous gel was directly decomposed by thermal treatment,resulting in obtaining rutile crystalline SnO_2 particles with a narrow size distribution typically in the range of 20 nm～40 nm.

Rheological behavior of ZnO suspension with thermosensitive poly(N-isopropylacrylamide) for colloidal processing of ceramics

Novel colloidal processing using thermosensitive poly（N-isopropylacrylamide） （PNIPAM） as a coagulating agent has beendeveloped to prepare complex-shaped ceramic components. In this work, the properties of PNIPAM aqueous solutions and therheological behavior of ZnO suspensions with PNIPAM were investigated. The results show that the PNIPAM solutions exhibitobvious thermosensitivity and its transition temperature is around 32℃. When the temperature is above 40℃ （Tc, the criticaltransition temperature of thermosensitive suspension）, the 50% ZnO （volume fraction） suspension with 8 mg/mL PNIPAM has asharp increase in viscosity and reaches up to 11.49 Pa·s at 50℃, displaying strong elasticity. The main reasons are the increase ofeffective volume fraction attributed to precipitation of PNIPAM segments and the flocculation between ZnO powder particles. Inaddition, the maximum solid loading （volume fraction） at 20 ℃ is higher than that at 40℃, which proves that the phase transition ofPNIPAM can induce the flocculation of suspension.

SYNTHESIS OF POLYMERIC β-CYCLODEXTRIN SUPPORTED BY CROSSLINKED POLY(ACRYLAMIDE-co-VINYLAMINE)AND ITS CATALYSIS OF THE HYDROLYSIS OF p-NITROPHENYL ACETATE

Polymeric β-cyclodextrin (β-CD) supported by crosslinked poly(acrylamide-co-vinylamine) was synthesized as anartificial analog of hydrolytic enzyme and its catalysis of the hydrolysis of p-nitrophenyl acetate (p-NPA) was theninvestigated. The result showed that the polymer-supported β-CD could accelerate the hydrolytic reaction of p-NPA morequickly than β-CD itself and crosslinked poly(acrylamide-co-vinylamine) alone. The acceleration rate of the polymer-supported β-CD was about 10 times as fast as that of free β-CD in 0.01 mol/L phosphate buffer (pH 7.4) containing 32%DMSO at 37±0.1℃ when the molar amount of β-CD units in the polymer was equal to that of free β-CD in the experiments.The enhanced acceleration of thc polymer-supported β-CD should be ascribed to the cooperative contribution of theinclusion effect of β-CD ring and the nucleophilic effect of amino groups on the polymeric support.

Molecular Dynamics Study of Interaction between Acrylamide Copolymers and Alumina Crystal

Four acrylamide polymer flocculants, anionic polyacrylamide P（AA-co-AM）, cationic poly- acrylamide P（DMB-co-AM）, nonionic polyacrylamide P（AM）, and hydrophobical polyacry- lamide P（OA-co-AM） have been prepared by copolymerizing with acrylic acid, cationic monomer dimethylethyl （acryloxyethyl） ammonium bromide （DMB） and hydrophobical monomer octadecyl acrylate with acrylamide. The interactions between the flocculants with the （012） surface of alumina crystal （A1203） have been simulated by molecular dynamics method. All the polymers can bind tightly with A1203 crystal, the interaction between the O of polymers and A1 of the （012） surface of A1203 is significantly strong. The order of binding energy is as follows： P（DMB-co-AM）〉P（OA-co-AM）〉P（AA-co-AM）〉P（AM）, implying a better flocculation performance of P（DMB-co-AM） than the others. Analy- sis indicates that binding energy is mainly determined by Coulomb interaction. Bonds are found between the O atoms of the polymers and the A1 atoms of A1203. The poly- mers＇ structures deform when they combine with A1203 crystal, but the deformation en- ergies are low and far less than non-bonding energies. Flocculation experiments in sus- pension medium of l%Kaolin show a transmittancy of 90.8% for 6 mg/L P（DMB-co-AM） and 73.0% for P（AM）. The sequence of flocculation performance of four polymers is P（DMB-co-AM）〉P（OA-co-AM）〉P（AA-co-AM）〉P（AM）, which is in excellent agreement with the simulation results of binding energy.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL POLYMER ELECTROLYTE BASED ON ACRYLONITRILE/N-[4-(AMINOSULFONYL)PHENYL]ACRYLAMIDE COPOLYMERS

Acrylonitrile/N-[4-（aminosulfonyl）phenyl]acrylamide （AN/ASPAA） copolymers were synthesized and used as a host of lithium ion conducting electrolytes. The composition, molecular weight and molecular weight distribution of AN/ASPAA copolymers were determined, and the influence of copolymer composition on the glass temperature of AN/ASPAA copolymers and the ion conductivity of electrolytes were investigated. The molecular weights of AN/ASPAA copolymers were lower than those of AN and ASPAA homopolymers due to the cross-termination reaction. The glass temperatures of AN/ASPAA copolymers increased as the molar fraction of ASPAA units in copolymers increased. The lithium ion conductivities of the polymer electrolytes increased initially as the molar fraction of ASPAA units in copolymers increased, and a maximum conductivity was achieved when the molar fraction of ASPAA in the copolymer was 16.8%.