SCIENTIFIC PRINCIPLES FOR MODIFICATION OF WATER-SOLUBLE POLYMERS. FORMATION OF MACROMOLECULAR COMPLEXES

The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.

Fabricating a reactive surface on the fibroin film by a room-temperature plasma jet array for biomolecule immobilization

A simple dielectric barrier discharge（DBD） jet array was designed with a liquid electrode and helium gas.The characteristics of the jet array discharge and the preliminary polymerization with acrylic acid（AA） monomer were presented.The plasma reactor can produce a cold jet array with a gas temperature lower than 315 K,using an applied discharge power between 6 W and 30 W（V dis × I dis）.A silk fibroin film（SFF） was modified using the jet array and AA monomer,and the treated SFF samples were characterized by atomic force microscopy（AFM）,scanning electron microscopy（SEM）,Fourier transform infrared spectroscopy（FTIR）,and contact angle（CA）.The deposition rate of the poly acrylic acid（PAA） was able to reach 300 nm/min,and the surface roughness and energy increased with the AA flow rate.The FTIR results indicate that the modified SFF had more carboxyl groups（-COOH） than the original SFF.This latter characteristic allowed the modified SFF to immobilize more quantities of antimicrobial peptide（AP,LL-37） which inhibited the Escherichia coli（E.Coli） effectively.

Preparation and Characterization of the Modified Polyvinylidene Fluoride (PVDF) Hollow Fibre Microfiltration Membrane

A novel thermally induced graft polymerization technique was used to modify a polyvinylidene fluoride （PVDF） hollow fibre microfiltration membrane. An artificial neural network （ANN） was applied to optimize the prepared condition of the membrane. The optimized dosing of acrylic acid （AA）, acrylamide （AM）, N, N＇- methylenebisacrylamide （NMBA） and potassium persulphate （KSP） designed by ANN was that AA was 40.63 ml/L; AM acted as 6.25 g/L; NMBA was 1.72 g/L and KSP was 1.5 g/L, respectively. The thermal stability of the PVDF modified hollow fibre membrane （PVDF-PAA） was investigated by thermogravimetric （TG） and differential scanning calorimetry （DSC） analysis. The polycrystallinity of the PVDF-PAA membrane was evaluated by X-ray diffraction （XRD） analysis. The complex formation of the modified membrane was ascertained by Fourier transform infrared spectroscopy （FTIR）. The morphology of the PVDF-PAA membrane was studied by environmental scanning electron microscopy （ESEM）. The surface compositions of the membrane were analyzed by X-ray photoelectron spectroscopy （XPS）. The adsorption capacity of Cu^2＋ ion on the PVDF-PAA hollow fibre membrane was also investigated.

Polyacrylate modified Cu electrode for selective electrochemical CO_(2) reduction towards multicarbon products

Highly selective production of value-added multicarbon(C^(2+))products via electrochemical CO_(2) reduction reaction(eCO_(2)RR)on polycrystalline copper(Cu)remains challenging.Herein,the facile surface modification using poly(α-ethyl cyanoacrylate)(PECA)is presented to greatly enhance the C^(2+)selectivity for eCO_(2)RR over polycrystalline Cu,with Faradaic efficiency(FE)towards C^(2+)products increased from30.1%for the Cu electrode to 72.6%for the obtained Cu-PECA electrode at-1.1 V vs.reversible hydrogen electrode(RHE).Given the well-determined FEs towards C^(2+)products,the partial current densities for C^(2+)production could be estimated to be-145.4 mA cm~(-2)for the Cu-PECA electrode at-0.9 V vs.RHE in a homemade flow cell.In-situ spectral characterizations and theoretical calculations reveal that PECA featured with electron-accepting-C≡N and-COOR groups decorated onto the Cu electrode could inhibit the adsorption of^(*)H intermediates and stabilize the^(*)CO intermediates,given the redistributed interfacial electron density and the raised energy level of d-band center(E_(d))of Cu active sites,thus facilitating the C-C coupling and then the C^(2+)selective production.This study is believed to be guidable to the modification of electrocatalysts and electrodes with polymers to steer the surface adsorption behaviors of reaction intermediates to realize practical eCO_(2)RR towards value-added C^(2+)products with high activity and selectivity.

Ring-Opening Polymerization of a Benzyl-Protected Cyclic Ester towards Functional Aliphatic Polyester

Monomer design strategy has become a powerful tool to access polymers with desired and diverse functionalities. Here, we designed a novel monomer 2-((benzyloxy)methyl)-1,4-oxathiepan-7-one (BTO) via installing a benzyl ether side chain to the structure of 1,4-oxathiepan-7-one (OTO). The ring-opening polymerization of BTO with Zn1 as the catalyst demonstrated the characteristics of living polymerization with turnover frequency (TOF) up to 2520 h^(−1). With a [BTO]_(0)/[Zn1]_(0)/[I]_(0) feed ratio of 2000/2/1, polymer with high number-average molecular weight (Mn = 536 kDa) and narrow dispersity (Ð = 1.06) was obtained. The produced polymer with a glass transition temperature of -17℃ behaved as an elastomer at room temperature. Consequently, the monomer BTO was copolymerized with _(L)-LA to modulate the mechanical properties of P(L-LA). When the BTO content is 10%, the copolymer exhibits excellent strength (24 MPa) and elongation at break (270%), affording a crystalline, hard, and tough plastic material that combines the high ductility of P(BTO) and the high modulus of P(_(L)-LA). In addition, the oxidation of P(BTO) to P(BTO)-SO_(2) led to an improvement of T_(g) from -17℃ to 38℃. Debenzylation of P(BTO)-SO_(2) afforded P(BTO)-SO_(2)-OH containing free hydroxyl groups. Ultimately, P(BTO) could be hydrolyzed under a base condition to recover the corresponding hydroxyl acid intermediate, which could be used to prepare the monomer again and complete the closed-loop from monomer to polymer to monomer.

Surface Modification of Polypropylene by Ethylene Plasma and Its Induced β-Form in Polypropylene

This study aims to investigate the chemical structure and morphology of plasmapolymers produced by deposition of ethylene on the surface of polypropylene. The deposition films（sediments） of ethylene plasma on the surface of polypropylene are nonuniform, and the characterization results indicate the existence of hydroxyl groups and aldehyde（or ketone） groups in the sediments. The sediment of ethylene plasma on the polypropylene surface could induce the growth of β-form crystals in the surface layer of polypropylene.

Photo-grafting Poly(acrylic acid) onto Poly(lactic acid) Chains in Solution

Poly(lactic acid)(PLA)is one of the most important bio-plastics,and chemical modification of the already-polymerized poly(lactic acid)chains may enable optimization of its material properties and expand its application areas.In this study,we demonstrated that poly(lactic acid)can be readily dissolved in acrylic acid at room temperature,and acrylic acid can be graft-polymerized onto poly(lactic acid)chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet(UV)irradiation.Similar photo-grafting polymerization of acrylic acid(PAA)has only been studied before in the surface modification of polymer films.The graft ratio could be controlled by various reaction parameters,including irradiation time,benzophenone content,and monomer/polymer ratios.This photo-grafting reaction resulted in high graft ratio(graft ratio PAA/PLA up to 180%)without formation of homopolymers of acrylic acid.When the PAA/PLA graft ratio was higher than 100%,the resulting PLA-g-PAA polymer was found dispersible in water.The pros and cons of the photo-grafting reaction were also discussed.

Preparation of a Crosslinked Chitosan Coated Calcium Sulfate Whisker and Its Reinforcement in Polyvinyl Chloride

A calcium sulfate whisker （CSW） coated with glutaraldehyde crosslinked chitosan （GACS） was prepared to reinforce polyvinyl chloride （PVC） in this study. The results show that the optimum concentration of both chitosan （CS） and glutaraldehyde （GA） is 0.05 wt%. The tensile strength, impact strength, flexural modulus and vicat softening temperature of the PVC composite with 12 wt% of modified CSW are in- creased by 1 Z5%, 40.4%, 0.8% and 3.8% compared with those of the PVC composite with 12 wt~ of unmodified CSW, and by 2.9%, 42.4%, 2Z1% and 6.8% compared with those of pure PVC, respectively. The dynamic mechanical analysis results indicate that the modified CSW/PVC composite exhibits much higher storage modulus and glass transition temperature than those of unmodified CSW/PVC composite and pure PVC. In addition, the modified CSW/PVC composite also demonstrates good thermal properties with a high rapidest decomposition temperature （Trvd） and char residue. The scanning electron microscopy images of tensile-fractured surfaces show that the modified CSW has a strong interfacial adhesion with PVC matrix.