Preparation and Characterization of Interpenetration Polymer Network Films Based on Poly(vinyl alcohol) and Poly(acrylic acid) for Drug Delivery

A series of full interpenetrating polymer network (full-IPN) films of poly(acrylic acid) (PAA)/poly (vinyl alcohol) (PVA) were prepared by radical solution polymerization and sequential IPN technology. Attenuated total reflectance-Fourier transform infrared spectroscopy, swelling properties, mechanical properties, morphology, and glass transition temperature of the films were investigated. FTIR spectra analysis showed that new interaction hydrogen bonds between PVA and PAA were formed. Swelling property of the films in distilled water and different pH buffer solution was studied. Swelling ratio increased with increasing PAA content of IPN films in all media, and swelling ratio decreased with increasing PVA crosslink degree. Tensile strength and elongation at break related not only to the constitution of IPNs but also to the swelling ratio of IPNs.

遥爪丁腈共聚物的增韧环氧－聚氨酯IPN及PVC共混物的合成与表征

Ⅰ. 增韧环氧／聚氨酯互穿网络聚合物的合成与表征 用部分环氧树脂与丁腈羧反应，进行端基转化，制得端环氧基丁腈－环氧共聚物与环氧树脂的混合物，经叔胺固化后，得到增韧环氧（TEpx）。制备了两种IPN体系，体系1为增韧环氧／蓖麻油聚氨酯IPN，体系2为增韧环氧／聚醚聚氨酯IPN。用红外光谱研究了动力学，研究结果是，对于体系1，－OH基与－NCO基的反应速度大于环氧基的聚合速度，因此，IPN体系中，PU网络的形成比环氧网络快。环氧上的－OH基与蓖麻油上的羟基相似。同属伸羟基，它也会与－NCO基反应，因此，所形成的IPN的两网络间，存在着一定程度的化学交联。在增韧环氧的分子结构中，含有丁腈羧低聚物链段，使得增韧环氧与蓖麻油聚氨酯的相容性较好，该因素对这种IPN形态结构的形成，是很重要的，从动态力学性能的测试结果，能说明这个问题，即玻璃化转变峰很宽，在一定组成时，半峰宽几乎达100 ℃。对于体系2，聚氨酯相起反应的羟基是伯羟基，它与－NCO基的反应速度比环氧中的羟基与－NCO基的反应速度大得多。此外，体系中的两组分，即增韧环氧与聚醚聚氨酯的相容性不好，反应速度的差别与相容性的差别，均将导致反应体系中相分离程度的增大。这在tanZ-T曲线上表现得很明显，出现了两个相距甚远的玻璃化转变峰。利用透射电子显微镜对两个IPN体系进行了形态观察，这些IPN具有特殊的结构，既有增韧环氧所存在的两相结构，又有IPN的两相结构。Ⅱ. 聚氯乙烯－丁腈羟低聚物共混物的合成与表征 制备了高聚物（PVC）－低聚物（HTBN）共混物，研究了该共混物的力学性能，阻尼性能及形态结构。研究结果表明，在HTBN中，丙烯腈含量较高时，随着HTBN加入量的增加，PVC的阻尼峰均有不同程度的加宽加高。在力学性能方面，共混物的抗张强度、伸长率也随低聚物中丙烯腈含量的高低而变化，丙烯腈含量较高时（25％，36％），随HTBN加入量的增加，性能变化不大，而丙烯腈含量较低时（15％，5％），当HTBN的加入达一定量时，性能发生突降。这些现象的出现，主要与相容性有关，HTBN中丙烯腈含量高，极性大，与PVC混溶性好，因而阻尼性能、力学性能均好。而HTBN中丙烯腈含量低，与PVC之间的粘合力不好，即混溶性不好，因而共混物性能不好。由TEM照片看，该共混体系的形态结构为细胞状结构，细胞内存在着界面模糊的两相结构，在低丙烯腈含量（15％）时，存在着部分界面清晰的两相结构，形态观察的结果与性能测定的结果一致。

Spontaneous volume transition of polyampholyte nanocomposite hydrogels based on pure electrostatic interaction

A circular system is employed in this paper to investigate the swelling behaviors of polyampholyte hydrogels; this circular system can effectively eliminate the disturbance of various factors and keep the surrounding environment constant. It is found that there exists a spontaneous volume transition to the collapsed state of polyampholyte hydrogels, which is attributed to the overshooting effect, and the transition can occur repeatedly under certain conditions. C-13 NMR is employed to investigate the swelling behavior of polyampholyte hydrogels.

Sulphonated Tetramethyl Poly(ether ether ketone)/Epoxy/Sulphonated Phenol Novolac Semi-IPN Membranes for Direct Methanol Fuel Cells

The sulphonated phenol novolac (PNBS) which was used as a curing agent of epoxy was synthesised from phenol novolac (PN) and 1,4-butane sultone and confirmed by FTIR and H-1 NMR. The degree of sulphonation (DS) in PNBS was calculated by H-1 NMR. The semi-IPN membranes composed of sulphonated tetramethyl poly(ether ether ketone) (STMPEEK) (the value of ion exchange capacity is 2.01 meq g(-1)), epoxy (TMBP) and PNBS were successfully prepared. The semi-IPN membranes showed high thermal properties which were measured by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) With the introduction of the corss-linked TMBP/PNBS, the mechanical properties, dimensional stability, methanol resistance and oxidative stability of the membranes were improve in comparison to the pristine STMPEEK membrane.

Thermo- and pH-sensitive poly(vinylmethyl ether)/carboxymethylchitosan hydrogels crosslinked using electron beam irradiation or using glutaraldehyde as a crosslinker

BACKGROUND: Stimuli-sensitive or intelligent hydrogels have been investigated for many biomedical and pharmaceutical applications. Those hydrogels with dual sensitivity will have more extensive potential applications. The aim of the work presented was to prepare a series of thermo- and pH-sensitive hydrogels based on poly(vinylmethyl ether) (PVME) and carboxymethylchitosan (CMCS). The hydrogels were crosslinked using electron beam irradiation (EB) or using glutaraldehyde (GA) as a crosslinker at room temperature.

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of IPN aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug.

Preparation and Characterization of Nanostructured and High Transparent Hydrogel Films with pH Sensitivity and Application

Novel nanostructured, high transparent, and pH sensitive poly(2-hydroxyethyl methacrylate-co-methacryliac acid)/poly(vinyl alcohol) (P(HEMA-co-MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA-co-MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV-vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostructured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied.

Tunable Multiresponsive Methacrylic Acid Based Inverse Opal Hydrogels Prepared by Controlling the Synthesis Conditions

Methacrylic acid based inverse opal hydrogels (MIOHs) have been prepared by controlling the synthesis conditions, including cross-linker content, solvent content, and water content in solvent mixtures to explore the effect of the synthesis conditions (especially solvent content and mixture) on the response performance. Various response events (pH, solvent, ionic strength, 1,4-phenylenediamine dihydrochloride (PDA) response) have been investigated. For pH, solvent response, the same response behaviors have been observed: both the increased solvent (only ethanol) content and the enhanced water content in solvent will lead to the reduced response level of MIOHs compared to that of the increased cross-linker content. However, two different kinds of response behaviors for ionic strength response have been found by adjusting the synthesis conditions. The kinetics of pH response shows characteristics of a diffusion-limited process, and the equilibrium response time is about 20 min, which cannot be reduced by changing the synthesis conditions.

Synthesis of biodegradable thermo- and pH-responsive hydrogels for controlled drug release

Novel intelligent hydrogels composed of biodegradable and pH-sensitive poly(L-glutamic acid) (PGA) and temperature sensitive poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (PNH) were synthesized and characterized for controlled release of hydrophilic drug. The influence of pH on the equilibrium swelling ratios of the hydrogels was investigated. A higher PNH content resulted in lower equilibrium swelling ratios. Although temperature had little influence on the swelling behaviors of the hydrogels, the changes of optical transmittance of hydrogels as a function of temperature were marked, which showed that the PNH part of hydrogel exhibited hydrophobic property at temperature above the lower critical solution temperature (LCST). The biodegradation rate of the stimuli-sensitive hydrogels in the presence of enzyme was directly proportional to the PGA content. Lysozyme was chosen as a model drug and loaded into the hydrogels.

Study on the synthesis and performance of hydrogels with ionic monomers and montmorillonite

Two series of the nanocomposite hydrogels were synthesized by in-situ solution polymerization. One pre-gel solution was obtained by directly dispersing the montmorillonite (MMT) powder into aqueous monomer solution and the other pre-gel solution was obtained by mixing monomer aqueous solution and the dispersion of MMT. The structure and performance of two series of hydrogels in dry state were studied by XRD, Raman spectroscopy, TEM and Al-27 MAS NMR. Compressing test results showed that the gel strength of the hydrogels prepared by the latter method was much higher than that by the former method. When acryloyloxyethyl trimethyl ammonium chloride (DAC) was introduced into the system, hydrogels with excellent nanostructure could be synthesized. The result of Al-27 MAS NMR suggested that the chemical environment of aluminum in MMT was changed by the introduction of DAC due to the interaction between the groups of DAC and MMT layers. Thus, the combination of copolymerizing with strong polar monomers and using the dispersion of MMT were the effective ways to obtain tranocomposite hydrogel of MMT and ionic monomers. The nanostructure of the hydrogel improved the gel strength, while the swelling ratio of the hydrogel depended on synergic effects of multifunctional groups.

Preparation and antibacterial effects of PVA-PVP hydrogels containing silver nanoparticles

The poly(vinyl alcohol)/ poly(N-vinyl pyrrolidone) (PVA-PVP) hydrogels containing silver nanoparticles were prepared by repeated freezing-thawing treatment. The silver content in the solid composition was in the range of 0.1-1.0 wt %, the silver particle size was from 20 to 100 nm, and the weight ratio of PVA to PVP was 70 : 30. The influence of silver nanoparticles on the properties of PVA-PVP matrix was investigated by differential scanning calorimeter, infrared spectroscopy and UV-vis spectroscopy, using PVA-PVP films containing silver particles as a model. The morphology of freeze-dried PVA-PVP hydrogel matrix and dispersion of the silver nanoparticles in the matrix was examined by scanning electron microscopy. It was found that a three-dimensional structure was formed during the process of freezing-thawing treatment and no serious aggregation of the silver nanoparticles occurred. Water absorption properties, release of silver ions from the hydrogels and the antibacterial effects of the hydrogels against Escherichia coli and Staphylococcus aureus were examined too. It was proved that the nanosilver-containing hydrogels had an excellent antibacterial ability.