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.

Hydrogel of biodegradable cellulose derivatives. I. Radiation-induced crosslinking of CMC

Radiation crosslinking of carboxymethylcellulose (CMC) with a degree of substitution (DS) from 0.7 to 2.2 was the subject of the current investigation. CMC was irradiated in solid-state and aqueous solutions at various irradiation doses. The DS and the concentration of the aqueous solution had a remarkable affect on the crosslinking of CMC. Irradiation of CMC, even with a high DS, 2.2 in solid state, and a low DS, 0.7 in 10% aqueous solution, resulted in degradation. However, it was found that irradiation of CMC with a relatively high DS, 1.32, led to crosslinking in a 5% aqueous solution, and 20% CMC gave the highest gel fraction. CMC with a DS of 2.2 induced higher crosslinking than that with a DS of 1.32 at lower doses with the same concentration. Hence, it was apparent that a high DS and a high concentration in an aqueous solution were favorable for high crosslinking of CMC. It is assumed that; high radiation crosslinking of CMC was induced by the increased mobility of its molecules in water and by the formation of CMC radicals from the abstraction of H atoms from macromolecules in the intermediate products of water radiolysis. A preliminary biodegradation study confirmed that crosslinked CMC hydrogel can be digested by a cellulase enzyme. (C) 2000 John Wiley & Sons, Inc.

Amperometric enzyme electrode for the determination of hydrogen peroxide based on sol-gel/hydrogel composite film

A new type of organic-inorganic composite material was prepared by sol-gel method, and a peroxidase biosensor was fabricated by simply dropping sor-gel-peroxidase mixture onto glassy carbon electrode surface. The sol-gel composite film and enzyme membrane were characterized by Fourier-transform infrared (FT-IR) spectroscopy and EQCM, the electrochemical behavior of the biosensor was studied with potassium hexacyanoferrate(II) as a mediator, and the effects of pH and operating potential were explored for optimum analytical performance by using amperometric method. The response time of the biosensor was about 10 s; the linear range was up to 3.4 mM with a detection limit of 5 x 10(-7) M. The sensor also exhibited high sensitivity (15 mu A mM(-1)) and good long-term stability. In addition, the performance of the biosensor was investigated using flow injection analysis (FIA), and the determination of hydrogen peroxide in real samples was discussed. (C)2000 Elsevier Science B.V. All rights reserved.

Amperometric biosensor for hydrogen peroxide based on sol-gel/hydrogel composite thin film

A reagentless amperometric hydrogen peroxide biosensor was developed. Horseradish peroxidase (HRP) was immobilized in a novel sol-gel organic-inorganic hybrid matrix that is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP). Tetrathiafulvalene (TTF) was employed as a mediator and could lower the operating potential to -50 mV (versus Ag/AgCl). The sensor achieved 95% of the steady-state current in 15 s. Linear calibration for hydrogen peroxide was up to 1.3 mM with the detection limit of 2.5 x 10(-7)M. The enzyme electrode retained about 94% of its initial activity after 30 days of storage in a dry state at 4 degreesC.

Hydrazines probe of interaction of horseradish peroxidase with cryo-hydrogel

The interaction between horseradish peroxidase (HRP) and the cryo-hydrogel was probed by using hydrazines which show high specificity of the reaction of the edge in the prosthetic heme of horseradish peroxidase. For comparison, the interaction of hydrazine with the horseradish peroxidase adsorbed on graphite electrode was also carried out by using steady-state response of the enzyme electrode and cyclic voltammetry. In order to obtain a proper explanation of the kinetic parameters for the enzymatic reaction, the theoretical expressions of I-max and K-M' in the Michaelis-Menten equation for the experimental system were provided. (C) 1997 Elsevier Science B.V.

Cyro-hydrogel for the construction of a tyrosinase-based biosensor

A new immobilization method for construction of a tyrosinase based biosensor is described. A simple physical freezing technique was adopted for preparation. The immobilized enzyme yields specific activities that are more than 22% of the soluble enzyme. The enzyme electrode can be stored in dry state for more than three months without any loss of activity. The biosensor was applied to the determination of several phenols and o-diphenols. The lowest detect limit is 0.02 mu mol/1 and the linear range was 1.0 X 10(-7)-1.0 X 10(-4) mol/1 for catechol. The kinetic parameters have also been calculated.

The direct electrochemistry of cryo-hydrogel immobilized myoglobin at a glassy carbon electrode

A cryo-hydrogel membrane (CHM) immobilized at a glassy carbon (GC) electrode is reported for the direct electron transfer of redox proteins. The most attractive characteristics of this CHM were its hydrophilic micro-environment for incorporated proteins to retain their activities, its high ability for protection against interference of denatured and adsorbed proteins at the electrode, its potential applications for various proteins or enzymes, as well as its high mechanical strength and thermal stability. A clear well developed and stable redox wave was obtained for commercially available horse heart myoglobin without further purification, giving a peak to peak separation Delta E(p) = 93 mV at 5 mV s(-1) and the formal electrode potential E(0)' = -0.158 V (vs. Ag/AgCl). The formal heterogeneous electron transfer rate constant was calculated as k(0)' = 5.7 X 10(-4) cm s(-1) at pH 6.5, showing rapid electron transfer was achieved. The pH controlled conformational equilibria, acid state --> natural state --> basic I state --> basic II state, of myoglobin at the CHM GC electrode in the pH range 0-13.8 were also observed and are discussed in detail.

VOLTAMMETRY OF CYTOCHROME-C ENTRAPPED IN HYDROGEL MEMBRANE ON GRAPHITE ELECTRODE

The voltammetric behavior of cytochrome c entrapped in hydrogel membranes at paraffin wax-impregnated spectroscopic graphite electrodes (WISGE) was studied in this paper. A pair of well-defined peaks appeared at +70 mV (vs. Ag/AgCl). Beside these two peaks, another pair of peaks emerged at around +225 mV. Further investigations suggested that at least three states of cytochrome c existed in the membranes due to the special structure of the hydrogel. The native conformation of cytochrome c molecules was stabilized by the hydrophilic environment that was formed by the hydroxyl structure of the membranes and facilitated the cytochrome c electron transfer reaction at +70 mV. The molecules directly adsorbed on the surface of the graphite electrode were responsible for the redox peaks at around +225 mV. Whether the adsorption peaks were detectable or not was related to the thickness of membranes and the pre-retaining time before the formation of membranes.

A cryo-hydrogel immobilized protein electrode for direct electron transfer of myoglobin

The direct electron transfer process of horse heart myoglobin, which was immobilized into a new type of cryo-hydrogel membrane on a glassy carbon electrode surface, was studied and the characteristics of this cryo-hydrogel immobilized protein electrode were discussed.

水凝胶的制备及壳聚糖的改性和应用

水凝胶用作创口敷料时有很多的优点。壳聚糖是天然的阳离子多糖,已经在很多领域得到了应用。我们制备了几种具有抑菌能力的水凝胶敷料，同时利用可生物降解聚酯和多聚肽对壳聚糖进行了修饰，得到了一些新的结果。 本论文的工作主要包括以下两部分： 一.含有抗生素或纳米银粒子的水凝胶的制备和表征。 1．载药聚乙烯醇/聚乙烯基吡咯烷酮/壳聚糖（PVA-PVP-Chitosan）复合水凝胶的制备和抑菌性能评价。采用循环冷冻－熔融与辐射交联相结合的方法制备出了PVA-PVP-chitosan复合水凝胶，测定了凝胶的溶胀率、凝胶含量、力学强度和结晶性能，并考察了所用壳聚糖分子量，冷冻－熔融循环处理次数和辐射剂量对凝胶性能的影响。然后通过溶胀法将抗生素（环丙沙星）和壳寡糖载入水凝胶中，考察了它们的体外释放行为。同时利用琼脂糖平板法检验了载药凝胶的抑菌能力，结果表明它们可以有效抑制革兰氏阳性菌和革兰氏阴性菌的繁殖和生长。 2．含纳米银-PVA-PVP水凝胶的制备和抑菌性能评价。通过循环冷冻－熔融法制备了含银的PVA-PVP复合水凝胶。以含银的PVA-PVP复合膜为模型，利用DSC、红外光谱、紫外－可见光谱和X-射线衍射考察了掺入的纳米银与PVA-PVP网络的相互作用。利用扫描电镜观察了PVA-PVP凝胶的网络结构和银纳米粒子在网络中的分布。利用琼脂糖平板法和LB肉汤法对含银PVA-PVP凝胶的抑菌性能进行了评价，结果证明这种水凝胶可以有效抑制大肠杆菌和金黄色葡萄球菌的生长和繁殖。 二. 壳聚糖的改性和应用。 1．发展了一种制备聚ε－己内酯（PCL）接枝壳聚糖共聚物的新方法，并且由合成的接枝共聚物在水中自组装得到纳米粒子。利用DLS、AFM和SEM对纳米粒子进行了表征，结果显示制备的纳米粒子为圆球形或椭圆形。利用茚三酮显色法准确测定了活性胺基的含量，发现纳米粒子表面活性胺基的数量可以通过改变PCL接枝度进行调节。 2．由6-O-三苯甲基壳聚糖引发赖氨酸NCA的开环聚合得到了聚赖氨酸（PLL）接枝壳聚糖阳离子共聚物。利用红外光谱、核磁共振和GPC对接枝共聚物的分子结构和分子量进行了表征。通过动态光散射测量发现接枝共聚物可以和小牛胸腺DNA形成粒径在100~340 nm之间的复合物。凝胶阻滞电泳证明接枝共聚物对质粒DNA的结合和保护能力要优于壳聚糖。细胞转染实验证明接枝共聚物对293T和Hela细胞的转染效率要远远高于壳聚糖原料和PLL。同时，接枝共聚物的转染效率对PLL的聚合度有明显的依赖性，增加PLL聚合度有助于提高接枝共聚物的转染效率。这种新型的阳离子接枝共聚物有望用作高效基因载体。

Preparation of Mn substituted La-hexaaluminate catalysts by using supercritical drying

LaMnxAl12-xO19 catalysts were prepared from NH4OH and metal nitrates solutions. Supercritical drying (SCD) and conventional oven drying (CD) methods were used to extract the water in the hydrogel. The effects of drying methods on properties of the catalysts were investigated by means of TEM, N-2-adsorption, thermogravimetry (TG)-differential thermal analysis (DTA) and X-ray diffraction. SCD method is beneficial to maintain high surface area and improving catalytic activity for methane combustion of the catalyst. The specific surface area and pore volume of LaMn1Al11O19 catalyst prepared by SCD method are 28 m(2)/g and 0.23 cm(3)/g, respectively, and the ignition of methane could be carried out at 450degreesC. However, those of the CD catalyst prepared from the same precursor are 15 m(2)/g, 0.11 cm(3)/g and 530 degreesC, respectively. Suitable Mn content (0 less than or equal to x less than or equal to 2) could promote the formation of LaMnAl11O19 hexaaluminate, while further addition of Mn (2 less than or equal to x less than or equal to 6) cause the formation of LaMnO3. (C) 2003 Elsevier B.V All rights reserved.

Synthesis and characterization of a novel two-component organogelator based on ion-bonded discotic complex

A novel ion-bonded discotic complex was prepared from 2,3,6,7,10,11-hexakis(N,N-dimethylaminopropylaminocarbonylmethoxy)triphenylene (HDTP) and 4'-dodecyloxybiphenyl-4-carboxylic acid (DBC) by ionic self-assembly (ISA) route and characterized by Fourier transform infrared (FTIR) spectrum. We found that the complex can self-assemble into stable gels in aromatic hydrocarbons. Nanofibers with diameters of 50-130 nm were observed in the gels by transmission electron micrograph (TEM).

Ultrasound-promoted chiral fluorescent organogel

In this paper, we have described a chiral binaphthyl-based fluorescent organogel. Very interestingly, similar to sonocrystallisation of organics, ultrasound can promote the gelation while it cannot occur spontaneously at relatively high temperature or low concentration. The fluorescence enhancement of the gel obtained via ultrasound irradiation is observed. In solution there exist rapid dynamic equilibria between (S)-1 oligomers. The association interactions both between gelator molecules and between solvent and gelator molecules could together effect the helical growth of distorted (S)-1 nanocrystals.

Recent developments in intelligent biomedical polymers

Intelligent polymers or stimuli-responsive polymers may exhibit distinct transitions in physical-chemical properties, including conformation, polarity, phase structure and chemical composition in response to changes in environmental stimuli. Due to their unique 'intelligent' characteristics, stimuli-sensitive polymers have found a wide variety of applications in biomedical and nanotechnological fields. This review focuses on the recent developments in biomedical application of intelligent polymer systems, such as intelligent hydrogel systems, intelligent drug delivery systems and intelligent molecular recognition systems. Also, the possible future directions for the application of these intelligent polymer systems in the biomedical field are presented.