Eco-Synthesis of PVA/Chitosan Hydrogels for Biomedical Application

A drug delivery system based on physically cross-linked poly vinyl alcohol (PVA)/chitosan blend hydrogels for the release of sparfloxacin antibiotic as a model for drugs was described. Eco-synthesis in current work is based on synthesizing a hydrogel without using chemical crosslinking agents like in the conventional method. In addition all materials are used are non- toxic, safe, non-carcinogenic and can be accepted by the human body without danger. The swelling behavior was tested to be dependent on pH as temperature as well as time and number of freezing thawing cycles. The physical properties of the hydrogels, such as swelling percent, dissolution percent, gel fraction and mechanical properties was assessed. The antimicrobial activity of hydrogels having different compositions was evaluated for both gram positive and gram negative bacteria. Furthermore, the release of antibiotic from hydrogels prepared using the freeze—thawed process was studied. Results obtained disclose that the swelling percent of the hydrogels is pH- dependent and increases by increasing the chitosan percent and decreases with increasing the time and number of freezing cycle. With respect to the antimicrobial activity of the prepared hydrogels, display a positive effect for both gram positive and gram negative bacteria. Freeze-thawed hydrogels could serve as drug delivery system to release sparfloxacin in acidic medium. Indeed, the release percent of sparfloxacin relies on both pH and temperature.     

Potassium Release Kinetics and Water Retention of Controlled-Release Fertilizers Based on Chitosan Hydrogels

Controlled release fertilizer (CRF) hydrogels were prepared from poly(vinyl alcohol), poly(vinyl alcohol)/chitosan and chitosan using glutaraldehyde as a crosslinker. Intermolecular interactions of the CRF hydrogels were elucidated using FTIR. Water absorbency characteristics of the CRF hydrogels were also studied. It was found that the CRF hydrogels exhibited the equilibrium swelling ratio (SR) in the range 70–300%. The water retention of soil containing the CRF hydrogels was also examined. It was found that the CRF hydrogels increased the water retention of the soil. After 30 days, soil containing the PVA-, PVA/CS- and CS-hydrogels showed the water retention capacities of 25%, 10% and 4%, respectively. While the soil without the CRF hydrogel had already given off most of the water. The release behavior of potassium from the CRF hydrogels, both in deionized water and in soil, was investigated. In soil, the potassium release mechanism from the PVA- and PVA/CS-hydrogels were non-Fickian diffusion. On the other hand, the CS hydrogel showed, n value that was close to 1.0 corresponding to case II transport. In deionized water, all the CRF hydrogels showed small values of release exponent (n < 0.5) indicating a quasi-Fickian diffusion mechanism.     

Structure and Property of Porous Polyvinylalcohol Hydrogels for Microorganism Immobilization

The porous polyvinylalcohol (PVA) hydrogel was prepared by chemical crosslinking in the saturated boric acid solution with sodium bicarbonate (SBC) as porogen. It was found that addition of SBC decreased the mechanical strength of the gel beads, while the gel permeability was improved. The equilibrium swelling rate and the swelling rate constant k of gel beads increased significantly by addition of SBC. Most of water in PVA hydrogel was in the form of free water and freezing bound water. With increasing SBC content, the total water content of the gel increased, in which the free water content increased remarkably, due to the formation of a large number of pores, and in the meantime, n values, characterizing the mole content of non-freezing bound water, were also improved greatly, indicating of the enhancement of the interaction between PVA molecules and water molecules. SEM observation showed that by adding SBC, many pores formed on the surface and inside gels, which provided channels for microbial metabolites. Microorganism could be successfully entrapped in the porous PVA beads, and addition of SBC made COD removal rate of the gel beads increase significantly.     

Design and Characterization of PVA–Methacrylic Acid Based Smart Polymeric System for Controlled Release of Metoprolol

In the present work covalently crosslinked smart polymeric system of hydrogel based on poly vinyl alcohol (PVA) and methacrylic acid (MA) was designed by free radical polymerization with different compositions using glyoxal (40 % water solution) as crosslinker. It was observed that swelling of hydrogel had a pronounced enhancing effect on increasing the concentration of MA due to availability of more ionized carboxylic groups of MA but produced an opposite effect on increasing the concentration of glyoxal owing to less porous structure. As far as PVA is concerned, swelling did not show significant effect on increasing the concentration of PVA. Hydrophilic polymer PVA rich in hydroxyl group pertained to be highly interactive with water. It was examined that the release of metoprolol tartrate decreased with increased concentration of glyoxal, but increased with increase in concentration of MA. PVA/MA hydrogel was characterized by Fourier transform infrared spectroscopy and X-ray diffraction to study the structure and crystallinity of hydrogel respectively. Morphology was studied through scanning electron microscopy. Furthermore differential scanning calorimetry and thermogravimetric analysis were also performed to characterize thermal stability. It may be concluded that the mechanism of drug release was mainly non-Fickian diffusion.     

Crosslinked Polyacrylamide Composite Hydrogels Impregnated with Fly Ash: Synthesis,Characterization and Their Application as Fractures Sealant for High Water Producing Zones in Oil and Gas Wells

Polymeric hydrogels are designed to serve many purposes in various fields of human endeavor. Herein, crosslinked polyacrylamide (PAM) composite hydrogels impregnated with coal fly ash (CFA) were synthesized, characterized and tested as fracture sealing agents in high water producing permeable zones in petroleum industry. The concept of utilizing CFA as an inorganic additive in the matrix of hydrogel emanates from the fact that CFA constitutes majorly alumina and silica. Both chemical oxides can induce the CFA to promote the inherent properties of hydrogel. Polyethyleneimine (PEI) was chosen as the crosslinking agent. Neat PAM/PEI hydrogel and PAM/PEI–CFA hydrogels at various CFA loadings (0.5, 1 and 2 wt%) were synthesized via a transamidation reaction pathway. The developed hydrogels were characterized by hybrid rheometer, FTIR, SEM and XRD instruments. Rheological results reveal that the PAM/PEI–CFA composite hydrogels embedded with various CFA quantities were more elastic than the neat PAM/PEI hydrogel, indicating the dispersion and reinforcing effect of CFA. The functional groups of these hydrogels were confirmed by the FTIR while SEM analysis show that the surface micrographs of neat PAM/PEI hydrogel and PAM/PEI–CFA1 hydrogel were porous in several regions. In contrast, the micrographs of PAM/PEI–CFA2 and PAM/PEI–CFA3 hydrogels demonstrated dense and “net-like” structural patterns. Further, XRD analysis revealed that CFA impregnation has a significant effect on the bulk structural properties of the fabricated hydrogels. The swelling rates of these hydrogels were determined by the gravimetric method and their diffusion parameters evaluated using Fickian diffusion and Schott-order kinetic models. Efficacy of the PAM/PEI–CFA composite hydrogel as fractures sealant in oil and gas wells was conducted at a typical reservoir temperature, 90 °C, and the outcome demonstrated considerable sealing potency.     

Preparation and Properties of Chitosan–PVA Fibers Produced by Wet Spinning

Chitosan fibers were prepared by wet spinning in three stages. Initially, a polymer solution of chitosan and polyvinyl alcohol (PVA) was solidified in a mixture of potassium hydroxide and ethanol. The polymers were then crosslinked with sodium tripolyphosphate (TPP) or glutaraldehyde, and finally dried in methanol or acetone. The effect of these conditions was evaluated based on scanning electron microscopy images, water-holding capacity, and swelling and mechanical properties. The miscibility of the mixture was evaluated using Fourier Transform Infrared spectroscopy and differential scanning calorimetry. The results obtained showed that chitosan fibers containing 45% (v/v) PVA and crosslinked using TPP have properties similar to those of commercial sutures prepared using other biomaterials.     

Water Remediation: PVA-Based Magnetic Gels as Efficient Devices to Heavy Metal Removal

Scientific and technological researches are devoted to obtain materials capable of retaining different kinds of pollutants, contributing to contamination solutions. In this context, hydrogels have emerged as great candidates because of their excellent absorption properties as well as good mechanical, thermal and chemical properties. More specifically, ferrogels (magnetic gels) present the extra advantage of being easily manipulated by a permanent magnet. Here, we present the results derived from the application of ferrogels as efficient tools to extract heavy metal pollutants from wastewater samples. The gels were prepared following the method of freezing and thawing of a polyvinyl alcohol aqueous solution with magnetic nanoparticles coated with polyacrylic acid. Ferrogels were fully characterized and their ability to retain Cu²⁺ and Cd²⁺, as model heavy metals, was studied. Thus kinetics and mechanisms of adsorption were evaluated and modeled. The concentration of MNPs on the PVA matrix was key to improve the adsorption capability (approximately the double of retention is improved by the MNPs addition). The adsorption kinetics was determined as pseudo-second order model, whereas the Langmuir model was the most appropriate to explain the behavior of the gels. Finally reuse ability was evaluated to determine the real potential of these materials, the ferrogels demonstrated high efficiency up to about five cycles, retaining about 80–90% of their initial adsorption capability. All the results indicated that the materials are promising candidates able to compete with the commercial technology regarding to water remediation.     

Preparation and Properties of a Chitosan–Hyaluronic Acid-Polypyrrole Conductive Hydrogel Catalyzed by Laccase

Electro conductive hydrogels, consisting of chitosan (CS), hyaluronic acid (HA), and polypyrrole (PPy), were prepared via an in situ enzymic polymerization of pyrrole in the CS–HA hydrogel, using laccase as the catalyst. This CS–HA–PPy composite hydrogel showed good conductivity. The chemical structure and morphology of this conductive hydrogel were studied by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction technique. For CS–HA–PPy and CH–HA hydrogel, the temperature at which fastest decomposition occurred was 260 and 244 °C, respectively. That means the thermal stability of CS–HA–PPy is better than CS–HA hydrogel. The conductive hydrogel also showed excellent swelling and deswelling behaviors.     

Effect of Ionizing Radiation on the Morphological,Thermal and Mechanical Properties of Polyvinyl Alcohol/Polyethylene Glycol Blends

Blends of water—soluble polymers based on Poly vinyl alcohol (PVA) and Polyethylene glycol (PEG) have been prepared by the solution casting technique. The effect of various doses of γ-radiation on the structural properties of PVA/PEG polymer blends with all its compositions has been investigated. From the visual observation of all the blend compositions, it was found that, the best compatibility of the blend is up to 40% PVA/60%PEG. The structure–Property behavior of all the prepared blends before and after γ-irradiation was investigated by IR Spectroscopy, thermogravimetric analysis (TGA), mechanical properties and Scanning electron microscope (SEM). The gel content and the swelling behavior of the PVA/PEG blends were investigated. It was found that the gel content increases with increasing irradiation dose and PVA concentration in the blend. Swelling percent increased as the composition of PEG increased in the blend. The results obtained by FTIR analysis and SEM confirm the existence of possible interaction between PVA and PEG homopolymers. TGA of PVA/PEG blend, before and after γ-irradiation, showed that the unirradiated and irradiated PVA/PEG blends are more stable against thermal decomposition than pure PVA. Improvement in tensile mechanical properties of PVA/PEG blends was occurred.     

Preparation conditions and swelling equilibria of biodegradable hydrogels prepared from microbial poly(γ-glutamic acid) and poly(ε-lysine)

Biodegradable hydrogels prepared by -irradiation from microbial poly(amino acid)s are reviewed. pH-sensitive hydrogels were prepared by means of -irradiation of poly(-glutamic acid) (PGA) produced byBacillus subtilis IFO3335 and poly(-lysine) (PL) produced byStreptomyces albulus in aqueous solutions. The preparation conditions, swelling equilibria, hydrolytic degradation, and enzymatic degradation of these hydrogels were studied. A hydrogel with a wide variety of swelling behaviors has been produced by -irradiation from a mixture solution of PGA and PL.Paper presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995, Durham, New Hampshire, USA.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.     

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of T_g (glass transition temperature), T_m (melting point temperature), and T_max (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.     

Toughening of Polyvinyl Alcohol Hydrogel Through Co-Crosslinking and its Wastewater Treatment Performance by Immobilizing with Microorganism

In order to improve the hydraulic impact resistance of the polyvinyl alcohol (PVA) hydrogel as microorganism immobilization carrier and meet the requirements of long-time aeration of sewage treatment, the toughening PVA hydrogel beads were prepared by co-crosslinking with polyoxypropylene triol (PPG) through the boric acid (H₃BO₃)-chemical crosslinking method. It was found that PPG could increase the consumption of H₃BO₃, participated and accelerated the crosslinking reaction of PVA, and the pore size of the surface layer and core layer of the hydrogel beads can be controlled. With increasing PPG content, the shear storage modulus (G’) and the effective network density (ν_e) increased first, reached maximum in presence of 2 wt% PPG, and decreased afterwards. A relatively low content of PPG could promote the formation of relatively uniform and dense network structure in PVA hydrogel, resulting in an improvement of the mechanical property and long-term hydraulic stability of the gel beads. By addition of PPG, the capillary water absorption capacity of PVA hydrogel can be enhanced and the high permeability can be kept well. When applying in waste water treatment, the value of the oxygen uptake rate (OUR) and COD removal rate of the PVA hydrogel immobilized with activated sludge had no obvious difference with addition of PPG, and a high microbial activity can be maintained.     

Preparation and Characterization of Gamma Irradiated Sugar Containing Starch/Poly (Vinyl Alcohol)-Based Blend Films

Blends based on different ratios of starch (35–20%) and plasticizer (sugar; 0–15%) keeping the amount of poly(vinyl alcohol) (PVA) constant, were prepared in the form of thin films by casting solutions. The effects of gamma-irradiation on thermal, mechanical, and morphological properties were investigated. The studies of mechanical properties showed improved tensile strength (TS) (9.61 MPa) and elongation at break (EB) (409%) of the starch-PVA-sugar blend film containing 10% sugar. The mechanical testing of the irradiated film (irradiated at 200 Krad radiation dose) showed higher TS but lower EB than that of the non-radiated film. FTIR spectroscopy studies supported the molecular interactions among starch, PVA, and sugar in the blend films, that was improved by irradiation. Thermal properties of the film were also improved due to irradiation and confirmed by thermo-mechanical analysis (TMA), differential thermo-gravimetric analysis (DTG), differential thermal analysis (DTA), and thermo-gravimetric analysis (TGA). Surface of the films were examined by scanning electron microscope (SEM) image that supported the evidence of crosslinking obtained after gamma irradiation on the film. The water up-take and degradation test in soil of the film were also evaluated. In this study, sugar acted as a good plasticizing agent in starch/PVA blend films, which was significantly improved by gamma radiation and the prepared starch-PVA-sugar blend film could be used as biodegradable packaging materials.     

Biodegradable Chitosan Hydrogels for In Vitro Drug Release Studies of 5-Flurouracil an Anticancer Drug

Novel semi-interpenetrating network (semi-IPN) hydrogels based on biodegradable chitosan and poly(N-isopropylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) were prepared by free radical addition polymerization. Fourier transform infrared spectra and scanning electron microscopy were used to characterize the semi-IPN hydrogels and the results showed that chitosan and poly(N-isopropylacrylamide-co-2-acrylamide-2-methyl-1-propanesulfonic acid) semi-IPN hydrogels were coupled by the interaction of the functional groups present in NIPAAm, CS and AMPS units. The PNIPAAm and P(NIPAAm-AMPS)/CS hydrogels have lower critical solution temperature and the same was confirmed with the help of differential scanning calorimetry as well as with the temperature dependent swelling curves. The model anti cancer drug, 5-fluorouracil (5-FU) was loaded into the semi-IPN hydrogels, at ambient temperature. The 5-FU loading capacity and release behaviour were investigated with these hydrogels acting as carriers for controlled release. The released 5-FU concentration was calculated with the help of UV spectrophotometer at 266.5?nm.     

Preparation of Cellulose/Xanthan Gum Composite Films and Hydrogels Using Ionic Liquid

This paper reports the preparation of cellulose/xanthan gum composite films and hydrogels through gelation with an ionic liquid. Mixtures of cellulose and xanthan gum in desired weight ratios with an ionic liquid, 1-butyl-3-methylimidazolium chloride (BMIMCl), were thinly placed on a Petri dish and heated at 100 °C for 9 h to obtain the solutions. Then, the solutions were left standing at room temperature for 1 day for the progress of gelation. The resulting ion gels were subjected to Soxhlet extraction with ethanol to remove BMIMCl, followed by drying under ambient conditions to obtain the composite films. The crystalline structures of the polysaccharides and the mechanical properties were evaluated by powder X-ray diffraction measurement and tensile testing of the films, respectively. The ion gels in various cellulose/xanthan gum weight ratios, which were prepared in a test tube by the same procedure, were immersed in water for the exchange of disperse media to obtain the cellulose/xanthan gum composite hydrogels. Water contents of all the materials were higher than 90 %. The mechanical properties of the hydrogels were evaluated by compressive testing.     

Biodegradable Films Based on Blends of Gelatin and Poly (Vinyl Alcohol): Effect of PVA Type or Concentration on Some Physical Properties of Films

The aim of this work was to develop biodegradable films based on blends of gelatin and poly (vinyl alcohol) (PVA), without a plasticizer. Firstly, the effect of five types of PVA with different degree of hydrolysis (DH) on the physical properties of films elaborated with blends containing 23.1% PVA was studied. One PVA type was then chosen for the study of the effect of the PVA concentration on the mechanical properties, color, opacity, gloss, and water solubility of the films. The five types of PVA studied allowed for films with different characteristics, but with no direct relationship with the DH of the PVA. Therefore, the PVA Celvol^®418 with a DH = 91.8% was chosen for the second part, because they produced films with greater tensile strength. The PVA concentration affected all studied properties of films. These results could be explained by the results of the DSC and FTIR analyses, which showed that some interactions between the gelatin and the PVA occurred depending on the PVA concentration, affecting the crystallinity of the films.     

A Novel Packaging Film from Cassava Starch and Natural Rubber

Currently, there is an environmental pollution problem generated in part by packaging materials produced from non-biodegradable synthetic polymers made from petroleum. However, these can be replaced with biodegradable materials made from cassava starch (CS) and natural rubber (NR). In the work described, a novel biopolymer film was obtained from the CS and NR using glycerol (GE) as a plasticizer in a water-based system. The physical properties of an 95/5 CS/NR blend films with the addition of NR and with varying GE contents were studied based on their swelling ratio, moisture content, moisture absorption, mechanical properties and biodegradability in soil. The results showed that the moisture content and moisture absorption tended to be directly proportional to the GE content, while the moisture content and moisture absorption of the sample decreased as a function of the NR content. The swelling ratio of the 95/5 CS/NR blend slightly decreased as a function of the NR and GE content. Surprisingly, the best swelling ratio of 350% was found at 10% NR. The elongation at break of the CS/NR blend was improved by the addition of GE. The contact angle of the 95/5 CS/NR blend decreased as a function of the GE. With increased NR in the composite, an increasing, trend in the contact angle was found. Further, the 95/5 CS/NR blend exhibited good transparency when it was applied as a coating to delay the ripening of bananas, the results were positive. Moreover, the film showed decomposition well in natural soil.     

Mechanical Properties with the Functional Group of Additives for Starch/PVA Blend Film

This paper deals with the mechanical properties and degree of swelling (DS) of starch/PVA blend film with the functional groups i.e., hydroxyl and carboxyl group, of additives. Starch/PVA blend films were prepared by using the mixing process. Glycerol (GL) with 3 hydroxyl group, sorbitol (SO) with 6 hydroxyl group, succinic acid (SA) with 2 carboxyl group, malic acid (MA) with 1 hydroxyl and 2 carboxyl group, tartaric acid (TA) with 2 hydroxyl and 2 carboxyl group and citric acid (CA) with 1 hydroxyl and 3 carboxyl group were used as additives. The results of measured tensile strength (TS) and elongation (%E) verified that both hydroxyl and carboxyl group as a functional groups increased the flexibility and strength of the film. Values of DS for GL-added and SA-added films were low. However, DS values of the films added MA, TA or CA with both hydroxyl and carboxyl group were comparatively high. When the film was dried at low temperature, the properties of the films were evidently improved. The reason is probably because the hydrogen bonding was activated at low temperature.     

水合改性对钙基吸收剂循环捕集CO2的影响

在钙基吸收剂捕集CO2的过程中，吸收剂转化率会随着循环次数的增加而迅速降低。钙基吸收剂的水合改性作为改善吸收剂循环转化率的主要方法之一受到了国内外学者的广泛关注。总结了目前国内外研究者对不同的吸收剂、循环捕集条件下的水合改性方法的研究成果。结果表明，在循环过程中的不同阶段对吸收剂进行水合处理后得到的效果不同。其中，在碳酸化阶段、煅烧阶段、循环捕集前预处理以及煅烧后对吸收剂水合改性．吸收剂捕集CO2的能力均得到了改善；碳酸化反应后对吸收剂进行水合处理是否对循环吸收有利还存在争议。目前，利用水合改性的方法提高钙基吸收剂循环捕集CO2能力的机理还存在争议，且水合改性后的吸收剂机械性能差以及此方法能耗高的问题尚待解决。