Formulation and Characterization of Sodium Alginate g-Hydroxy Ethylacrylate Bio-Degradable Polymeric Beads: In Vitro Release Studies

Novel type of highly swollen beads were prepared by grafting 2-hydroxyethylacrylate onto biodegradable Sodium alginate (SA) via free-radical polymerization using potassium persulphate as an initiator and Triprolidine hydrochloride as a model drug. Evidence of grafting was obtained by fourier transform infrared spectroscopic technique. Morphological properties of the beads were studied by SEM analysis. Thermal properties and crystallinity of the beads were characterized using differential scanning calorimetry and thermogravimetric analysis and X-ray diffraction techniques, respectively. Dissolution experiments were performed to study the release profiles at 37?°C in phosphate buffer solution (pH-7.4). Effect of monomer content, crosslinking agent and drug/polymer ratio on swelling properties and release profiles were also comparatively studied. A dissolution result concludes that drug release decreases with increasing crosslinker content. The highest release (96%) was obtained for the beads prepared with 0.5?mL crosslinking agent. Equilibrium swelling degree also supports the drug release profiles confirming SA-g-HEA beads showed better release profiles compare to plain SA beads.     

Influence of Glutaraldehyde Crosslinking and Alkaline Post-treatment on the Properties of Chitosan-Based Films

Depending on the modifications proposed, chitosan films present different characteristics, for instance correlated to hydrophilicity, chemical and mechanical properties. The aim of this study was to evaluate the influence of glutaraldehyde crosslinking and an alkaline post-treatment with NaOH on the characteristics of chitosan based films. Films were obtained by casting and characterized by thickness, swelling degree, mechanical and thermal properties and chemical structure. The water vapor permeability (WVP) was also evaluated for food packaging application. It was observed that crosslinking and NaOH post-treatment have great influence on the chitosan films characteristics. Crosslinking reduced the swelling degree of films and increased its fragility, whereas NaOH treatment also reduces the swelling degree and changes mechanical properties, acting in the same way as a crosslinker. The WVP analyses showed that the basic treatment could substitute the glutaraldehyde crosslinking for film water stability, without greatly compromising the barrier properties of chitosan based films.     

Adsorption Kinetics of Dyes in Single and Binary Systems Using Cyanoguanidine-Crosslinked Chitosan of Different Deacetylation Degrees

The crosslinking of chitosan with cyanoguanidine shows some advantages, such as the improved the stability in acid solutions and the decrease of adsorbent cost. In this work, cyanoguanidine-crosslinked chitosan and pure chitosan were prepared to apply in the adsorption of Food Yellow 4 (FY4) and Food Blue 2 (FB2), in single and binary systems. Effects of pH and deacetylation degree (DD) of chitosan in adsorption were evaluated. The adsorbents were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The kinetic data were analyzed by pseudo-first order, pseudo-second order and Avrami models. The conditions of pH 3 and DD 95% were the more suitable to reach the highest adsorption capacities in all experimental assays. Under these conditions, the adsorption capacities for FY4 were approximately of 392 and 200 mg g^?1 and, for FB2 were approximately of 370 and 184 mg g^?1, respectively, in the single and binary systems. The Avrami model was suitable to represent the kinetic curves in all conditions, and the highest adsorption capacities were found for FY4 in binary aqueous system, being for the pure chitosan of 229 mg g^?1 and crosslinked chitosan of 218 mg g^?1. The Langmuir and extended Langmuir models presented a good fit to the equilibrium data in both systems. It was found that, the chitosan crosslinked with cyanoguanidine improved the chemical stability of chitosan as adsorbent.     

Recovery of gold by chicken egg shell membrane-conjugated chitosan beads

We have successfully prepared a bead-type adsorbent from two materials with different adsorption characteristics. Heavy metals were removed by greatly swollen egg shell membrane-conjugated chitosan beads. The egg shell membrane accumulated and removed precious metal ions from a dilute aqueous solution with a high affinity in a short contact time. Experiments suggested that chitosan beads could take up gold ions with great capacity and selectivity by conjugation with egg shell membrane. Under certain conditions, the selective removal of gold and copper in a mixture of gold and copper ions by egg shell membrane-conjugated chitosan beads was 100% and 2%, respectively. Egg shell membrane-conjugated chitosan beads can be seen as a promising material to recover gold in wastewater from various industries, such as electroplating.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Tailored Natural Polysaccharides Beads as Green Sorbents for Efficient Lysozyme Adsorption

Herein, we prepared alginate (SA)/carboxymethyl cellulose (CMC) gel beads through Ca²⁺ and glutaraldehyde (GA) crosslinking and investigated their adsorption performance on lysozyme from aqueous solution. Taking advantage of the abundant active carboxyl groups on SA and CMC, the obtained SA/CMC gel beads present an excellent integrated lysozyme adsorption performance with a high capacity of 236.34 mg g^?1, short equilibrium time of 8 h, ease of elution, and good reusability. Furthermore, the resultant SA/CMC gel beads also possess unique selectivity for positively charged proteins, confirmed by the method of sodium dodecyl sulfate polyacrylamide gel electrophoresis. Considering the nature of biopolymers and advantages of favorable physical properties, high efficiency, cost-effectiveness, intriguing adsorption capacity and easier separation from the reaction system, the SA/CMC gel beads may find more potential in protein separation and purification than that of synthetic material.     

交联壳聚糖/沸石复合吸附剂的制备及性能

用沸石负载由缩水甘油基三乙基氯化铵交联的壳聚糖,制得了性能良好的交联壳聚糖/沸石复合吸附剂。研究了该吸附剂应用性能的影响因素,探讨了该吸附剂的吸附性、沉降性和重复使用性,利用FTIR仪和高倍透射电子显微镜对该吸附剂的结构进行了表征。实验结果表明:壳聚糖的交联度为0.93、交联壳聚糖与沸石的质量比为0.045时,制得的交联壳聚糖/沸石复合吸附剂对腐殖酸的去除率可达81.4%,吸附量为4.07mg/g;交联壳聚糖/沸石复合吸附剂对腐殖酸的吸附性能较沸石有显著提高,沉降时间较交联壳聚糖明显缩短;经二次洗脱后腐殖酸去除率仍可达80.2%,腐殖酸吸附量为4.01mg/g。     

Removal of Linear and Branched p-Alkylphenols from Aqueous Solution by Combined Use of melB Tyrosinase and Chitosan Beads

In this study, melB tyrosinase was applied for enzymatic removal of linear and branched p-alkylphenols from aqueous solutions. First, systematic studies were carried out to estimate the effects of the process parameters such as the temperature, pH value, and enzyme dose on quinone conversion of p-cresol as a model phenol compound. A variety of p-alkylphenols were removed from aqueous solutions through the tyrosinase-catalyzed quinone conversion and subsequent nonenzymatic adsorption of quinone derivatives on chitosan beads at pH 6.0 and 30 °C under the optimum conditions determined for p-cresol. The % removal values of 98–100 were obtained for p-n-alkylphenols. Branched p-alkylphenols with a weak estrogenic activity containing 4-tert-butylphenol and 4-tert-pentylphenol, which underwent no quinone conversion by commercially available mushroom tyrosinase in the absence of H₂O₂, were also effectively removed by further increasing either the melB tyrosinase concentration or the amount of added chitosan beads. The present technique is much effective in the fact that a series of reactions rapidly progress under mild conditions and the chitosan beads can be readily separated from the reaction medium after the enzymatic treatment.     

交联壳聚糖季铵盐吸附剂的制备及其对重金属离子的吸附

以壳聚糖为原料、二甲基二烯丙基氯化铵（DMDAAC）为接枝单体、甲醛为预交联剂、环氧氯丙烷为交联剂,通过反相乳液聚合制备出交联壳聚糖季铵盐吸附剂,并将其用于吸附Ni（Ⅱ）和Cr（Ⅵ）。考察了吸附时间、溶液初始浓度、溶液pH等因素对吸附效果的影响。实验结果表明：该吸附剂对Ni（Ⅱ）和Cr（Ⅵ）的吸附过程遵循拟二级动力学方程,吸附等温线符合Langmuir方程;在30 ℃条件下,Ni（Ⅱ）和Cr（Ⅵ）的溶液初始浓度均为1 mmol/L时,该吸附剂吸附Ni（Ⅱ）和Cr（Ⅵ）的最佳溶液pH分别为7和6,对应的平衡吸附量分别为1.18,1.99 mmol/g;该吸附剂可用盐酸再生,重复使用性能良好。     

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.     

Fabrication of Polypyrrole/Chitosan Nanocomposite Aerogel Monolith for Removal of Cr(VI)

Three-dimensional polypyrrole/chitosan nanocomposite monoliths are fabricated by polymerization of pyrrole in chitosan aqueous solution. The static polymerization of pyrrole monomer and the cross-linking of chitosan by glutaraldehyde occur simultaneously, resulting in the self-assembly of polypyrrole/chitosan nanocomposite aerogel monolith. The addition of methyl orange and glutaraldehyde and the static reaction play key roles in the formation of the self-standing aerogel monolith. The as-prepared monolith with larger specific surface area exhibits much better adsorption capability for Cr(VI) removal in comparison with that prepared without the addition of glutaraldehyde. The adsorption process and adsorption isotherms are found to well follow the pseudo-second-order and Langmuir models, respectively. Furthermore, this polypyrrole/chitosan nanocomposite monolith is stable and recyclable. About 73.5% of the initial adsorption capability is kept after eight adsorption–desorption cycles. The polypyrrole/chitosan nanocomposite monolith can be a promising candidate for the efficient removal of Cr(VI).     

Poly(Acrylic Acid) Grafted Sodium Alginate Di-Block Hydrogels as Efficient Biosorbents; Structure-Property Relevance

Naturally-based poly(acrylic acid) grafted sodium alginate di-block hydrogels were investigated as high efficiency biosorbents for copper(II) ion. The grafted di-block hydrogel was characterized using FTIR, TGA and SEM techniques. Blank and immobilized algal biosorbent beads formed via 2.0% (w/w) calcium ions were also investigated. Batch adsorption experiments revealed optimal pH dependence of copper(II) ion biosorption at pH 5.5 with high efficient copper(II) ion uptake of 98.5 mg/g. The dynamics studies showed that the high efficiency copper(II) ion biosorption followed pseudo-second order kinetics with significant contribution of intraparticle diffusion mechanism. The equilibrium data fitted to Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) adsorption isotherm models. Thermodynamics parameters for copper(II) biosorption on blank and immobilized algal beads depicted the spontaneous nature of the biosorption process. Such high efficiency, feasibility, simplicity, and low cost properties adapt the di-block biosorbent to be the next generation promising biosorbents for water decontamination and to help in the recovery of the missing ecologic harmony.     

Enhancement of Sedimentation Velocity of Heavy Metals Loaded Hydroxyapatite Using Chitosan Extracted from Shrimp Waste

In this study, synthesize hydroxyapatite (HA) suspensions sedimentation was used after usual terms as support for adsorption of heavy metals ions. Thus, the effectiveness of chitosan, produced from shrimp waste, in the flocculation of turbid suspensions resulting from the treatment of water contaminated with heavy metals was studied by adsorption on HA. Different particles sizes of HA were mainly controlled in this work (an average of granule size ranging from 1.6 to 63 μm). The results of Cu²⁺ and Zn²⁺ adsorption on HA showed relatively fast kinetics, with removal extent of 88–95 % by varying the initial total metal concentration. High removal rates were obtained for Cu²⁺. Chitosan was found to be able to eliminate by flocculation more than 98 % of turbid suspensions generated by metals adsorption on HA after only 30 min of sedimentation. Effects of pH and dose of chitosan on the coagulation–flocculation process were also studied. The optimal dose of chitosan was found between 0.2 and 2 mg/L which corresponds to an optimal pH ranging from 6 to 7.     

Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of \({\text{UO}}_{2}^{{2+}}\) from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of \({\text{UO}}_{2}^{{2+}}\) by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R²?=?0.99) and probability F-values (F?=?2.24?×?10^??10) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of \({\text{UO}}_{2}^{{2+}}\) ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.     

Influence of the Concentrations of Chitosan and Glycerol on Edible Film Properties Showed by Response Surface Methodology

The individual and interactive effects of glycerol and chitosan concentrations on edible film properties were investigated using response surface methodology. The results of ANOVA indicated that all the independent variables exhibited significant effect on the film properties. Chitosan concentration had a positive effect on CO₂ permeability and negative effect on O₂ while the glycerol concentration had a positive effect on permeability to both gases. Regarding water vapor permeability, the chitosan concentration had a negative effect, whereas the glycerol had no influence. Moreover, both chitosan and glycerol concentration influenced the elongation at break point (%A), and only glycerol concentration had a significant effect on tensile strength. Optimization by desirability approach was carried out on the independent variables to get the optimum levels within the experimental conditions. It was found that 1.5 % of chitosan and 25 % of glycerol (wt/wt of chitosan) retarded respiration and showed a strong permeability to water vapor.     

Experimental and Modeling Studies for the Removal of Crystal Violet Dye from Aqueous Solutions using Eco-friendly <Emphasis Type="Italic">Gracilaria corticata</Emphasis> Seaweed Activated Carbon/Zn/Alginate Polymeric Composite Beads

This research article describes, an eco-friendly activated carbon prepared from the Gracilaria corticata seaweeds which was employed for the preparation of biodegradable polymeric beads for the efficient removal of crystal violet dye in an aqueous solution. The presence of chemical functional groups in the adsorbent material was detected using FTIR spectroscopy. The morphology and physical phases of the adsorbent materials were analyzed using SEM and XRD studies respectively. Batch mode dye adsorption behavior of the activated carbon/Zn/alginate polymeric beads was investigated as a function of dosage, solution pH, contact time, initial dye concentration and temperature. Maximum dye removal was observed at a pH of 5.0, 1 g of adsorbent dosage with 60 mg/L dye concentration, 50 min of contact time and at 30 °C. The equilibrium modeling studies were analyzed with Freundlich and Langmuir adsorption isotherms and the adsorption dynamics was predicted with Lagergren’s pseudo-first order, pseudo-second order equations and intra particle diffusion models. The process of dye removal followed a pseudo second-order kinetics rather than pseudo first order. The thermodynamic parameters like standard Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined and the results imply that the adsorption process was spontaneous, endothermic and increases the randomness between the adsorbent and adsorbate. The results from the experimental and correlation data reveal that the Gracilaria corticata activated carbon/Zn/alginate polymeric beads have proved to be an excellent adsorbent material for the removal of CV dye.     

Chitosan Functionalization with Amino Acids Yields to Higher Copper Ions Adsorption Capacity

Chitosan (Chi) beads were conjugated with three different amino acids [namely, glutamic acid (GLU), methionine (MET), and taurine (TAU)] aiming to increase the divalent copper ions uptake in aqueous media. Scanning Electron Microscopy evidenced the development of a large porous structure after amino acid functionalization, associated with the increase in a number of amino groups in the polymer backbone. X-Ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectra analyses were also employed to assess the conjugation of these three different amino acids in chitosan backbone. Adsorption experiments were conducted in a batch process, at 298 K, and kinetic data indicated a slightly better fitting for the pseudo-first-order model when compared to pseudo-second order. Intraparticle diffusion model suggested a three-step mechanism for Cu(II) adsorption kinetics, limited by the third step, the intraparticle diffusion. The isotherm data fitting to the traditional Langmuir and Freundlich models indicated a better fit for the former case. The amino acid conjugation resulted in the increase of the maximum adsorption capacity for Cu(II) from 1.30 mmol g^?1 prior to amino acid conjugation to values as high as 2.31 mmol g^?1, 2.40 mmol g^?1 and 2.68 mmol g^?1 for Chi–TAU, Chi–GLU, and Chi–MET, respectively. These results are attributed to the introduction of additional amino groups and new carboxylate and amino acid residues into the chitosan backbone, which might also be explored for amino acid demanding applications.     

改性壳聚糖处理微生物浸矿废水

为解决采矿行业微生物浸矿酸性废水中和处理沉渣多、固液分离困难的问题,采用柠檬酸钠和环氧氯丙烷改性处理的壳聚糖在pH=2.2条件下吸附模拟废水中的Cu²⁺和Fe³⁺,用正交实验优化了壳聚糖改性工艺条件。实验结果表明,最适宜的工艺条件为：处理100 mL壳聚糖质量分数为2%的壳聚糖-冰醋酸溶液,柠檬酸钠缓冲溶液加入量200 mL,环氧氯丙烷加入量300 mL,反应时间6 h。改性壳聚糖对Fe³⁺的最大吸附容量为6.703 7 mg/g,对Cu²⁺的最大吸附容量为4.378 7 mg/g,Fe³⁺和Cu²⁺在改性壳聚糖上的吸附是单分子层形式。     

Synthesis of Gum Acacia Capped Polyaniline-Based Nanocomposite Hydrogel for the Removal of Methylene Blue Dye

In this research work, a novel gum acacia capped polyaniline-based nanocomposite hydrogel (GPA NCHs) was developed and evaluated for the adsorptive removal of cationic methylene blue dye (MB) from aqueous solutions. Firstly, Gum acacia (GA) capped Polyaniline (PANI) dispersion was synthesized by using dispersion polymerization. Then, a water-swellable hydrogel network consisting of GA-PANI and acrylamide (AM) was obtained by using N,N′ -methylene-bisacrylamide (MBA) as a cross-linker, and ammonium persulphate/N,N,N′,N′-tetramethylethylenediamine (APS/TMEDA) as an initiating system. The developed materials were characterized by UV–visible, FTIR, XRD, SEM–EDX and TEM techniques. The microscopy studies revealed that GA-PANI nanoparticles have a granular morphological surface with an average size of?~?40–100 nm. Removal of MB dye from aqueous system was performed by adsorption studies in batch equilibrium mode with different dosage of GA-PANI, MB concentration, pH and temperatures. The adsorption data revealed that the absorption capacity of GPA NCHs highly depends on the dosage of GA-PANI, pH and concentration of the MB dye. The maximum percentage of MB removal onto GPA 1.0 NCHs was found to be 89% at pH 10 with a dye concentration of 10 mg L^?1. The equilibrium adsorption data were also analyzed by different models to understand the adsorption process. The results revealed that the adsorption process followed the pseudo-second-order kinetics and it fit well in Langmuir and Freundlich adsorption isotherms with a maximum adsorption capacity of 35.41 mg g^?1. These studies demonstrate that the GPA NCHs could be a promising adsorbent material for the removal of MB dye from contaminated aqueous systems.

     

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.