Application of Synthetic Monomers Grafted Xanthan Gum for Rhodamine B Removal in Aqueous Solution

The rapid industrialisation and population growth have led to a steady fall in freshwater supplies worldwide. As a result, water systems are affected by modern methods upon use due to secondary contamination. The application of novel adsorbents derived from natural polymer holds a great promise in addressing challenges in water treatment. In this study, the UV irradiation technique was used to prepare acrylamide (AAm) monomer, and acrylic acid (AA) monomer grafted xanthan gum (XG) copolymer. Furthermore, the factors affecting rhodamine B (RhB) adsorption from aqueous media, such as pH, dosage, concentration, and time were also investigated. The FTIR results confirmed the formation of graft copolymer by the strong vibrational bands at 1709 cm-1 and 1612 cm-1 for AA and AAm, respectively. Additionally, more irregular, porous and wrinkled surface observed from SEM of XG-g-AAm/AA indicated copolymerization interaction of monomers. The optimum conditions for removing RhB dye with a maximum adsorption capacity of 313 mg/g at 25 0C from aqueous solution were pH approximately 5, initial dye concentration = 200 ppm, adsorbent dose = 30 mg. Also, the detailed investigation of the isothermal and adsorption kinetics of RhB from aqueous solution showed that the adsorption of the dye followed a Freundlich model (R2 = 0.96333) and pseudo-second-order kinetics. The results further indicated that this absorbent based on XG had the universality to remove dye through the mechanism of chemical adsorption. The outstanding adsorption potential of the grafted copolymer could be used to remove cationic dyes from aqueous solution as a low-cost product.

Sustainable Hydrogel Nanocomposites Based on Grafted Chitosan and Clay for Effective Adsorption of Cationic Dye

Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (qm) was found to increase from 2173 mg g−1 until 2221 mg g−1 by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

A Dynamic Mechanical Thermal T-Peel Test Approach to Characterize Interfacial Behavior of Polymeric Textile Composites

Basic understanding of interfacial mechanisms is of importance for the development of polymer composites. For this purpose, we need techniques to analyze the quality of interphases, their chemical and physical interactions and their strength and fracture resistance. In order to investigate the interfacial phenomena in detail, advanced characterization techniques are favorable. Dynamic mechanical thermal analysis (DMTA) using a rheological system is a sensitive tool. T-peel tests were performed with this system, to investigate the temperature-dependent peel behavior of woven textile composites. A model system was made of polyamide (PA) woven fabric laminated with films of polypropylene (PP) or PP modified by grafting with maleic anhydride (PP-g-MAH). Firstly, control measurements were performed with solely PP matrixes. Polymer melt investigations, as well as the extensional stress, extensional viscosity and extensional relaxation modulus at -10°C, 100 °C and 170 °C, demonstrate similar viscoelastic behavior for films made of PP-g-MAH and its non-modified PP-control. Frequency sweeps have shown that PP-g-MAH has a zero phase viscosity of around 1600 Pa·s and PP-control has a similar zero phase viscosity of 1345 Pa·s. Also, the gelation points are similar at 2.42*104 Pa (118 rad/s) and 2.81*104 Pa (161 rad/s) for PP-control and PP-g-MAH, respectively. Secondly, the textile composite was analyzed. The extensional stress of PA66 fabric laminated with either PP-control or PP-g-MAH at -10 °C, 25 °C and 170 °C for strain rates of 0.001 – 1 s-1 was investigated. The laminates containing the modified PP need more stress for T-peeling. However, the strengthening effect due to the modification decreases by increasing temperature and at 170 °C, just above the melting temperature of the matrix, the difference disappears. Independent of the matrix used in the textile composite, there is a decrease of extensional stress by increasing temperature. It appears that the more viscous is the matrix, the weaker the laminar adhesion. Possibly, the measurement is influenced by the fact that the laminate becomes stiffer at lower temperatures. Adhesive lap-shear testing at room temperature supports the findings obtained with the T-peel test. Additional analysis of the textile composite at the microscopic level ensures that the fibers are well embedded in the matrix. Atomic force microscopy (AFM) imaging of a cross section of the composite shows no gaps between the fibers and matrix. Measurements of the water contact angle show that the MAH grafted PP is more polar than the virgin-PP, and that suggests a more favorable chemical interaction of PP-g-MAH with PA, compared to the non-modified PP. In fact, this study indicates that T-peel testing by DMTA is a technique to achieve more insights into polymeric textile composites.

Kinetics and Thermodynamics Adsorption of Phenolic Compounds on Organic-Inorganic Hybrid Mesoporous Material

Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH3)3 was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values ​​obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.

Functionalization of Polypropylene with Chiral Monomer for Improving Hemocompatibility

Polypropylene (PP) is one of the most commonly used plastics because of its low density, outstanding mechanical properties, and low cost. However, its drawbacks such as low surface energy, poor dyeability, lack of chemical functionalities, and poor compatibility with polar polymers and inorganic materials, have restricted the application of PP. To expand its application in biomedical materials, functionalization is considered to be the most effective way. In this study, PP was functionalized with a chiral monomer, (S)-1-acryloylpyrrolidine-2-carboxylic acid ((S)-APCA), by free-radical grafting in the solid phase. The grafting degree of PP-g-APCA was determined by chemical titration method, and the chemical structure of functionalized PP was characterized by FTIR spectroscopy, which confirmed that the chiral monomer (S)-APCA was successfully grafted onto PP. Static water contact angle results suggested that the surface hydrophilicity of PP was significantly improved by solid phase grafting and assistance of surface water treatment. Protein adsorption and platelet adhesion results showed that hemocompatibility of PP was greatly improved by grafting the chiral monomer.

Adsorption of Phenol and 4-Hydroxybenzoic Acid onto Functional Materials

The objective of this study was to investigate the removal of two organic pollutants; 4-hydroxybenzoic acid (p-hydroxybenzoic acid) and phenol from synthetic wastewater by the adsorption on mesoporous materials. In this context, the aim of this work is to study the adsorption of organic compounds phenol and 4AHB on MCM-41 and FSM-16 non-grafted (NG) and other grafted (G) by trimethylchlorosilane (TMCS). The results of phenol and 4AHB adsorption in aqueous solution show that the adsorption capacity tends to increase after grafting in relation to the increase in hydrophobicity. The materials are distinguished by a higher adsorption capacity to the other NG materials. The difference in the phenol is 14.43% (MCM-41), 14.55% (FSM-16), and 16.72% (MCM-41), 13.57% (FSM-16) in the 4AHB. Our adsorption results show that the grafted materials by TMCS are good adsorbent at 25 °C.

Cold Plasma Surface Modified Electrospun Microtube Array Membrane for Chitosan Immobilization and Their Properties

Electrospun microtube array membranes (MTAMs) made of PLLA (poly-L-lactic acid) have wide potential applications in tissue engineering. However, their surface hydrophobicity and poor biocompatability have limited their further usage. In this study, the surface of PLLA MTAMs were made hydrophilic by introducing extra functional groups, such as peroxide, via an acetic acid plasma (AAP). UV-graft polymerization of acrylic acid (G-AAc) was then used to produce carboxyl group on MTAMs surface, which bonded covalently with chitosan through EDC / NHS crosslinking agents. To evaluate the effects of the surface modification on PLLA MTAMs, water contact angle (WCA) measurement and cell compatibility tests were carried out. We found that AAP treated electrospun PLLA MTAMs grafted with AAc and, finally, with chitosan immobilized via crosslinking agent, exhibited improved hydrophilic and cell compatibility.

Polymer Mediated Interaction between Grafted Nanosheets

Polymer-particle interactions can be effectively utilized to produce composites that possess physicochemical properties superior to that of neat polymer. The incorporation of fillers with dimensions comparable to polymer chain size produces composites with extra-ordinary properties owing to very high surface to volume ratio. The dispersion of nanoparticles is achieved by inducing steric repulsion realized by grafting particles with polymeric chains. A comprehensive understanding of the interparticle interaction between these functionalized nanoparticles plays an important role in the synthesis of a stable polymer nanocomposite. With the focus on incorporation of clay sheets in a polymer matrix, we theoretically construct the polymer mediated interparticle potential for two nanosheets grafted with polymeric chains. The self-consistent field theory (SCFT) is employed to obtain the inhomogeneous composition field under equilibrium. Unlike the continuum models, SCFT is built from the microscopic description taking in to account the molecular interactions contributed by both intra- and inter-chain potentials. We present the results of SCFT calculations of the interaction potential curve for two grafted nanosheets immersed in the matrix of polymeric chains of dissimilar chemistry to that of the grafted chains. The interaction potential is repulsive at short separation and shows depletion attraction for moderate separations induced by high grafting density. It is found that the strength of attraction well can be tuned by altering the compatibility between the grafted and the mobile chains. Further, we construct the interaction potential between two nanosheets grafted with diblock copolymers with one of the blocks being chemically identical to the free polymeric chains. The interplay between the enthalpic interaction between the dissimilar species and the entropy of the free chains gives rise to a rich behavior in interaction potential curve obtained for two separate cases of free chains being chemically similar to either the grafted block or the free block of the grafted diblock chains.

The Effects on Yield and Yield Components of Different Level Cluster Tip Reduction and Foliar Boric Acid Applications on Alphonse Lavallee Grape Cultivar

This study was carried out to determine the effects of Control (C), 1/3 Cluster Tip Reduction (1/3 CTR), 1/6 Cluster Tip Reduction (1/6 CTR), 1/9 Cluster Tip Reduction (1/9 CTR), 1/3 CTR + Boric Acid (BA), 1/6 CTR + BA, 1/9 CTR + BA applications on yield and yield components of four years old Alphonse Lavallee grape variety (Vitis vinifera L.) grown on grafted 110 Paulsen rootstock in Konya province in Turkey in the vegetation period in 2015. According to the results, the highest maturity index 21.46 with 1/9 CTR application; the highest grape juice yields 736.67 ml with 1/3 CTR + BA application; the highest L* color value 32.07 with 1/9 CTR application; the highest a* color value 1.74 with 1/9 CTR application; the highest b* color value 3.72 with 1/9 CTR application were obtained. The effects of applications on grape fresh yield, cluster weight and berry weight were not found statistically significant.

Studying the Effect of Nanoclays on the Mechanical Properties of Polypropylene/Polyamide Nanocomposites

Nanocomposites based on polypropylene/polyamide 66 (PP/PA66) nanoblends containing organophilic montmorillonite (OMMT) and maleic anhydride grafted polypropylene (PP-g-MAH) were prepared by melt compounding method followed by injection molding. Two different types of nanoclays were used in this work. DELLITE LVF is the untreated nanoclay and DELLITE 67G is the treated one. The morphology of the nanocomposites was studied using the XR diffraction (XRD). The results indicate that the incorporation of treated nanoclay has a significant effect on the impact strength of PP/PA66 nanocomposites. Furthermore, it was found that XRD results revealed the intercalation, exfoliation of nanaclays of nanocomposites.

Effect of Modified Layered Silicate Nanoclay on the Dynamic Viscoelastic Properties of Thermoplastic Polymers Nanocomposites

This work aims to investigate the structure–property relationship in ternary nanocomposites consisting of polypropylene as the matrix, polyamide 66 as the minor phase and treated nanoclay DELLITE 67G as the reinforcement. All PP/PA66/Nanoclay systems with polypropylene grafted maleic anhydride PP-g-MAH as a compatibilizer were prepared via melt compounding and characterized in terms of nanoclay content. Morphological structure was investigated by scanning electron microscopy. The rheological behavior of the nanocomposites was determined by various methods, viz melt flow index (MFI) and parallel plate rheological measurements. The PP/PP-g-MAH/PA66 nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PP, PA66, and nanoclay. SEM results revealed the formation of nanocomposites as the nanoclay was intercalated and exfoliated. In the ternary nanocomposites, the rheological behavior showed that, the complex viscosity is increased with increasing the nanoclay. The results showed that the use of nanoclay affects the variations of storage modulus (G′), loss modulus (G″) and the melt elasticity.

Using 3-Glycidoxypropyltrimethoxysilane Functionalized SiO2 Nanoparticles to Improve Flexural Properties of Glass Fibers/Epoxy Grid-Stiffened Composite Panels

Lightweight and efficient structures have the aim to enhance the efficiency of the components in various industries. Toward this end, composites are one of the most widely used materials because of durability, high strength and modulus, and low weight. One type of the advanced composites is grid-stiffened composite (GSC) structures, which have been extensively considered in aerospace, automotive, and aircraft industries. They are one of the top candidates for replacing some of the traditional components, which are used here. Although there are a good number of published surveys on the design aspects and fabrication of GSC structures, little systematic work has been reported on their material modification to improve their properties, to our knowledge. Matrix modification using nanoparticles is an effective method to enhance the flexural properties of the fibrous composites. In the present study, a silanecoupling agent (3-glycidoxypropyltrimethoxysilane/3-GPTS) was introduced onto the silica (SiO2) nanoparticle surface and its effects on the three-point flexural response of isogrid E-glass/epoxy composites were assessed. Based on the Fourier Transform Infrared Spectrometer (FTIR) spectra, it was inferred that the 3-GPTS coupling agent was successfully grafted onto the surface of SiO2 nanoparticles after modification. Flexural test revealed an improvement of 16%, 14%, and 36% in stiffness, maximum load and energy absorption of the isogrid specimen filled with 3 wt.% 3- GPTS/SiO2 compared to the neat one. It would be worth mentioning that in these structures, considerable energy absorption was observed after the primary failure related to the load peak. In addition, 3- GPTMS functionalization had a positive effect on the flexural behavior of the multiscale isogrid composites. In conclusion, this study suggests that the addition of modified silica nanoparticles is a promising method to improve the flexural properties of the gridstiffened fibrous composite structures.

Synthesis and Properties of Chitosan-Graft Polyacrylamide/Gelatin Superabsorbent Composites for Wastewater Purification

Superabsorbent polymers received much attention and are used in many fields because of their superior characters to traditional absorbents, e.g., sponge and cotton. So, it is very important but challenging to prepare highly and fast-swelling superabsorbents. A reliable, efficient and low-cost technique for removing heavy metal ions from wastewater is the adsorption using bio-adsorbents obtained from biological materials, such as polysaccharides-based hydrogels superabsorbents. In this study, novel multi-functional superabsorbent composites type semi-interpenetrating polymer networks (Semi-IPNs) were prepared via graft polymerization of acrylamide onto chitosan backbone in presence of gelatin, CTS-g-PAAm/Ge, using potassium persulfate and N,N’-methylene bisacrylamide as initiator and crosslinker, respectively. These hydrogels were also partially hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. The formation of the grafted network was evidenced by Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Thermogravimetric Analysis (TGA). The porous structures were observed by Scanning Electron Microscope (SEM). From TGA analysis, it was concluded that the incorporation of the Ge in the CTS-g-PAAm network has marginally affected its thermal stability. The effect of gelatin content on the swelling capacities of these superabsorbent composites was examined in various media (distilled water, saline and pH-solutions). The water absorbency was enhanced by adding Ge in the network, where the optimum value was reached at 2 wt. % of Ge. Their hydrolysis has not only greatly optimized their absorption capacity but also improved the swelling kinetic.These materials have also showed reswelling ability. We believe that these super-absorbing materials would be very effective for the adsorption of harmful metal ions from wastewater.

The Effect of Surface Modifiers on the Mechanical and Morphological Properties of Waste Silicon Carbide Filled High-Density Polyethylene

Waste silicon carbide (waste SiC) filled high-density polyethylene (HDPE) with and without surface modifiers were studied. Two types of surface modifiers namely; high-density polyethylene-grafted-maleic anhydride (HDPE-g-MA) and 3-aminopropyltriethoxysilane have been used in this study. The composites were produced using a two roll mill, extruder and shaped in a hydraulic compression molding machine. The mechanical properties of polymer composites such as flexural strength and modulus, impact strength, tensile strength, stiffness and hardness were investigated over a range of compositions. It was found that, flexural strength and modulus, tensile modulus and hardness increased, whereas impact strength and tensile strength decreased with the increasing in filler contents, compared to the neat HDPE. At similar filler content, the effect of both surface modifiers increased flexural modulus, impact strength, tensile strength and stiffness but reduced the flexural strength. Morphological investigation using SEM revealed that the improvement in mechanical properties was due to enhancement of the interfacial adhesion between waste SiC and HDPE.

Kinetic Modeling of Transesterification of Triacetin Using Synthesized Ion Exchange Resin (SIERs)

Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH-were prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen- Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were welldescribed by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Graft Copolymerization of Methyl Methacrylate onto Cellulose in Homogeneous Medium – Effect of Solvent and Initiator

Homogeneous graft copolymerization of methyl methacrylate (MMA) onto cellulose was carried out in N, N – dimethyl acetamide/LiCl (DMAc/LiCl) and dimethyl sulfoxide/ paraformaldehyde (DMSO/PF) solvent system taking ceric ammonium nitrate (CAN), benzoyl peroxide (BPO) and tin (II)-2-ethyl hexanoate [Sn(Oct)2] as initiators. Different grafting parameters like graft yield (GY), grafting efficiency (GE) and total conversion of monomer to polymer (TC) were evaluated at different reaction conditions of temperature, time, and variation of the amount of monomer and initiator. The viscosity average molecular weight of grafted PMMA and number of grafts per cellulose chain were also calculated. The products were characterized by FT-IR and 1H-NMR analyses and possible reaction mechanisms were deduced. Thermal degradation of the grafted products was also studied by thermo-gravimetric analysis (TG) and differential thermo-gravimetry (DTG).

Manufacturing Process of a Novel Biomass Composite Inspired from Cellular Structure of Wood

A novel biomass composite inspired from wood porous structure was manufactured by impregnating vinyl monomer into wood cellular structure under vacuum conditions, and initiating the monomer for in situ polymerization through a thermal treatment. The vacuum condition was studied, and the mechanical properties of the composite were also tested. SEM observation shows that polymer generated in the wood porous structure, and strongly interacted with wood matrix; and the polymer content increased with vacuum value increasing. FTIR indicates that polymer grafted onto wood matrix, resulting chemical complex between them. The rate of monomer loading increased with increasing vacuum value and time, accordance with rate of polymer loading. The compression strength and modulus of elasticity linearly increased with the increasing rate of polymer loading. Results indicate that the novel biomass composite possesses good mechanical properties capable of applying in the fields of construction, traffic and so forth.

Seasonal Variations and Different Irrigation Programs on Nutrient Concentrations of 'Starkrimson Delicious' Apple Variety

This study was aimed to determine seasonal variations of leaf nutrient concentrations to define nutrient needs related to growing period and to compare irrigation programs in terms of nutrient uptake. In this study,'Starkrimson Delicious' variety grafted onto seedling rootstock was used during 2009-2010 growing seasons. The study was conducted at E─ƒirdir Fruit Growing Research Station. Leaf samples were taken in five different sample seasons (May, June, July, August and September). Four different pan coefficients (0.50, 0.75, 1.0, 1.25) were applied during drip irrigation treatments in 7 days irrigation interval. Leaf K, Mg, Ca, P, Fe, Zn, Mn and Cu concentrations were determined. The results showed that among the seasonal changes, the highest concentrations of K, Mg, P and Mn in leaves were recorded in May, followed by a decrease in the other months, while in contrast Ca and Fe showed the lowest concentration in May. Results of the study demonstrate that among irrigation programs K and Cu concentration in plants was significantly influenced. Cu concentrations decreased with seasonal variations and different irrigation programs. Thus, nutrient needs of 'Starkrimson Delicious'apple trees at different growth stages should be taken into consideration before making effective fertilization program.

Swelling Behavior and Cytotoxicity of Maleic Acid Grafted Chitosan

Chitosan is an attractive polysaccharide obtained by deacetylation of an abundant natural biopolymer called chitin. Chitin and chitosan are excellent materials. To improve the potential of chitin and chitosan modification is needed. In the present study, grafting of maleic acid on to chitosan by cerium ammonium nitrate in acetic acid solution was investigated with use of a microwave and reflux system. The grafted chitosan was characterized by using a Fourier-transform infrared spectrometry. The solubility and swelling behavior of grafted chitosans were determined in acetate buffer (pH 3.6), citrophosphate buffer (pH 5.6 and pH 7.0), and boric buffer (pH 9.2) solutions. The sample obtained by microwave system with use of a chitosan/maleic anhydride/ceric ammonium nitrate 0.2/3.922/0.99 gram of raw material within 30 minute showed the maximum swelling ratio (13.6) in boric buffer solution.

A Novel Strategy for Oriented Protein Immobilization

A new strategy for oriented immobilization of proteins was proposed. The strategy contains two steps. The first step is to search for a docking site away from the active site on the protein surface. The second step is trying to find a ligand that is able to grasp the targeted site of the protein. To avoid ligand binding to the active site of protein, the targeted docking site is selected to own opposite charges to those near the active site. To enhance the ligand-protein binding, both hydrophobic and electrostatic interactions need to be included. The targeted docking site should therefore contain hydrophobic amino acids. The ligand is then selected through the help of molecular docking simulations. The enzyme α-amylase derived from Aspergillus oryzae (TAKA) was taken as an example for oriented immobilization. The active site of TAKA is surrounded by negatively charged amino acids. All the possible hydrophobic sites on the surface of TAKA were evaluated by the free energy estimation through benzene docking. A hydrophobic site on the opposite side of TAKA-s active site was found to be positive in net charges. A possible ligand, 3,3-,4,4- – Biphenyltetra- carboxylic acid (BPTA), was found to catch TAKA by the designated docking site. Then, the BPTA molecules were grafted onto silica gels and measured the affinity of TAKA adsorption and the specific activity of thereby immobilized enzymes. It was found that TAKA had a dissociation constant as low as 7.0×10-6 M toward the ligand BPTA on silica gel. The increase in ionic strength has little effect on the adsorption of TAKA, which indicated the existence of hydrophobic interaction between ligands and proteins. The specific activity of the immobilized TAKA was compared with the randomly adsorbed TAKA on primary amine containing silica gel. It was found that the orderly immobilized TAKA owns a specific activity twice as high as the one randomly adsorbed by ionic interaction.