Unprecedented Chitin and Chitosan: A Chemical Overview

Chitin and Chitosan are polysaccharide polymers. Polysaccharide is a carbohydrate whose molecules consist of a number of sugar molecules bonded together. It contains more than 5,000 acetylglucosamine and glucosamine (sugar) units, respectively and their molecular weights are over one million Daltons. Most of the naturally occurring polysaccharides are neutral or acidic in nature, whereas Chitin and Chitosan are examples of highly basic polysaccharides. Chitin is isolated from crab and shrimp waste and is a renewable resource. It is widely accepted that this biopolymer is an important biomaterial in many aspects. This review explores the various aspects of Chitin research.     

Chitin and Chitosan Extracted from Shrimp Waste Using Fish Proteases Aided Process: Efficiency of Chitosan in the Treatment of Unhairing Effluents

Extraction and depolymerisation of chitin and chitosan from shrimp waste material was carried out using fish proteases aided process. A high deproteinization level (80 %) was recorded with an Enzyme/Substrate ratio of 10 U/mg. The demineralization of shrimp waste was completely achieved within 6 h at room temperature in HCl 1.25 M, and the residual content of calcium in chitin was below 0.01 %. The degree of N-acetylation, calculated from the ¹³C CP/MAS-NMR spectrum, was 85 %. The chitin obtained was converted to chitosan by N-deacetylation. X-ray diffraction patterns also indicated two characteristics crystalline peaks approximately at 10° and 20° (2θ). Chitosan was then evaluated in the treatment of unhairing effluents from the tanning industry. A result showed that chitosan as a coagulant has good performance in alkaline pH and at concentration of 0.5 g/L. Within these conditions, chitosan could decrease turbidity value, total suspended solids (89 % at 1.5 g/L), biological oxygen demand (33.3 % at 1.5 g/L) and chemical oxygen demand (58.7 % at 1.5 g/L).     

Study on the Physico-mechanical Properties of Photo-cured Chitosan Films with Oligomer and Acrylate Monomer

Chitosan films were prepared from dried prawn shell via chitin and then tensile properties like tensile strength (TS) and elongation at break (Eb) of the films were evaluated. Six formulations were developed using methyl methacylate (MMA) monomer and aliphatic urethane diacrylate oligomer (M-1200) in methanol along with photoinitator (Darocur-1664). Then the films were soaked in the formulations and irradiated under UV radiation at different doses for the improvement of physico-mechanical properties of chitosan films. The cured films were characterized by measuring TS, Eb, polymer loading (PL), water absorption and gel content properties. The formulation containing 43% MMA and 15% oligomer in methanol solution showed the best performance at 20th UV pass for 4 min soaking time.     

Using Chitosan as a Coagulant in Recovery of Organic Matters from the Mash and Lauter Wastewater of Brewery

Chitosan is a natural biopolymer which can be used to replace aluminum salts and chemical polymers as a coagulant to avoid the human health problems caused by the residual of aluminum and chemical polymers in water. Chitin is a major component in shrimp and crab shells, and chitosan can be produced from chitin via a deacetylated process. Since the biodegradation of chitin is very slow, large amount of discards from the processing of crustaceans has become a major concern in seafood industry. Therefore, more works are need to find the possible applications of chitin, chitosan and their derivatives. This research used chitosan as a coagulant to recover wheat dregs in the wastewater from washing the mash and the lauter unit in a brewery, and regards this study as an example to understand the influences of the characters of the wastewater on the treatment plant of brewery. The result shows that the␣wastewater from the mash and the lauter units can have the best treatment efficiency at the coagulant dosage of 120 mg/L in the original pH 4.5. Increasing the solution pH decreased the turbidity removal efficiency. The dominant mechanisms for chitosan to remove colloids in the␣wastewater are charge bridging and neutralization, and the later becomes less significant in␣the high pH. The coagulant of chitosan removed most of the colloidal form organic matter in the wastewater, but it has only little effect on the removal of dissolving organic matter. Chitosan is a natural material, after coagulation the sludge from the mash and lauter wastewater can serve directly as an animal husbandry fodder after been dehydrated. Therefore, the loading to wastewater treatment plant and the cost of treatment could be reduced.     

Simplified Fabrication of Optically Transparent Composites Reinforced with Nanostructured Chitin

Optically transparent films reinforced with micro to nano scale chitin particles were successfully developed in this study. Chitin composites based on micro scale particles which are larger than the optical wavelength do not cause light scattering provided that chitin particles are composed of nano structure networks which allow monomer impregnation and polymerization. This could lead a simplified process for fabricating transparent composites. The composites reinforced by the chitin micro particles not only retained the transparency of the plastic but also helped the effectiveness of its co-efficient of thermal expansion as similar to chitin nanofibers. Furthermore, chitin nanofibers transparent films are thermally stable against temperature as high as 200 °C for a long period of time. This could lead to number of important commercial applications, and is a significant move towards the sustainable utilization of marine bio-resources.     

甲壳素和壳聚糖在水处理中的应用

介绍了天然有机高分子化合物——甲壳素和壳聚糖的制备、化学结构和特性，阐述了其在水处理中的应用及发展前景。甲壳素和壳聚糖的来源广泛，其性能优良、无毒、无公害、可生物降解，可用作吸附剂、絮凝剂、分离膜材料、离子交换剂和杀菌剂，是一类非常有开发利用前景的新型水处理材料。     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Oyster shell as substitute for aggregate in mortar.

Enormous amounts of oyster shell waste have been illegally disposed of at oyster farm sites along the southern coast of Korea. In this study to evaluate the possibility of recycling this waste for use as a construction material, the mechanical characteristics of pulverized oyster shell were investigated in terms of its potential utilization as a substitute for the aggregates used in mortar. The unconfined compressive strengths of various soil mortar specimens, with varying blending ratios of cement, water and oyster shell, were evaluated by performing unconfined compression tests, and the results were compared with the strengths of normal cement mortar made with sand. In addition, the effect of organic chemicals on the hardening of concrete was evaluated by preparing ethyl-benzene-mixed mortar specimens. The long-term strength improvement resulting from the addition of fly ash was also examined by performing unconfined compression tests on specimens with fly-ash content. There was no significant reduction in the compressive strength of the mortars containing small oyster shell particles instead of sand. From these test data, the possible application of oyster shells in construction materials could be verified, and the change in the strength parameters according to the presence of organic compounds was also evaluated.     

Improvement of Physico-mechanical Properties of Chitosan Films by Photocuring with Acrylic Monomers

Natural polymer, chitosan was obtained from dried prawn shell waste through the preparation of chitin and was characterized. Thin film of chitosan was prepared by casting method from its 2% chitosan solution. Mechanical properties like tensile strength (TS), elongation at break (Eb) of chitosan film were studied. Five formulations were developed with 2-ethyl-2-hydroxy methyl-1,3-propandiol trimethacrylate (EHMPTMA), a trifunctional monomer and 2-ethylhexyl acrylate (EHA), a monofunctional monomer in the presence of photoinitiator Darocur-1664 (2%). The film was soaked in those monomer formulations in dissimilar soaking times and irradiated under UV-radiation at different radiation intensities for the improvement of the properties of chitosan film. The cured films were then subjected to various characterization tests like TS, Eb, polymer loading (PL), water absorbency, gel content etc. The formulation, containing 25% EHMPTMA and 73% EHA showed the best performance at 10th UV passes of UV radiation for 4 min soaking time.     

A novel method for the preparation of silver/chitosan-O-methoxy polyethylene glycol core shell nanoparticles

Uniformly sized silver/chitosan-O-methoxy polyethylene glycol (chitosan-O-MPEG) core shell nanoparticles with different degree of substitution were synthesized. Thus, N-phthaloyl chitosan is reacted with polyethylene glycol monomethyl ether iodide in the presence of silver oxide by the following steps. At first, amino groups of chitosan are protected by fourfold excess of phthalic anhydride. Then N-phthaloyl chitosan is reacted with an appropriate amount of monomethyl ether iodide in the presence of silver oxide and lastly N-phthaloyl groups are removed to yield silver/chitosan-O-MPEG core shell nanoparticles. Structure of prepared silver/chitosan-O-MPEG core shell nanoparticles have been characterized by UV/Vis spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray diffraction, and scan electron microscopy (SEM-EDX). Experimental results revealed that the prepared silver core particles had the size 18?±?2?nm. Core shell structure with chitosan-O-MPEG-coating had the size 40?±?2?nm.     

Chitin biodegradation and wound healing in tree bark tissues

Chitin biodegradation and wounded bark tissue healing were demonstrated in several evergreen and deciduous trees by dressing with a sheet of chitin-containing films or sponges. Chitinase activities in the tree bark tissues around the wounds were enhanced by this treatment up to four times those of the untreated wounds. Significant seasonal changes of chitinase activities were observed with the bark and leaf tissues of deciduous trees, but few with those of evergreen trees. A sheet of chitin films implanted or dressed in the tree bark tissues was biodegraded within 4 to 24 weeks after implantation and was assimilated into the wounded bark tissues, resulting in the stimulation of the wounded bark tissue healing.     

Effects of oyster shell on soil chemical and biological properties and cabbage productivity as a liming materials

Oyster shell, a byproduct of shellfish-farming in Korea and containing a high amount of CaCO(3), has a high potential to be used as a liming material in agriculture. However, the agricultural utilization of oyster shell is limited due to its high concentration NaCl. The oyster-shell meal collected had a low concentration of water soluble NaCl (mean 2.7 g kg(-1)), which might be a result of stacking the material for 6 months in the open field. It has a very similar liming potential with calcium carbonate, with 3.4 and 3.8 Mg ha(-1) for silt loam (SiL, pH 6.2) and sandy loam (SL, pH 5.8) to bring the soil pH to 6.5, respectively. To determine the effect of crushed oyster-shell meal on improving soil chemical and biological properties and crop plant productivity, oyster-shell meal was applied at rates of 0, 4, 8, 12, and 16 Mg ha(-1) before transplanting Chinese cabbage (Brassica campestris L.) in the two soils mentioned above. Soil pH was significantly increased to 6.9 and 7.4 by 16 Mg ha(-1) shell meal application (4 times higher level than the recommendation) in SiL and SL, respectively, at harvesting stage. The effect of liming was found higher in SL compared to SiL soil, probably due to the different buffering capacity of the two soils. The concentration of NaCl and EC value of soils were found slightly increased with shell meal applications, but no salt damage was observed. Oyster-shell meal application increased soil organic matter, available P, and exchangeable cations concentrations. The improved soil pH and nutrient status significantly increased the microbial biomass C and N concentrations and stimulated soil enzyme activities. With the exception of acid phosphomonoesterase (PMEase) activity, which decreased with increasing soil pH in SL but slightly increased in SiL, the activities of urease and alkali PMEase increased markedly with increasing soil pH by shell meal application. The improved soil chemical and biological properties resulted in increased crop productivity. The highest yield in Chinese cabbage was achieved following the application of 8 Mg ha(-1) oyster-shell meal. Conclusively, crushed oyster shell could be used as an alternative liming material to restore the soil chemical and microbial properties in upland soil and to increase crop productivity.     

Autotrophic Biological Denitrification for Complete Removal of Nitrogen from Septic System Wastewater

The overall objective of this research was to develop a reliable, robust, and maintenance-free passive system for biological denitrification in on-site wastewater treatment systems. The process relies on sulfur oxidizing denitrifying bacteria in upflow packed bioreactors. Since this process consumes alkalinity, it is necessary to add a solid-phase buffer that can scavenge the H⁺ as it is generated by the biologically-mediated reaction and arrest the drop in the pH value. This study investigated the use of limestone, marble chips and crushed oyster shell as solid-phase buffers that provide alkalinity. Two bench-scale upflow column reactors and two field-scale bioreactors were constructed and packed with sulfur pellets and an alkalinity source. The pilot scale bioreactors (∼200 L each) were installed at the Massachusetts Alternative Septic System Test Center (MASSTC) in Sandwich, MA. The pilot-scale bioreactors performed better when oyster shell was used as the solid-phase buffer vis-à-vis marble chips. In both (pilot-scale and laboratory-scale) systems, denitrification rates were high with the effluent NO₃ ⁻ —N concentration consistently below 8 mg/L.     

Environmental Effects Monitoring in Sydney Harbor During Remediation of One of Canada's Most Polluted Sites: A Review and Lessons Learned

This article reviews a comprehensive marine environmental effects monitoring program (MEEMP) comprised of components capable of detecting changes in the marine environment over short or extended temporal scales during remediation of one of Canada's most polluted sites at the Sydney Tar Ponds. The monitoring components included: water and sediment quality, amphipod toxicity testing, mussel tissue, crab hepatopancreas tissue, and benthic community assessments. The MEEMP was designed to verify the impact predictions for the remediation project (i.e., no immediate damage to the marine ecosystem through remediation activities). Some components were capable of providing conclusive data (e.g., sediment and water quality), while others only yielded data that were inconclusive or difficult to attribute to remediation activities (e.g., intertidal community assessments and amphipod toxicity testing). Components that provided only inconclusive results or were difficult to attribute to remediation activities were discontinued, resulting in substantial cost savings during the project, but without compromising the overall objectives of the program, which was to monitor for potential adverse environmental effects of remediation on the marine environment in Sydney Harbor and to verify environmental effects predictions made in the Environmental Impact Statement for the project. The rationale for discontinuing certain MEEMP components and discussion of conclusive results are incorporated into “lessons learned” for environmental remediation practitioners and regulators working on similar large‐scale multiyear remediation projects. © 2014 Wiley Periodicals, Inc.     

Solubility parameters for determining optimal solvents for separating PVC from PVC-coated PET fibers

Poly(vinyl chloride) (PVC) in PVC-coated poly(ethylene terephthalate) (PET) fabrics can be separated through dissolution in a suitable solvent, leaving only the PET fibers. We investigated the solubility of PVC in 30 solvents using swelling tests. The results were compared with those obtained using the Hansen, Gutmann, Swain, E _T(30), and Kamlet–Taft parameters. For this purpose, Gaussian plots of the PVC swellability versus solubility parameter were used to decide the applicability of the solubility parameter system. Only Gutmann’s electron acceptor–donor parameter (AN + DN) and the Kamlet–Taft parameters β and π* could describe the PVC-solvent system satisfactorily. Tetrahydrofuran (THF), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), cyclohexanone, and cyclopentanone were tested for separating PVC from PET at different temperatures. THF dissolved PVC at 20 °C, while cyclohexanone and cyclopentanone did so at 40 °C. Traces of PVC remained on the PET fibers when DMF was used. Complete dissolution of PVC was not achieved at any temperature with MEK. The present work shows that solubility parameters are a helpful tool for the search for suitable solvents. It shows also that solubility parameters have to be selected carefully, since their usefulness depends strongly on the polymer properties.     

Two decision analysis approaches: Choosing a chemical analysis method

This article illustrates how two different decision analysis (DA) methods can be used to assist in making environmental remediation decisions. The two DA methods are Multiattribute Utility Theory (MAUT) and the Analytic Hierarchy Process (AHP). MAUT and AHP differ greatly in their underlying philosophies. MAUT employs an interval scale and constructs utility functions that quantify the total utility to the decision maker of each technology alternative; AHP employs a ratio scale and uses pairwise comparisons to produce a final ranking of the alternatives that reflects the decision maker's comparative preferences. In this study, the same technology was ranked first by both methods; however, the remaining rankings did not agree. Also, statistical analysis indicated that some score differences may be statistically insignificant. These results are presented and discussed along with a comparison of the features, advantages, and disadvantages of these two DA approaches.     

Effect of the Incorporation of Lysozyme on the Properties of Jackfruit Starch Films

Jackfruit starch based biodegradable films containing lysozyme were characterized for their antimicrobial activity, thickness, solubility, water vapor permeability and mechanical properties. The biodegradable films had good appearance and antimicrobial activity against Micrococcus lysodeikticus. The thickness of the biodegradable films were not affected by the variation in pH, but the addition of lysozyme increased the thickness, the thickest films being those with the highest lysozyme concentrations. The variation in pH of the filmogenic solutions affected the solubility of the biodegradable films, water solubility being greatest at pH 7.0 and with the highest lysozyme concentration. The permeability of the biodegradable films was increased by incorporating lysozyme. The lysozyme concentration and pH variation caused changes in the mechanical properties. The addition of 8% lysozyme increased the tensile strength and Young’s modulus for all the pH values studied. With respect to the release of antimicrobial activity, the diffusion of lysozyme was shown to follow Fickian transport mechanism.     

Preparation of Chitin/Cellulose Films Compatibilized with Polymeric Ionic Liquids

This paper reports the preparation of chitin/cellulose films compatibilized with polymeric ionic liquids. In-situ (co)polymerization of polymerizable ionic liquids, 1-(3-methacryloyloxypropyl)-3-vinylimidazolium bromide (1) and 1-methyl-3-vinylbenzylimidazolium chloride (3), was carried out in the presence of a radical initiator, AIBN, in the chitin/cellulose solution with ionic liquid solvents (1-butyl-3-methylimidazolium acetate and chloride, BMIMOAc and BMIMCl, respectively), followed by the appropriate procedure to give the desired films. The presence of the polymeric ionic liquid in the film was confirmed by the IR measurement. The powder X-ray diffraction analysis suggested that crystalline structures of the polysaccharides were largely disrupted in the film, as same as that of a chitin/cellulose film prepared by the AMIMOAc/BMIMCl system. These results were different from the XRD result of a chitin/cellulose film prepared by the 1-allyl-3-methylimidazolium bromide/BMIMCl system reported in our previous study, in which some crystalline structures were still remained in the film. Furthermore, the mechanical properties of the present films were evaluated by tensile testing, which were affected by the molar ratios of the polymeric ionic liquids to the polysaccharides and the compositional ratios of the two units 1 and 3.     

Evaluation of Extracted Chitosan from Portunus Pelagicus for the Preparation of Chitosan Alginate Blend Scaffolds

In recent years there is a growing need in generating a biocompatible and cost effective porous scaffold for tissue engineering purposes. Therefore, this study focused on conversion of the shell waste of locally available crab variety P.pelagicus (Blue swimming crab) into the chitosan scaffold. As the poor mechanical strength of chitosan limits its usage in tissue engineering, it was blended with alginate. The scaffolds were prepared by the freeze gelation method which requires less time and minimum energy, with fewer residual solvent and easier to scale up. To the best of our knowledge there are no reports on scaffold preparation from the extracted chitosan, blended with alginate by freeze gelation method. The biological properties of chitosan-alginate scaffolds (Cts–Alg) were evaluated and compared with those of chitosan scaffolds. The prepared scaffolds were characterized by SEM, swelling property, in vitro enzymatic degradation, and hemo, biocompatibility properties. Chitosan-alginate scaffolds had an average pore size of 40 μm and tensile strength of 0.564 ± 0.0.018 % MPa. Its swelling ratio was 27.5 ± 0.28 %, with mass loss percentage of 10 ± 0.33 % after 4 weeks of degradation. It has exhibited good hemocompatible properties too. Mouse fibroblast 3T3 cells were able to adhere and proliferate well in the blended scaffold. All these results indicated that chitosan-alginate scaffold is a suitable alternative substitute for tissue engineering.     

催化显色分光光度法测定水中银

论述了目前测定水中银的常见方法，验证了银对亚铁氰化钾与邻菲罗啉反应的催化作用，建立了测定水中银的催化显色分光光度法。