The effect of reaction time and temperature during heterogenous alkali deacetylation on degree of deacetylation and molecular weight of resulting chitosan

The objective of the study is to elucidate the effect of reaction time and temperature during heterogenous alkali reaction on degree of deacetylation (DD) and molecular weight (MW) of the resulting chitosans, and to establish the reaction conditions to obtain desired DD and MW chitosan products. Chitin was extracted from red shrimp process waste. DDs and MWs were determined by infrared spectroscopy (IR) and static light scattering, respectively. The results are as follow: The DD and MW of chitin obtained were 31.9% and 5637 kDa, respectively. The DD of the resulting chitosan increased along with reaction time and/or reaction temperature. The DDs of the resulting chitosan that were obtained from 140°C were higher than those reacted at 99°C. The highest DD of the resulting chitosans after alkali deacetylation at 99 and 140°C were 92.2 and 95.1%, respectively. The DDs of chitosans increased fast at the beginning of reaction process then slowed over time. The reaction rate and rate constant of the deacetylation reaction decreased with increasing DD of the reactant. The MWs of chitosans decreased along with the deacetylation time. MW of those chitosans reacted at 140°C are smaller than those at 99°C. The rate of chitosan degradation was above 43.6%/h in the initial stage, then decreased to about 20%/h. The degradation rate constants raised substantially in the late stage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2917–2923, 2003     

壳聚糖脱乙酰度测定方法研究新进展

主要介绍近年来壳聚糖脱乙酰度测定方法研究新进展,概述了双突跃电位滴定法——加酶预处理、光纤折射传感法、拉曼光谱法、库仑滴定法等测定原理与特点,并作出比较,为相关科学研究和工业生产测定方法的选择提供理论参考。     

壳聚糖脱乙酰度测定方法研究新进展

主要介绍近年来壳聚糖脱乙酰度测定方法研究新进展,概述了双突跃电位滴定法——加酶预处理、光纤折射传感法、拉曼光谱法、库仑滴定法等测定原理与特点,并作出比较,为相关科学研究和工业生产测定方法的选择提供理论参考。     

Effect of degree of deacetylation of chitosan on the kinetics of ultrasonic degradation of chitosan

The objective of the study was to explore the effect of the degree of deacetylation (DD) of the chitosan used on the degradation rate and rate constant during ultrasonic degradation. Chitin was extracted from red shrimp process waste. Four different DD chitosans were prepared from chitin by alkali deacetylation. Those chitosans were degraded by ultrasonic radiation to different molecular weights. Changes of the molecular weight were determined by light scattering, and data of molecular weight changes were used to calculate the degradation rate and rate constant. The results were as follows: The molecular weight of chitosans decreased with an increasing ultrasonication time. The curves of the molecular weight versus the ultrasonication time were broken at 1‐h treatment. The degradation rate and rate constant of sonolysis decreased with an increasing ultrasonication time. This may be because the chances of being attacked by the cavitation energy increased with an increasing molecular weight species and may be because smaller molecular weight species have shorter relaxation times and, thus, can alleviate the sonication stress easier. However, the degradation rate and rate constant of sonolysis increased with an increasing DD of the chitosan used. This may be because the flexibilitier molecules of higher DD chitosans are more susceptible to the shear force of elongation flow generated by the cavitation field or due to the bond energy difference of acetamido and β‐1,4‐glucoside linkage or hydrogen bonds. Breakage of the β‐1,4‐glucoside linkage will result in lower molecular weight and an increasing reaction rate and rate constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3526–3531, 2003     

紫外测定壳聚糖脱乙酰度方法的探讨

分别采用直接、一阶导数、多波长和双内标等4种紫外分光光度法测定壳聚糖的脱乙酰度,评价4种紫外测定方法,并与胶体滴定、电位滴定和氢核磁3种测定方法进行了比较。结果表明,采取上述紫外法测定壳聚糖脱乙酰度值均高于胶体滴定和氢核磁测定值。故准确测定高脱乙酰度壳聚糖的脱乙酰度,紫外法非首选方法。     

红外光谱法测定壳聚糖脱乙酰度

以碱量法为对比方法,考察了基于A1655／A3450和A1320／A1420的2种红外光谱计算壳聚糖脱乙酰度方法的准确性。结果表明,红外光谱法虽精密度低于碱量法,但基于A1655／A3450的红外测试结果与碱量法基本相吻合;基于A1320／A1420加的红外光谱计算结果略高于碱量法,与商家标注值相吻合,且不受样品含少量水、残酸或残碱的影响。红外光谱法是一种较为理想的壳聚糖脱乙酰度测定方法,同时采用A1655／A3450和A1320／A1420计算更利于得到准确的测定结果。     

The effect of the Pt deposition method and the support on Pt dispersion on carbon nanotubes

Carbon nanotube supported platinum (Pt/CNTs) catalysts prepared by different Pt deposition methods and on different CNT supports were studied. Colloidal based methods were demonstrated to be more effective than other wet chemistry deposition methods (e.g., impregnation and precipitation) for the preparation of highly dispersed Pt/CNTs. Pt catalyst supported on CNTs with a dispersion uniformity comparable to that supported on carbon powder was achieved using a zwitterionic surfactant 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as stabilizer in a monitored pH environment. It was experimentally observed that oxygen-containing surface functionalities on CNTs can greatly affect the catalyst particle dispersion by manipulating Pt anchoring and/or nucleating sites. Furthermore, it was revealed that the performance of Pt/CNTs based fuel cell is strongly dependent on the electrode fabrication method.     

壳聚糖脱乙酰度测定方法的总结与比较

测定壳聚糖脱乙酰度(DD)的方法主要分为三类:①光谱法:紫外、红外光谱和核磁法;②破坏样品法:色谱法、差示扫描量热和元素分析法;③滴定法:酸碱、电位和胶体滴定等方法。对壳聚糖脱乙酰度测定方法进行总结与比较,为研究者选择最佳的壳聚糖脱乙酰度测定方法提供理论依据。     

Effect of molecular weight and degree of deacetylation of chitosan on urea adsorption properties of copper chitosan

Copper chitosan complexes prepared by different specifications of chitosan and copper sulfate were used as urea sorbents. Experimental results showed that the adsorption capacity for urea of copper chitosan increased with an increasing degree of deacetylation and decreasing molecular weight of chitosan. The urea adsorption capacity of copper chitosan was 120.0 mg/g, when 1.0 g of copper chitosan was admitted to 100 mL of a 1300 mg/mL (pH 6.0) urea solution, with chitosan degree of deacetylation of 84.3% and viscosity molecular weight of 6.5 × 10⁵, at 37°C for 8 h. No elution of the copper from the copper chitosan could be detected under the optimal conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1520–1523, 2003     

Decoration of carbon nanotubes with chitosan

In this letter, a non-destroyable surface decoration of carbon nanotubes with biopolymer chitsoan via a controlled surface-deposition and crosslinking process is described. The method utilizes the emulsifying capacity of chitosan, the completely different water-solubility of chitosan in acidic and basic solutions, and the crosslinking reaction among chitosan polymers. As the pristine structures of the carbon nanotubes are not recomposed under those treatments, the unique properties of the pristine carbon nanotubes have not been compromised. Combining the properties of carbon nanotubes and the versatility and biocompatibility of chitosan, these chitosan surface-decorated carbon nanotubes could find potential applications in biosensing, gene and drug delivering as well as other chemical and biological applications.     

Effects of the molecular weight and the degree of deacetylation of chitosan oligosaccharides on antitumor activity

Effects of the degree of deacetylation (DDA) and the molecular mass of chitosan oligosaccharides (CTS-OS), obtained from the enzymatic hydrolysis of high molecular weight chitosan (HMWC), on antitumor activity was explored. The DDA and molecular weights of CTS-OS were determined by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-TOF MS) analysis. The CTS-OS were found to be a mixture of mainly dimers (18.8%), trimers (24.8%), tetramers (24.9%), pentamers (17.7%), hexamers (7.1%), heptamers (3.3%), and octamers (3.4%). The CTS-OS were further fractionated by gel-filtration chromatography into two major fractions: (1) COS, consisting of glucosamine (GlcN)(n), n = 3-5 with DDA 100%; and (2) HOS, consisting of (GlcN)(5) as the minimum residues and varying number of N-acetylglucosamine (GlcNAc)(n), n = 1-2 with DDA about 87.5% in random order. The cytotoxicities, expressed as the concentration needed for 50% cell death (CC(50)), of CTS-OS, COS, and HOS against PC3 (prostate cancer cell), A549 (lung cancer cell), and HepG2 (hepatoma cell), were determined to be 25 μg·mL(-1), 25 μg·mL(-1), and 50 μg·mL(-1), respectively. The HMWC was approximately 50% less effective than both CTS-OS and COS. These results demonstrate that the molecular weight and DDA of chitosan oligosaccharides are important factors for suppressing cancer cell growth.     

The effect of carbon nanotube properties on the degree of dispersion and reinforcement of high density polyethylene

The efficacy with which a range of nanotubes could reinforce a high density polyethylene (HDPE) matrix was investigated, in relation to nanotube diameter, purity, functionalization, alignment and nanotube bulk density. Composites were prepared by melt blending multiwall carbon nanotubes (MWNTs) with high density polyethylene (HDPE), followed by the injection molding of tensile specimens. At a 5 wt% loading, the most effective nanotubes were those of large diameter, received in an aligned form with low bulk density, producing a 66% increase in elastic modulus and a 69% improvement in yield stress. This was contradictory to theoretical mechanics calculations that predicted an increasing degree of reinforcement for nanotubes of reduced diameter. This difference was explained by the higher degree of dispersion observed in the composites with MWNTs of greater diameter.     

Evaluation of molar weight and deacetylation degree of chitosan during chitin deacetylation reaction: Used to produce biofilm

Chitosan is a polysaccharide derived from chitin, mainly of crustacean shells and shrimp wastes. The utilization of chitosan is related to the molar weight and deacetylation degree of the biopolymer. The aim of this work is to study the chitin deacetylation reaction, by the viscosity average molar weight and deacetylation degree of chitosan as a function of reaction time. Deacetylation was carried out in concentrated alkaline solution, 421 g L⁻¹, at 130 °C and the reaction occurred during 4 h. Chitosan paste obtained after 20, 90 and 240 min was used to produce biofilms, which were characterized according water vapor permeability and mechanical properties (tensile strength and percentage tensile elongation at break). During the reaction time deacetylation degree reached 93%, and a 50% reduction in the viscosity average molar weight value in relation to the value of the first 20 min of reaction was found Both reactions presented a kinetic behavior of the pseudo-first order. Biofilm produced from the paste of chitosan with high deacetylation degree showed higher water vapor permeability (WVP), tensile strength (TS) and elongation (E) when compared to films with a low deacetylation.     

碳纳米管/壳聚糖复合材料的研究进展

碳纳米管/壳聚糖复合材料是一种新型的生物复合材料,具有独特的结构以及优良的力学、生物、电化学等性能。本文综述了碳纳米管/壳聚糖复合材料的各种制备方法,并详细讨论了溶液共混法、静电自组装法、逐层自组装法等方法的优缺点。还概括了碳纳米管/壳聚糖复合材料在电化学分析、生物传感器、电驱动等领域的应用进展,并展望了其主要研究方向和发展趋势。     

Effect of processing technique on the dispersion of carbon nanotubes within polypropylene carbon nanotube‐composites and its effect on their mechanical properties

Carbon nanotube‐reinforced polymer composites are being investigated as promising new materials having enhanced physical and mechanical properties. With regards to mechanical behavior, the enhancements reported thus far by researchers are lower than the theoretical predictions. One of the key requirements to attaining enhanced behavior is a uniform dispersion of the nanotubes within the polymer matrix. Although solvent mixing has been used extensively, there are concerns that any remaining solvent within the composite may degrade its mechanical properties. In this work, a comparison is carried out between solvent and “solvent‐free” dry mixing for dispersing multiwall carbon nanotubes in polypropylene before further melt mixing by extrusion. Various weight fractions of carbon nanotubes (CNTs) are added to the polymer and their effect on the mechanical properties of the resulting composites is investigated. Enhancements in yield strength, hardness, and Young's modulus when compared with the neat polymer, processed under similar conditions, are observed. Differences in mechanical properties and strain as a function of the processing technique (solvent or dry) are also clearly noted. In addition, different trends of enhancement of mechanical properties for the solvent and dry‐mixed extrudates are observed. Dry mixing produces composites with the highest yield strength, hardness, and modulus at 0.5 wt% CNT, whereas solvent mixing produces the highest mechanical properties at CNT contents of 1 wt%. It is believed that this difference is primarily dependent on the dispersion of CNTs within the polymer matrix which is influenced by the processing technique. Field emission scanning electron microscopy analysis shows the presence of clusters in large wt% CNT samples produced by dry mixing. Samples produced by solvent mixing are found to contain homogeneously distributed CNTs at all CNT wt fractions. CNT pull‐out is observed and may explain the limited enhancement in mechanical properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

The effect of pH and ionic strength on the dispersion of carbon nanotubes in poly(acrylic acid) solutions

The dispersion of three kinds of acid‐treated carbon nanotubes (CNTs) in poly(acrylic acid) (PAA) aqueous solution of different pH and ionic strengths (varied by NaCl, KCl and ZnCl₂) was investigated by visual observation, zeta potential, particle size analysis, transmission electron microscopy and scanning electron microscopy. Visual observation revealed that the dispersion of CNTs acid treated at 60 °C for 3 h and at 80 °C for 2 h was poor in aqueous solutions with pH < 2 or pH > 12. The poor dispersion of acid‐treated CNTs may be improved by adding PAA. In particular, PAA improved the dispersion of CNTs with greater COOH content. In a low pH solution (pH 1.5), a higher PAA content resulted in poorer CNT dispersion while in a high pH solution (pH 12.5), a higher PAA content led to better CNT dispersion. For superior dispersion in a basic aqueous solution (pH 12.5), experimental data showed that a greater atomic radius or a higher cationic charge of the added salt may result in faster aggregation and thus precipitation of CNTs. Copyright © 2011 Society of Chemical Industry     

Diameter-selective dispersion of double-walled carbon nanotubes by lysozyme

We have utilized lysozyme to non-covalently functionalize and disperse double-walled carbon nanotubes (DWNTs) in aqueous solution. Lysozyme preferentially binds and disperses DWNTs with larger diameters. This is a facile and effective method to fractionalize and enrich DWNTs with certain diameters.     

Effect of degree of deacetylation on solubility of low‐molecular‐weight chitosan produced via enzymatic breakdown of chitosan

Chitosan has emerged as a unique biomaterial, possessing scope in diverse applications in the biomedical, food and chemical industries. However, its high molecular weight is a concern when handling the polymer. Various techniques have been explored for depolymerization of this polymer, wherein enzymes have emerged as the most economic method having minimum degrading effect on the polymer and resulting in formation of side products. Chitosan can be depolymerized using a broad range of enzymes. In this study, various enzymes like α‐amylase, papain, pepsin and bromelain were employed to depolymerize chitosan and convert it into its lower molecular weight counterpart. Further, attempts were made to elucidate the process of depolymerization of chitosan, primarily by determining the change in its viscosity and hence its molecular weight. The process of depolymerization was optimized using a one‐factor‐at‐a‐time approach. The molecular weight of the resultant chitosan was estimated using gel permeation chromatography and infrared spectroscopy. These studies revealed a considerable decrease in molecular weights of chitosan depolymerized by pepsin, papain, bromelain and α‐amylase, resulting in recovery of the low‐molecular‐weight chitosan of 76.09 ± 5, 74.18 ± 5, 55.75 ± 5 and 49.18 ± 5%, respectively. Maximum yield and depolymerization were obtained using pepsin and papain due to their enzymatic recognition pattern, which was also validated using studies involving molecular dynamics. © 2019 Society of Chemical Industry     

The fine dispersion of functionalized carbon nanotubes in acrylic latex coatings

Nanocomposites of a polymer and carbon nanotubes exhibit high electrical and thermal conductivity and enhanced mechanical properties in comparison to the polymer alone. Film formation from latex dispersions is an ideal way to create nanocomposite coatings with the advantages of solvent-free processing and a high uniformity of dispersion. It is shown here that carbon nanotubes functionalised with poly(vinyl alcohol) (PVA) can be blended with two types of acrylic latex to create stable colloidal dispersions without the need for added surfactant or emulsifier. Waterborne nanocomposite films with optical transparency can be formed. Microscopic analysis shows that the PVA-functionalized nanotubes are finely and uniformly dispersed in the polymer matrix.