质子化改性壳聚糖吸附硫酸根行为及其光谱分析

壳聚糖(CTS)具有活性基团氨基和羟基,可用作吸附剂。在酸性介质中其氨基容易质子化形成氨基正离子,具有吸附阴离子的能力,同时也导致吸附剂的溶解流失;进行交联处理可提高吸附剂的酸稳定性,但也导致吸附性能的下降。因此可进行氨基保护后进行交联以改善其酸溶液稳定性,再脱去氨基保护剂进行质子化处理以获得较好的对阴离子的吸附性能。以甲醛为氨基保护剂,戊二醛为交联剂,通过反相悬浮法制得交联壳聚糖(CCTS),对其进行质子化制得质子化改性壳聚糖吸附剂(P-CCTS),并首次将该吸附剂用于处理水溶液中的硫酸根离子。通过静态吸附实验,考察了质子化改性壳聚糖对硫酸根的吸附性能;利用X射线能谱元素分析(EDS)和红外光谱分析(FTIR)对该吸附剂的制备以及对硫酸根离子的吸附过程进行了表征,探索了交联反应和吸附反应的发生机理。实验结果表明：质子化改性壳聚糖吸附剂与交联壳聚糖相比,其对硫酸根离子的吸附性能提高了约10倍;甲醛、戊二醛的醛基与壳聚糖的交联反应主要发生在的氨基(—NH₂)和部分一级羟基(C₆—OH)上;质子化过程中交联壳聚糖的氨基与质子化剂形成了氯化壳聚糖氨盐;对硫酸根离子的吸附则主要是质子化氨基上氯离子与硫酸根离子的交换作用。     

壳聚糖的吸附行为及其FTIR光谱研究

用自制的壳聚糖对几种酸性染料和碱性染料模拟废水进行了吸附行为的研究,考察了吸附时间、壳聚糖脱已酰度及废水pH值对吸附效果的影响。研究表明,在吸附开始的20 min内,壳聚糖对碱性品红和番红花红的吸附已基本达到平衡,且用量只为活性炭用量的2／3的情况下,对染料的吸附效果与活性炭几乎相当;它对酸性大红的吸附过程呈现一级反应动力学特征。文章还采用傅里叶变换红外光谱对壳聚糖吸附染料的机理进行了探讨,研究发现,壳聚糖分子中存在的大量羟基参与了对碱性品红和番红花红的吸附。     

壳聚糖与五种过渡金属离子形成配合物的研究

差热分析法、红外光谱法研究了壳聚糖和5种过渡元素金属离子盐(Fe3 、Co2 、Ni2 、Cu2 、Zn2 )形成不同壳聚糖金属配合物变化特征.结果表明,由于壳聚糖分子中含有大量的-NH2、-OH基,与金属离子发生配位作用后,吸热和放热峰均发生了较大的位移,在3400cm-1羟基和氨基、1654.11cm-1处酰胺IR吸收峰均发生了相应的变化;而位于1379cm-1 C-H弯曲和-CH3对称变形振动吸收峰保持不变,表明壳聚糖与金属离子发生配位后稳定空间构象发生变化.     

和频光谱研究萃取剂TOPO分子在空气/水界面处的取向行为

采用和频光谱研究了萃取剂TOPO分子在空气/水界面处的取向行为。研究发现,在不同膜压条件下,TOPO分子在水表面排布的有序化程度不同。膜压越大,TOPO分子在水表面的堆积密度越大,其分子碳链的取向越倾向于垂直空气/水界面。研究萃取剂分子在界面的取向行为,可以为理解界面处萃取剂分子与目标待萃取离子的相互作用机理提供思路。     

硫酸交联壳聚糖干膜的13C CP MAS NMR研究

以不同浓度硫酸交联的壳聚糖干膜为研究对象,在国内首次采用¹³C CP MAS NMR技术从分子水平上对壳聚糖膜的结构进行研究,结果表明干膜壳聚糖分子的构象能直观地反映出膜的交联状况,交联状况与膜的分离性能密切相关,但仅对干膜的考察还不够全面.     

基于荧光光谱的脂质体制备与稳定性的研究

利用L-α-磷脂酰胆碱和胆固醇分子制备脂质体体系,通过监测脂质体内部包裹的对pH变化敏感的荧光指示剂8-羟基芘-1,3,6-三磺酸三钠盐的荧光强度变化实现对脂质体稳定性的表征。研究发现,在脂质体磷脂膜中引入一定比例的胆固醇分子有助于提高脂质体的稳定性(L-α-磷脂酰胆碱∶胆固醇=4∶1)。利用温水浴-液氮多次冻融循环,在强烈外界温差作用条件下,L-α-磷脂酰胆碱和胆固醇形成的贴壁薄膜重组成内外两侧均为亲水头部而疏水尾部均指向脂双层膜内部的稳定脂质体,在10min内稳定性高达99%,9 200s内稳定性依然可以达到92%。基于以上研究成果,我们在脂质体的外部环境中引入K+载体缬氨霉素,结果表明缬氨霉素可以成功的插入至磷脂双分子层膜中并高效运输K+。     

羧甲基壳聚糖与铕、铽配合物的合成和配位机理研究

用羧甲基壳聚糖分别与硝酸铕和硝酸铽反应,制备了羧甲基壳聚糖-铕和羧甲基壳聚糖-铽稀土配合物。用红外光谱和X射线光电子能谱(XPS)等分析测试手段对配合物进行表征。对配合物配位机理进行了初步的研究,配合物中羧甲基壳聚糖中不仅羧基参与了配位,氨基上的N原子和羟基氧原子也参与了配位。     

过渡金属表面γ-氨丙基三甲氧基硅烷膜的研究

本文对在过渡金属铁、镍电极表面制备得到的γ-氨丙基三甲氧基硅烷(γ-APS)膜进行了研究。实验中对硅烷膜用X-射线光电子能谱(XPS)、现场表面增强拉曼散射光谱(SERS)和原子力显微镜(AFM)进行了表征。X-射线光电子能谱(XPS)的结果发现存在两个N1s峰,表明γ-APS膜中的氨基有两种存在方式:自由氨基和质子化氨基。实验中还发现现场表面增强拉曼散射光谱(SERS)是研究金属/γ-APS体系中界面层结构非常有效的手段,SERS结果表明硅醇羟基和氨基发生了竞争吸附,且γ-APS分子在外加电位等条件的影响下吸附状态会发生一定变化。原子力显微镜(AFM)的表征结果在微观上显示电极表面的γ-APS膜上形成了一种较规则的微孔结构,这种结构可能与基底的性质有关。     

N-乙酰化壳聚糖的FTIR和XRD研究

壳聚糖分子的脱乙酰度(DD)是影响壳聚糖性质的主要因素之一。文章通过壳聚糖的N-乙酰化反应制备了不同脱乙酰度的壳聚糖。采用傅里叶变换红外光谱(FTIR)和X射线衍射(XRD)分别研究了由N-乙酰化反应得到的不同脱乙酰度的壳聚糖的红外光谱特性和晶体结构,并由此分别计算确定了样品的脱乙酰度和结晶度,探讨了N-乙酰化程度对壳聚糖脱乙酰度以及结晶度的影响。 由FTIR可知,随N-乙酰程度的增加,壳聚糖分子中剩余氨基的反应速度变慢。另外XRD也表明,伴随N-乙酰反应,壳聚糖分子的结晶区被破坏,规整度下降,并逐渐形成新的结晶区。     

双水相液膜微萃取咖啡因的动力学

自行设计了双水相支撑液相膜微萃取装置,以聚四氟乙烯徽孔膜为支撑,以磷酸三丁酯为有机萃取相,紫外光谱法研究了咖啡因稀水溶液的双水相液萃取。发现咖啡因以分子形式通过磷酸三丁酯有机液膜萃取进入HCl溶液中,萃取动力学受浓度差和收集液相中的化学反应控制,萃取率与咖啡因浓度成反比。     

Microwave-assisted covalent modification of graphene nanosheets with chitosan and its electrorheological characteristics

Biofunctionalization and manipulating of graphene nanosheets (GNS) are important for biomedical research and application. Chitosan (CS) modified graphene nanosheets have been successfully prepared under microwave irradiation in N,N-dimethylformamide medium, which involved the reaction between the carboxyl groups of graphene oxide nanosheets (GONS) and the amido groups of chitosan followed by the reduction of graphene oxide nanosheets into graphene nanosheets using hydrazine hydrate. The as-prepared graphene nanosheets-chitosan (GNS-CS) nanocomposites have been characterized by FTIR, TEM, FESEM, XRD and TG. The results showed that chitosan was covalently grafted onto the surface of graphene nanosheets via amido bonds. Solubility measurements indicated that the resultant nanocomposites dispersed well in aqueous acetic acid. Especially, the electrorheological (ER) properties of the GNS-CS nanocomposites have been investigated. It is believed that this new nanocomposites may be promising for biomedical applications.     

壳聚糖絮凝澄清蛇足石杉提取液的工艺研究

采用正交试验设计法考察了壳聚糖对蛇足石杉提取液的絮凝澄清效果。优选出的最佳工艺条件为:料液比(g/mL)为1:10,pH为5,反应温度50℃,壳聚糖浓度0.5g/L,反应时间60min,搅拌速度100r/min。在此条件下透光率可达81.6%。壳聚糖用于蛇足石杉提取液的絮凝澄清切实可行,并为后续的工艺改进提供了科学依据。     

叶绿素荧光及其在水分胁迫监测中的研究进展

水分胁迫是一种常见的植被胁迫状态,能够减小细胞水势,引起气孔关闭,破坏光合进程。叶绿素荧光是植物光合作用的探针,可以很好的反应植物生理特征,能够快速、灵敏、无损伤和深层次监测水分胁迫状态。由于叶绿素荧光的影响因素较多,使得水分胁迫与叶绿素荧光的关系比较复杂。从光合作用角度阐述了叶绿素荧光的产生原理,分析了叶绿素、叶片结构、冠层结构和环境因子等对叶绿素荧光的影响,总结了叶绿素荧光在水分胁迫监测中的应用;针对叶绿素荧光复杂的生理基础、影响因素及其在水分胁迫监测中的研究进展,提出了一些科学问题和未来的研究方向,为叶绿素荧光的进一步深入研究提供参考,为叶绿素荧光遥感的进一步应用提供理论支持,为陆地生态系统的准确评估提供借鉴。     

Probing the role of hydrolytically stable, 3-aminopropyl triethoxysilane crosslinked chitosan/graphene oxide membrane towards Congo red dye adsorption

In this investigation, the practicability of utilizing 3-aminopropyl triethoxysilane (3-APTES) crosslinked chitosan (Ch)/graphene oxide (GO) membranes were explored for adsorptive removal of anionic dyes from aqueous medium. Membranes were successfully fabricated through solution casting technique. Strong interactions amongst matrix (chitosan), 3-APTES, polyvinylpyrrolidone (PVP) and GO were confirmed by Infrared spectroscopy. Thermal stability of the chitosan was improved by adding graphene oxide and results were verified via thermogravimetric (TGA) analysis. Swelling and hydrolytic results confirmed that 2 %-Ch/PVP was a stable membrane while increasing the amount of 3-APTES in the chitosan nanocomposites membrane decreased its stability in aqueous medium. The adsorption characteristics of the membranes were evaluated by the adsorption of Congo red (CR) dye from aqueous medium. The adsorbent can remove 80% of CR from aqueous medium and follows second order kinetics. This study outlines the possibility of exploring green membranes which can be easily fit in various flow systems.     

In situ hybridization to chitosan/magnetite nanocomposite induced by the magnetic field

Chitosan/magnetite nanocomposite was synthesized induced by magnetic field via in situ hybridization in ambient condition. Results of XRD patterns and TEM micrographs indicated that magnetite particles with 10–20 nm were dispersed in chitosan homogeneously. An interesting result is that magnetite nanoparticles were assembled to form chain-like structures under the influence of the external magnetic field, which mimics the magnetite chains inside of magnetotatic bacteria. The saturated magnetization (Ms) of nano-magnetite in chitosan was 50.54 emu/g, which is as high as 54% of bulk magnetite. The remanence (Mr) and coercivity (Hc) were 4 emu/g and14.8 Oe, respectively, which indicated that magnetite nanoparticles were superparamagnetic. The key of route is that a pre-precipitated chitosan hydrogel membrane, used as chemical reactor, which controlled the precipitation of chitosan precipitation and in situ transformation of magnetite from the precursor simultaneously in the magnetic field environment.     

Octaarginine-modified chitosan as a nonviral gene delivery vector: properties and in vitro transfection efficiency

Protein transduction domains (PTD) have been identified to have the capacity to facilitate molecular cargo to translocate through cell membrane. This study aims to utilize the cell membrane penetrating ability of octaarginine oligopeptide, a simplified prototype of the PTD, to enhance the transfection efficiency of chitosan. Octaarginine-modified chitosan (R₈-CS) was synthesized as a gene transfer carrier by carbodiimide chemistry. The structure and composition of R₈-CSs were characterized using FTIR and ¹H NMR. Agarose gel electrophoresis assay showed that R₈-CS could efficiently condense the DNA. The particle size of R₈-CS/DNA complexes were determined to be around 100–200 nm. The nanoparticle complexes exhibited a spherical and compact morphology. R₈-CS demonstrated higher transfection activity and lower cytotoxicity as compared to the unmodified chitosan and also showed good serum resistance.     

Comparative performance study of four nanofiltration membranes in the separation of mercury and chromium

In this paper, four nanofiltration membranes, viz., (1) coating of N,O-carboxymethyl chitosan (NOCC) on polyethersulfone ultrafiltration (PES UF) substrate membrane; (2) chitosan and acrylonitrile butadiene styrene (ABS) in the blend ratio of 0:100 (ABS); (3) diethylenetriamine pentaacetic acid coating via casting method on PES UF substrate membrane (DC50); and (4) NOCC and cellulose acetate (CA) polymer blend solution (0.4?wt%) coated on a glass plate (NOCC?CCA), were selected from our previous work. By using these membranes, separation behaviour of mercury and chromium ions was studied at different operating conditions from their salt solutions. From the experimental data, it is evident that ABS membrane gave highest observed solute rejection (92.88 and 88.67?% for 10?ppm feed concentration of mercury sulphate?Cwater system and chromium sulphate?Cwater system, respectively) and NOCC?CCA membrane gave highest permeate volume flux. But from the rejection as well as permeate volume flux point of view, NOCC?CPES membrane is considered to be the best choice among all the membranes.     

Mechanically Robust,Electrically Conductive Biocomposite Films Using Antimicrobial Chitosan‐Functionalized Graphenes

An effective way of covalently functionalizing graphene with a chitosan polymer via a nitrene chemistry is demonstrated. The biofunctionalized graphene is prepared by the chemical reduction of graphene oxide using a nitrene chemistry, and then covalently grafting chitosan to the graphene surface. The effectiveness of the biofunctionalized graphene as a reinforcing filler (4 wt%) in a chitosan polymer matrix is verified by the dramatic enhancement of the mechanical properties (breaking stress = 330%, Young's modulus = 243%) and the electrical conductivity (0.3 S m^?1) without much loss in the elongation‐at‐break. The reinforcing effect can be explained by both the homogeneous dispersion of graphene within the matrix and the strong bond arising from the intrinsically intimate contact between the graphene and the matrix. The high antimicrobial activity of the biofunctionalized graphene compared with graphene oxide and chemically reduced graphene may be because of the presence of chitosan polymer on the edges of the graphene. The strong, antimicrobial graphene‐filled composite film can be used for food packaging and for coating various biomedical devices, where bacterial surface colonization is undesirable.     

Influence of hydrogen bonding on the generation and stabilization of liquid crystalline polyesters,poly(esteramide)s and polyacrylates

Induction and stabilization of liquid crystallinity through hydrogen bonding (HB) are now well-established. Interesting observations made on the influence of HB on LC behaviour of amido diol-based poly(esteramide)s, poly(esteramide)s containing nitro groups and azobenzene mesogen-based polyacrylates will be discussed. The use of amido diol as an important precursor for the synthesis of novel PEAs containing inbuilt di-amide linkage enabled generation of extensive hydrogen bondings between the amide-amide and amide-ester groups which stabilized the mesophase structures of the PEAs. The contributions of hydrogen bonding to the generation and stabilization of mesophase structures were plainly evident from the observation of liquid crystallinity even in PEAs prepared from fully aliphatic amido diols. Replacement of terephthaloyl units by isophthaloyl moiety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition temperatures as expected. The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, a smectic-to-nematic transition, were observed in the monomers and polymers based on 1,4-phenylene[bis-(3-nitroanthranilidic acid)] containing nitro groups. A smectic polymorphism was also observed as a combined effect of hydrogen bonded carboxyl groups and laterally substituted alkyl side chains in the case of azobenzene mesogen containing side chain polyacrylates. It was further shown that the presence of the mesophase enhances the non-linear optical (NLO) response of these polymers.