Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition

If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality.     

多糖化学合成研究进展

多糖是一类结构复杂的生物大分子,广泛分布于微生物、植物、动物等生物体中,参与众多重要的生命过程.然而,多糖研究一直受限于难以获得足量结构均一的多糖物质,这使得多糖的结构和功能研究及其相关的应用研究进展缓慢.近几十年来,随着糖合成技术的进步,糖的化学合成效率不断提高,人们开始关注复杂多糖的化学合成,并取得了一些进展.本文主要对多糖化学合成所涉及的糖基化方法、糖组装策略和代表性的合成工作进行综述,并对研究前景进行展望.     

Application of amino‐based chitosan cyclodextrin derivatives for the extraction of catechins in green tea with high‐performance liquid chromatography

Chitosan derivatives have been studied widely, but poor solubility in water restricts their applications. In this study, four types of amine‐based chitosan derivatives were prepared and modified further with beta‐cyclodextrin. The sequential microextraction of catechins ((+)‐catechin and (?)‐epigallocatechin gallate) from green tea powder by an optimized solid‐phase extraction method using these four derivatives was investigated. The optimal conditions for the extraction of catechins were 60°C for a 40 min extraction period. The purity and amount of each catechin were determined by high‐performance liquid chromatography. The different amines strengthened the extraction capacity of chitosan. Among the four types of amines, ethylene diamine grafted chitosan beta‐cyclodextrin had the highest extraction capacity to catechins. Therefore, this material was used in the extraction assay, and the standard curves of (+)‐catechin and (?)‐epigallocatechin gallate were linear over the concentration range, 0.25–500 µg/mL, after assaying five data points in duplicate. Solid‐phase extraction with the amino‐based chitosan beta‐cyclodextrin system is a new application of chitosan, which has potential applications in the extraction of bioactive compounds from plant materials or the removal of different impurities from specific extracts.     

柠檬果茶中游离态和键合态挥发性成分分析

以柠檬果茶为研究对象,建立了顶空固相微萃取前处理结合气相色谱质谱联用技术测定其中挥发性化合物的分析方法。采用开水冲泡对样品进行提取,通过Amberlite XAD-2大孔吸附树脂对柠檬果茶中的糖苷类挥发性组分键合,分离游离态和键合态化合物,甲醇溶剂作为洗脱剂对键合态化合物进行洗脱,Almondsβ-D-葡萄糖苷酶对其酶解。使用气质联用对样品中游离态和键合态挥发性成分进行检测,其结果根据数据库匹配和对比文献保留时间定性,内标法进行定量。结果表明,柠檬果茶中含有游离态物质24种,键合态物质16种,主要为(+)-柠檬烯、1-辛醇、橙花醇、(-)-4-萜品醇、alpha-松油醇等。方法为花果茶干燥工艺提供参考。     

Determination of Polysaccharide Hydrolyzates in Chinese Herbal Medicine by UltraHigh-Performance Liquid Chromatography-Quadrupole Time-of-Flight Mass Spectrometry and Evaporative Light Scattering Detection

Ultrahigh-performance liquid chromatography coupled with evaporative light scattering detector was used to optimize acid hydrolysis conditions of polysaccharides from Dendrobium candidum. The optimized conditions were the concentration of H₂SO₄, 0.4?M, hydrolysis temperature, 90°C, and hydrolysis time, 1?h. Ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry was used to obtain the total ion current chromatograms and determine the hydrolyzates of polysaccharides, such as monosaccharides, oligosaccharides, and some low-molecular weight polysaccharides from D. candidum, Cordyceps sinensis, and Ganoderma atrum. The accurate mass data were analyzed by chemometric tools, including an unsupervised analytical method, principal component analysis (one-way ANOVA, p?D. candidum polysaccharides from different locations and grades can be discriminated effectively by the principal component analysis scores. The quality predictive models showed a high value with a low prediction error calculated from both validation and training sets.     

Determination of Polysaccharides in Undaria pinnatifida by Ionic Liquid-Modified Silica Gel Size Exclusion Chromatography

Ionic liquid-modified silica particles with a large pore size were synthesized and used as the stationary phase for size exclusion chromatography coupled with a refractive index detector for the determination of polysaccharides, such as fucoidan, alginic acid, and laminarin from Undaria pinnatifida (seaweed). The molecular weight of polysaccharide was determined by a dextran standard curve (5–1100?kDa). The ionic liquid-modified silica column exhibited excellent size exclusion properties in separating laminarin from other components. The 1-butyl-3-methyl-imidazolium bis-(trifluoromethylsulfonyl)-amino silica column has superior resolution in laminarin separation than the other columns because the amino-group in ionic liquid provide π–π interactions due to aromaticity of the ring structure, which enhances the effect of the hydroxyl group in the target compound separation. The concentrations of polysaccharides were calculated using a standard linear equation to be 0.332–0.484?mg/g of fucoidan, 0.207–0.301?mg/g of alginic acid, and 0.154–0.297?mg/g of laminarin.     

Structural characterisation of a water-soluble polysaccharide from tissue-cultured Dendrobium huoshanense C.Z. Tang et S.J. Cheng

A water-soluble polysaccharide TC-DHPA4 with a molecular weight of 8.0 × 10⁵ Da was isolated from tissue-cultured Dendrobium huoshanense by anion exchange and gel permeation chromatography. Monosaccharide analysis revealed that the homogeneous polysaccharide was made up of rhamnose, arabinose, mannose, glucose, galactose and glucuronic acid with a molar ratio of 1.28:1:1.67:4.71:10.43:1.42. The sugar residue sequence analysis based on the GC-MS files and NMR spectra indicated that the backbone of TC-DHPA4 consisted of the repeated units:→6)-β-Galp-(1→6)-β-Galp-(1→4)-β-GlcpA-(1→6)-β-Glcp-(1→6)-β-Glcp-(→. The sugar residue sequences β-Glcp-(1→)-α-Rhap-(1→3)-β-Galp-(1→, β-Glcp-(1→4)-α-Rhap-(1→3)-β-Galp-(1→, β-Galp-(1→6)-β-Manp-(1→3)-β-Galp-(1→, and α-l-Araf-(1→2)-β-Manp-(1→3)-β-Galp-(1→ were identified as the branches attached to the C-3 position of (1→6)-linked galactose in the backbone.     

Efficient synthesis and characterization of new photoactive dextran esters showing nanosphere formation

Different types of photoactive dextran derivatives with high degree of substitution were prepared by an efficient and mild esterification of the biopolymer with 2-methoxycinnamic acid, [(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetic acid, and azobenzene-4-carboxylic acid via in situ activation of the carboxylic acid groups with N,N'-carbonyldiimidazole. The structures of the novel dextran esters were evaluated by means of NMR spectroscopy applying the perpropionylated samples. Perpropionylation yields samples soluble in chloroform and acetonitrile that are very useful solvents not only for NMR but also for UV-vis spectroscopic studies. The photochemistry was studied by NMR and UV-vis spectroscopy in the dissolved state and the changes observed may be used to control the properties. The photoactive dextran esters form spherical nanoparticles of a size below 200 nm that are of interest in the design of smart materials.     

NOVEL pH-SENSITIVE DRUG DELIVERY SYSTEM BASED ON NATURAL POLYSACCHARIDE FOR DOXORUBICIN RELEASE

A novel pH-sensitive nanoparticle drug delivery system (DDS) derived fl'om natural polysaccharide pullulan for doxorubicin (DOX) release was prepared.Pullulan was functionalized by successive carboxymethylization and amidation to introduce hydrazide groups.DOX was then grafted onto pullulan backbone through the pH-sensitive hydrazone bond to form a pullulan/DOX conjugate.This conjugate self-assembled to form nano-sized particles in aqueous solution as a result of the hydrophobic interaction of the DOX.Tr...