Antioxidative properties and enzymatic synthesis of ascorbyl FA esters

Efficient synthesis of unsaturated FA esters of ascorbic acid is possible with only a small excess of one of the reactants in t-amyl alcohol using Candida antarctica lipase as biocatalyst. Using free acids, we obtained yields that were comparable to yields reached using vinyl-activated acyl donors (71, 80, and 86% yields of esters with FA excesses of 1∶1, 1∶1.5, and 1∶2, respectively). As very low water activity is needed to achieve sufficiently high yields of product, molecular sieves were used to improve the ascorbyl ester yields. Ascorbyl oleate is more amorphous and has a much lower m.p. and lower enthalpy of fusion than ascorbyl palmitate. This leads to a higher solubility of ascorbyl oleate in oil, resulting in an increased antioxidant effect compared to that of the palmitate. In an accelerated storage test using deodorized rapeseed oil, samples incubated with ascorbyl palmitate showed noticeable oxidation after 1 wk of storage, whereas samples incubated with ascorbyl oleate displayed negligible oxidation for 9 and 4 wk at 30 and 40°C, respectively.     

Dendrimers: synthesis,applications, and properties

Dendrimers are nano-sized, radially symmetric molecules with well-defined, homogeneous, and monodisperse structure that has a typically symmetric core, an inner shell, and an outer shell. Their three traditional macromolecular architectural classes are broadly recognized to generate rather polydisperse products of different molecular weights. A variety of dendrimers exist, and each has biological properties such as polyvalency, self-assembling, electrostatic interactions, chemical stability, low cytotoxicity, and solubility. These varied characteristics make dendrimers a good choice in the medical field, and this review covers their diverse applications.     

Gold nanocages: synthesis, properties, and applications

Noble-metal nanocages comprise a novel class of nanostructures possessing hollow interiors and porous walls. They are prepared using a remarkably simple galvanic replacement reaction between solutions containing metal precursor salts and Ag nanostructures prepared through polyol reduction. The electrochemical potential difference between the two species drives the reaction, with the reduced metal depositing on the surface of the Ag nanostructure. In our most studied example, involving HAuCl(4) as the metal precursor, the resultant Au is deposited epitaxially on the surface of the Ag nanocubes, adopting their underlying cubic form. Concurrent with this deposition, the interior Ag is oxidized and removed, together with alloying and dealloying, to produce hollow and, eventually, porous structures that we commonly refer to as Au nanocages. This approach is versatile, with a wide range of morphologies (e.g., nanorings, prism-shaped nanoboxes, nanotubes, and multiple-walled nanoshells or nanotubes) available upon changing the shape of the initial Ag template. In addition to Au-based structures, switching the metal salt precursors to Na(2)PtCl(4) and Na(2)PdCl(4) allows for the preparation of Pt- and Pd-containing hollow nanostructures, respectively. We have found that changing the amount of metal precursor added to the suspension of Ag nanocubes is a simple means of tuning both the composition and the localized surface plasmon resonance (LSPR) of the metal nanocages. Using this approach, we are developing structures for biomedical and catalytic applications. Because discrete dipole approximations predicted that the Au nanocages would have large absorption cross-sections and because their LSPR can be tuned into the near-infrared (where the attenuation of light by blood and soft tissue is greatly reduced), they are attractive materials for biomedical applications in which the selective absorption of light at great depths is desirable. For example, we have explored their use as contrast enhancement agents for both optical coherence tomography and photoacoustic tomography, with improved performance observed in each case. Because the Au nanocages have large absorption cross-sections, they are also effective photothermal transducers; thus, they might provide a therapeutic effect through selective hyperthermia-induced killing of targeted cancer cells. Our studies in vitro have illustrated the feasibility of applying this technique as a less-invasive form of cancer treatment.     

α-Sulfonated fatty acids and esters: Manufacturing process,properties, and applications

α-Sulfonated fatty acid esters, because of their wide-range of application and biological properties, represent an interesting class of surfactants. A technical method for the preparation of α-sulfonated fatty acid esters is described. By using special reaction conditions it is possible to α-sulfonate saturated fatty esters directly without the use of solvents. The use of gaseous SO₃ gives the product in greater than 97% yield. A process for the bleaching of the α-sulfonated fatty esters has been developed, whereby a product of faultless color is produced without the necessity of further purification or separation techniques. The sulfonation and bleaching processes operate continuously. The process has been tried successfully on a commercial scale using the methyl esters of technical fatty acids. Methods for the preparation of α-sulfonated fatty acids are given. The chemical, technical, and biological properties of the α-sulfonated fatty acids and their esters are discussed. α-Sulfonated fatty esters possess good washing and foaming properties, have good biological degradability, possess good skin compatibility and low acute toxicity. They can be considered as surfactant components for phosphate-free or low-phosphate detergents. α-Sulfonated fatty acids and esters also possess other favorable technical properties which allow them to be used in cosmetics, as auxiliary agents in the production of fibers, plastics, and rubber, and in leather manufacture.     

Lanthanide-doped nanocrystals: synthesis, optical-magnetic properties, and applications

Because of the potential applications of lanthanide-doped nanocrystals in display devices, optical communication, solid-state lasers, catalysis, and biological labeling, the controlled synthesis of these new nanomaterials has sparked considerable interest. Nanosized phosphorescent or optoelectronic devices usually exhibit novel properties, depending on their structures, shapes, and sizes, such as tunable wavelengths, rapid responses, and high efficiencies. Thus, the development of facile synthetic methods towards high-quality lanthanide-doped nanocrystals with uniform size and shape appears to be of key importance both for the exploration of their materials properties and for potential applications. This Account focuses on the recent development in our laboratory of the synthesis and applications of lanthanide-doped nanocrystals. Since 2005, when we proposed a general strategy for nanocrystal synthesis via a liquid-solid-solution process, a range of monodisperse and colloidal lanthanide-doped fluoride, oxide, hydroxide, orthovanadate, thiooxide, borate, and phosphate nanocrystals have been successfully prepared. By rationally tuning the reaction conditions, we have readily synthesized nanostructures, such as hollow microspheres, nanorods, nanowires, hexagonal nanoplates, and nanobelts. By adjusting the different colloidal nanocrystal mixtures, we fabricated unique binary nanostructures with novel dual-mode luminescence properties through a facile ultrasonic method. By tridoping with lanthanide ions that had different electronic structures, we successfully achieved β-NaYF(4) nanorods that were paramagnetic with tuned upconversion luminescence. We have also used NaYF(4):Yb(3+)/Er(3+) conbined with magnetite nanoparticles as a sensitive detection system for DNA: NaYF(4):Yb(3+)/Er(3+) and Fe(3)O(4) nanoparticles were modified with two different DNA sequences. Then, the modified NaYF(4):Yb(3+)/Er(3+) nanoparticles were conjugated to the modified Fe(3)O(4) nanoparticles. These binary nanoparticles can be hybridized with a third DNA (target DNA) molecule and separated with the assistance of a magnetic field. In addition, a novel fluorescence resonance energy transfer (FRET) method for nonenzymatic glucose determination has been developed by using the glucose-modified LaF(3):Ce(3+)/Tb(3+) nanocrystals. By using bioconjugated NaYF(4):Yb(3+)/Er(3+) nanoparticles as the energy donor and bioconjugated gold nanoparticles as the energy acceptor, we successfully developed a simple and sensitive fluorescence resonance energy transfer (FRET) biosensor for avidin. Meanwhile, we also carried out preliminary studies to investigate possible applications of lanthanide-doped nanocrystals in catalysis and in dye-sensitized solar cells.     

金纳米棒的合成、光学特性、修饰及其在生物学中的应用

由于具有独特的光学和电子特性,金纳米棒受到人们越来越多的关注。金纳米棒的这些性质主要取决于它自身的形状、大小和长径比。尤其金纳米棒独特的、可调的表面等离子体共振特性,使其在生物标记、生物成像及生物医学等领域有非常广阔的应用前景。本论文详细介绍了金纳米棒的几种合成方法及其光学特性和金纳米棒的表面修饰手段,综述和比较了金纳米棒在生物分子探针技术、荧光探针和癌症诊断和光热治疗领域的研究进展,对其存在的问题做了具体分析并对金纳米棒在生物学中的应用方向进行了展望。     

DNA-mediated silver nanoclusters: synthesis, properties and applications

Fluorescent DNA-AgNCs have emerged as an alternative to standard emitters because of their unique properties: high fluorescent quantum yield, photostability, a broad pallet of colors (blue to near-IR), and the fact that their properties are easily modulated by the DNA sequence and environment. Applications as gene, ion, or small-molecule sensors have been reported.     

螯合型离子液体：合成、性质以及应用

配位型离子液体在过去一段时间内得到了广泛的关注。其中,螯合型离子液体因其存在多个配位点,因而可以通过螯合作用增强金属与配体的相互作用。根据金属在分子中所处的位置,可以将螯合型离子液体分为4种类型：阳离子螯合型离子液体、阴离子螯合型离子液体、阴阳离子螯合型离子液体和中性螯合型离子液体。对近年来报道的螯合型离子液体的合成、物理性质及其应用进行了综述,阐述了其存在的问题、面临的挑战和今后研究的方向。     

脂肪酶催化合成棕榈酸维生素C酯的研究

在溶剂相中,用固定化脂肪酶催化合成棕榈酸维生素C酯。研究了反应体系含水量、溶剂、反应温度、加酶量、加入分子筛等因素对反应的影响。结果表明,最佳反应条件为:Novo 435脂肪酶用量为反应物质量的4%,叔丁醇作溶剂,反应温度55℃,摇床转速200 r/min,反应时间36 h,转化率52%,产品纯度95%。     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

氨基酸表面活性剂的合成、性质及工业应用（续完）

正7毒性传统表面活性剂,特别是阳离子表面活性剂对水生生物具有很强的毒性。其急性毒性是由于表面活性剂在细胞-水界面处的吸附-离子相互作用现象。降低表面活性剂的cmc通常导致表面活性剂更强的界面吸附,通常导致其急性毒性升高。表面活性剂疏水链的长度增加也导致表面活性剂急性毒性增大。大部分AAS为对人体和环境(特别是对海洋生物)低毒或无毒,使其适合做为食品成分、药物     

两性聚丙烯酰胺的性质、合成与应用研究进展

两性聚丙烯酰胺属于两性聚电解质,是一种新型功能高分子。本文首先阐述了两性聚丙烯酰胺的结构和特性,包括等电点、电荷密度、分子链形态、浊度、黏度、吸附特性等;接着概括了目前较为普遍的两性聚丙烯酰胺的合成反应,包括大分子改性、接枝共聚、阴/阳离子单体共聚,以及丙烯酰胺与甜菜碱型单体共聚;还总结了两性聚丙烯酰胺的合成方法,包括:水溶液聚合、反向乳液聚合、反向微乳液聚合、悬浮聚合、辐射聚合等;最后总结了其在各领域的应用,尤其是在造纸工业中的助留助滤和纸张增强等应用。     

CL-20的合成、性能和应用研究进展

CL-20自成功合成以来,就以高密度、高能量在世界范围内获得广泛关注,其性能和应用的探索研究一直都是材料学的热点问题之一。介绍了近年关于CL-20研究的最新进展情况。     

Carbon nanotubes: properties,synthesis, purification,and medical applications

Current discoveries of different forms of carbon nanostructures have motivated research on their applications in various fields. They hold promise for applications in medicine, gene, and drug delivery areas. Many different production methods for carbon nanotubes (CNTs) have been introduced; functionalization, filling, doping, and chemical modification have been achieved, and characterization, separation, and manipulation of individual CNTs are now possible. Parameters such as structure, surface area, surface charge, size distribution, surface chemistry, and agglomeration state as well as purity of the samples have considerable impact on the reactivity of carbon nanotubes. Otherwise, the strength and flexibility of carbon nanotubes make them of potential use in controlling other nanoscale structures, which suggests they will have a significant role in nanotechnology engineering.     

Graphene aerogel and its composites: synthesis,properties and applications

Journal of Porous Materials - Graphene is an attractive material for many applications due to excellent inherent properties such as lower density, high mechanical strength, higher thermal...     

碳纳米环：生长机理、可控合成、性质和应用

碳材料是一类神奇的材料,碳原子可以通过sp、sp²或sp³杂化构筑不同微观结构的碳材料。目前,已经发现的碳的同素异形体有石墨、金刚石、富勒烯、碳纳米管、碳纳米环、石墨烯和石墨炔。富勒烯和石墨烯因性质独特、应用前景广阔,其发现者分别获得1996年和2010年诺贝尔奖。碳纳米环具有独特的环状结构、优异的机械强度及特殊的物理化学性能,也引起广泛关注。研究者从早期对碳纳米环进行理论计算、预测其性质,到现在已能够通过化学气相沉积、激光辐射、超声诱导自组装等方法制备不同尺寸的碳纳米环,并对其性质和应用进行探索。总结了近30年来有关碳纳米环的生长机理、可控合成、性质和应用等方面的研究进展,对其规模化合成与应用提出了建议与展望。     

超分子化合物的合成应用及性能研究的新进展

简要介绍了超分子化学的产生发展及应用。详细介绍了超分子化合物的合成自组装及选择性识别作用;新颖的金属超分子配合物的合成及自组装行为;新型超分子化合物的合成及在医药上的应用。并对超分子化学的发展进行了展望。     

A review on zeolite imidazole frameworks: synthesis,properties, and applications

Journal of Porous Materials - Zeolitic imidazolate frameworks (ZIFs) consist of transition metal ions (Zinc or Cobalt) and imidazolate (Im) linkers in tetrahedral coordination surrounded by...