Heterotricyclodecane XIX. Umlagerungen von 4,8-disubstituierten 2,6-Dioxa- und 2-Oxa-6-aza-adamantanen zu 4,10-disubstituierten 2,7-Dioxa- und 2-Oxa-7-aza-isotwistanen sowie -twistanen

Rearrangements of 4,8-disubstituted 2,6-dioxa- and 2-oxa-6-aza-adamantanes to 4,10-disubstituted 2,7-dioxa- and 2-oxa-7-aza-isotwistanes as well as -twistanes. Substitutions and rearrangements involving neighboring group participation starting from 4,8-diiodo-2,6-dioxa- and 4,8-diiodo-2-oxa-6-aza-adamantanes ( 5 and 6, 12 and 48 , resp.) were studied, yielding 4,8-disubstituted 2,6-dioxa- and 2-oxa-6-aza-adamantanes ( 7, 9, 39, 42 and 13, 15, 50, 52 , resp.), 4,10-disubstituted 2,7-dioxa- and 2-oxa-7-aza-isotwistanes ( 8, 10, 41, 43 and 14, 16, 51, 53 , resp.) and corresponding-twistanes ( 11 and 17 , resp.).     

伊敏褐煤中微量元素的地球化学特征及其无机-有机亲和性分析

采用脱矿物质、提取腐殖酸等方法结合ICP-MS对伊敏15_上、16_下煤中的32种微量元素的含量及其赋存特征进行了分析。与地壳克拉克值及中国侏罗-白垩纪煤和世界褐煤中微量元素含量相比,伊敏褐煤中微量元素没有明显富集。脱矿物质处理后,Ni明显富集,As略比原煤高,其他微量元素都低于原煤。原煤提取腐殖酸和脱矿物煤提取腐殖酸中Ni、Mo、Cd、Sn、W明显富集,这表明Ni、Mo、Cd、Sn、W和腐殖酸形成了稳定的有机态化合物。原煤提取腐殖酸残煤和脱矿物煤提取腐殖酸残煤中V、Ni、As富集,表明V、Ni、As与煤的大分子结构形成了稳定的有机态化合物。根据微量元素和灰分的相关性系数,把微量元素分为以下几类:无机富集元素Cr、U;亲无机元素Cu、Cd、In、Sn、Ga、Y、Zr、Hf、Bi、Th;偏无机元素Be、Sc、Rb、Sr、Nb、Cs、Ta、Pb;偏有机元素V、As、Tl、Ba、Se;亲有机元素Li、Co、W;有机富集元素Ni、Zn、Mo、Sb。     

Determination of carbamazepine and its impurities iminostilbene and iminodibenzyl in solid dosage form by column high-performance liquid chromatography

An accurate and precise RP-HPLC method was developed and validated for the determination of carbamazepine and its impurities iminostilbene and iminodibenzyl in a tablet formulation with fluphenazine as an internal standard. Buffer-methanol (50 + 50, v/v) was used as the mobile phase. During validation, specificity, linearity, precision, accuracy, LOD, LOQ, and robustness of the method were tested. The method was proven to be specific against placebo interference. Linearity was evaluated over the concentration range of 100-500, 0.05-0.25, and 0.1-0.5 microg/mL, and the r values were 0.9994, 0.9997, and 0.9979 for carbamazepine, iminostilbene, and iminodibenzyl, respectively. Intraday precision of the method was good, and RSD was below 2% for all analytes. The accuracy of the method ranged from 100.69 to 102.10, 99.76 to 102.66, and 99.26 to 100.08% for carbamazepine, iminostilbene, and iminodibenzyl, respectively. LOD was 0.0125, 0.025, and 0.05 microg/mL and LOQ was 0.05, 0.05, and 0.1 microg/mL for carbamazepine, iminostilbene, and iminodibenzyl, respectiviely. Robustness of the method was proven by using a chemometric approach. The method was successfully applied to the analysis of commercially available carbamazepine tablets and showed good repeatability, with RSD below 2%.     

Sixteen capillary electrophoresis applications for viral vaccine analysis

A broad range of CE applications from our organization is reviewed to give a flavor of the use of CE within the field of vaccine analyses. Applicability of CE for viral vaccine characterization, and release and stability testing of seasonal influenza virosomal vaccines, universal subunit influenza vaccines, Sabin inactivated polio vaccines (sIPV), and adenovirus vector vaccines were demonstrated. Diverse CZE, CE-SDS, CGE, and cIEF methods were developed, validated, and applied for virus, protein, posttranslational modifications, DNA, and excipient concentration determinations, as well as for the integrity and composition verifications, and identity testing (e.g., CZE for intact virus particles, CE-SDS application for hemagglutinin quantification and influenza strain identification, chloride or bromide determination in process samples). Results were supported by other methods such as RP-HPLC, dynamic light scattering (DLS), and zeta potential measurements. Overall, 16 CE methods are presented that were developed and applied, comprising six adenovirus methods, five viral protein methods, and methods for antibodies determination of glycans, host cell-DNA, excipient chloride, and process impurity bromide. These methods were applied to support in-process control, release, stability, process- and product characterization and development, and critical reagent testing. Thirteen methods were validated. Intact virus particles were analyzed at concentrations as low as 0.8 pmol/L. Overall, CE took viral vaccine testing beyond what was previously possible, improved process and product understanding, and, in total, safety, efficacy, and quality.     

Determination of carbohydrates and sweeteners in foods and biologically active additives by high-performance liquid chromatography

A method for the determination of large amounts of carbohydrates (glucose, lactose, maltose, mannose, sucrose, and fructose) and sweeteners (xylitol and sorbitol) by reversed-phase liquid chromatography with refractive index detection without derivatization has been developed. The limits of determination for glucose, fructose, and sucrose in liquid samples were 0.1 g/L, and for xylite, lactose, maltose, mannose, and sorbite, 1 g/L. In solid samples the limits of determination for glucose, fructose, and sucrose were 0.1%, and for xylite, lactose, maltose, mannose, and sorbite, 0.6%. The method is applicable to the analysis of samples of wine, juice, honey, cookies, dairy products, and biologically active additives. The developed method for the determination of carbohydrates and sweeteners in foods and biologically active additives was certified in the Mendeleev Institute for Metrology (St. Petersburg).     

Structures of new cucurbitane-type triterpenes and glycosides, karavilagenins and karavilosides, from the dried fruit of Momordica charantia L. in Sri Lanka

Three new cucurbitane-type triterpene called karavilagenins A, B, and C and five new cucurbitane-type triterpene glycosides called karavilosides I, II, III, IV, and V were isolated from the dried fruit of Sri Lanka Momordica charantia L. (Cucurbitaceae) together with two known cucurbitane-type triterpenes, 19(R)-methoxy-5beta,19-epoxycucurbita-6,23-dien-3beta,25-diol and 5,19-epoxycucurbita-6,23-diene-3,25-diol, and nine known cucurbitane-type triterpene glycosides, goyaglycosides-b, -c, and -d, and momordicosides F1, F2, G, I, K, and L. The structures of karavilagenins and karavilosides were elucidated on the basis of chemical and physicochemical evidence.     

Reaction of sulfolenes and their derivatives with some sulfur-containing nucleophiles

Reaction of 2-sulfolene, 4-hydroxy-2-sulfolene, 4-bromo- and 3-chloro-2-sulfolenes, 3-chloro-4-hydroxysulfolane, and 3,4-dibromo(dichloro)sulfolanes with sodium methane-, hexane-, allene-, benzene-, and p-toluenesulfinates and magnesium gave 3-methyl-, 3-hexyl-, 3-allyl-, 3-phenyl-, and 3-(p-tolylsulfonyl)sulfolanes, 3-methyl-, 3-phenyl-, and 3-(p-tolylsulfonyl)-4-hydroxysulfolanes, and 3-phenyl- and 4-phenylsulfonyl-2-sulfolenes.     

含希夫碱侧基聚酯及其锌配合物的合成和性能

经多步反应合成2种新型含希夫碱侧基聚酯(P5,P6),进一步与醋酸锌反应得到2种聚酯锌配合物(P5-Zn,P6-Zn)。 采用元素分析、FT-IR、UV-Vis、¹H NMR、GPC、TG、DSC和荧光光谱等技术手段对其结构和性能进行表征。 P5和P6均溶于四氢呋喃(THF)、氯仿(CHCl₃)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮法(NMP)等有机溶剂,P5-Zn和P6-Zn部分溶于THF及CHCl₃,溶于DMF、DMAc、DMSO、NMP等有机溶剂。 P5和P6的重均相对分子质量M_w及相对分子质量分布指数PDI分别为4164、6148 g/mol和1.42、1.43。 P5、P6、P5-Zn和P6-Zn的5%失重温度分别为339、348、367和358℃。 P5、P6、P5-Zn和P6-Zn的玻璃化转变温度T_g分别为88.8、123.3、39.8和63.8 ℃。 P5和P6的DMF溶液(5×10^-5 mol/L)在418和416 nm处发射弱紫色荧光,P5-Zn和P6-Zn的DMF溶液(5×10^-5 mol/L)在505和506 nm处发射强绿色荧光,固体P5-Zn和P6-Zn在527和532 nm处发射强绿色荧光。     

前列舒通胶囊中26种无机元素的分析

目的：明确造成前列舒通胶囊不同批次间差异的标志性无机元素,并进行安全性评价。方法：采用ICP-MS测定制剂中Al、As、B、Ba、Ca、Cd、Co、Cr、Cu、Fe、K、Mg、Mn、Mo、Na、Ni、Pb、Sb、Se、Sn、Sr、Ti、Tl、V、Zn和Hg元素含量并进行数据分析。运用主成分及综合评分结合聚类分析手段,确定制剂的特征性元素;进行元素含量和相关性分析,明确不同批次各元素的差异及元素之间的关系;以多元素含量为指标,绘制无机元素谱图。结果：19批样品中均未检测出Se、Mo、Sn、Sb、Tl和Hg,且Pb、Cd、As、Cu、Hg均符合限量标准,无机元素含量谱图趋势一致。主成分分析提取了4个主成分,确定元素B、K、Al、V、Cr、Ca、Ti、Na、Co和Mn可作为特征元素。主成分得分图将19批样品分为两类,聚类分析及综合评分结果与其一致,两类样品中各元素含量存在差异性。相关性分析中,明确了B与K、Al、Cr正相关,K与Cr、Co正相关,V与Cr、Mn正相关,Mn与Co正相关,Ca、Ti、Na两两正相关。结论：通过分析前列舒通胶囊中无机元素含量,确定了特征元素,为前列舒通胶囊质量全面控制研究提供科学依据。     

Environmentally Friendly Techniques and Their Comparison in the Extraction of Natural Antioxidants from Green Tea,Rosemary, Clove,and Oregano

Many current food and health trends demand the use of more ecological, sustainable, and environmentally friendly techniques for the extraction of bioactive compounds, including antioxidants. However, extraction yields and final antioxidant activities vary between sources and are highly influenced by the given extraction method and nature and ratio of the employed solvent, especially for total polyphenols, flavonoids, and anthocyanins, which are well recognized as natural antioxidants with food applications. This review focused on the most common extraction techniques and potential antioxidant activity in the food industry for various natural antioxidant sources, such as green tea, rosemary, clove, and oregano. Green extraction techniques have been proven to be far more efficient, environmentally friendly, and economical. In general, these techniques include the use of microwaves, ultrasound, high hydrostatic pressure, pulsed electric fields, enzymes, and deep eutectic solvents, among others. These extraction methods are described here, including their advantages, disadvantages, and applications.     

A Festschrift in honor of Akira Imamura��s 77th birthday, his recent retirement, and his many contributions to theoretical chemistry

The Imamura Festschrift Issue of Theoretical Chemistry Accounts is a special multifocus international issue commemorating the 77th birthday of Professor Akira Imamura and his many contributions to the fields of theoretical chemistry, polymer science, molecular biophysics, chemical physics, and molecular biology. This issue has contributions in theoretical developments of methods applicable to larger polymeric systems, for example, the elongation method pioneered by Professor Imamura and his group, and more recently by the groups of Professor Yuriko Aoki at Kyushu University and Professor Feng Long Gu at South China Normal University, supported by several funds from the Japan Science and Technology Agency (JST). In addition, there are contributions from top experimental and theoretical groups in the areas of nanotechnology, bionanotechnology, quantum transport theory, molecular biophysics, molecular electronics, and even molecular medicine and medical diagnostics, where the marriage between theory and experiment is very important to be able to fully understand, interpret, and utilize the wealth of new and exciting experimental data. The development of new and refined methods, and the extension of older more conventional methods, will be required for these fields to continue to evolve/co-evolve and develop, as they have in the last 60?years. But to evolve in a guided fashion (guided evolution), that is, to meet the needs and functions of not only the individual scientists and research groups but also of society in general, will require a concerted effort from not only experimentalists and theoreticians in each individual subdiscipline but also for them to work together and share their accumulated knowledge and experience, as is now being done in various research networks around the world, including the one originally initiated/formed by Professor Imamura and Professor Janos Ladik at the Third International Congress of Quantum Chemistry (ICQC) in Kyoto, Japan. Through this network, Professor Imamura has been able to pass on a wealth of knowledge, expertise, and experience to the current and future generations of scientists in Germany, the United States, and China, as Professor Imamura is still doing with his lectures both in Japan at Kyushu University and in China at South China Normal University, and previously in Erlangen at the University of Erlangen, in Heidelberg at the German Cancer Research Center (DKFZ) in Germany, and in Ithaca, New York at Cornell University in the United States. He has been a real example of the modern protean research scientist and professor who has continued to be in research and teaching, active well beyond the formerly set retirement age of 63 or 65 set by society. The idea that researchers and professors cannot be active in their 60s, 70s, and 80s has now also been shown to be a misconception that needs to be corrected at the funding and institutional levels. Too many very active, knowledgeable, and experienced researchers and professors have been forced to stand on the sidelines, while those who have replaced them have very little practical knowledge, expertise, and more importantly, life experience. A whole generation of young academics are being hired who have never worked a day in industry, never visited an industrial laboratory and/or research group, and hence are unable, (don??t know) and in many cases, unwilling to train and educate their students with the skills they need to not only work in industry but also to create new and exciting new industries. The idea that the large chemical and pharmaceutical companies and government laboartories will hire all of the ever increasing numbers of undergraduate and graduate (MSc and PhD) students no longer applies. The university mission is no longer just to teach, give knowledge, and to do research, but also to innovate, that is, to train the students to take their acquired knowledge from their text books and apply it with the newly acquired knowledge in the research laboratories to start and develop new industries and companies. But this means that the students need to be trained in the fields of engineering economics, finance, and scientific and international law, so that they are able to undertake such projects, in addition to understanding and applying their scientific knowledge. It will also require a concerted effort by funding agencies, state, local, federal, and even international bodies that seek to create and sustain strong economies and infrastructure, which will support and be supported by the highly motivated, trained, and educated work forces. The third pillar is now being established, but it needs to now be totally and completely integrated with the other establishments and infrastructure.     

Mononuclear,polynuclear, and cluster complexes of molybdenum and their reactions as models of biochemical systems and processes

Data on the composition, structure, and properties (electronic and geometric structure, optical properties, thermodynamic functions) of mononuclear, polynuclear, and cluster complexes of bi-, tri-, tetra-, penta-, and hexavalent molybdenum are summarized and correlated. The thermodynamics, kinetics, and mechanisms of the ligand exchange, protonation deprotonation, redox reactions, and formation decomposition of cluster cores of molybdenum complexes in aqueous solutions are characterized.     

Ziziphora clinopodioides Lam leaf aqueous extract mediated novel green synthesis of iron nanoparticles and its anti-hemolytic anemia potential: A chemobiological study

In this study, the aqueous extract Ziziphora clinopodioides was used to biosynthesis of iron nanoparticles. A green, productive, and environmentally method was developed for the valuable study and the effective preparation of the green-synthesis of iron nanoparticles using aqueous extracts from the leaf of Ziziphora clinopodioides as a result of reducing and stabilizing factor. The simplicity of the synthesis procedures and easy work up are the benefits of the present study. The structural and morphological characterization of green‐synthesized FeNPs was performed by Uv–Vis. and FT-IR spectroscopy, XRD, SEM, and EDX techniques. The SEM images have exhibited an equal and uniform spherical morphology in size of 30.04. We also investigated the anti-hemolytic anemia property of FeNPs in an animal model of hemolytic anemia. In vivo assay, induction of hemolytic anemia was done by phenylhydrazine in mice. FeNPs significantly reduced the weight and volume of liver and spleen and the concentration of pro-inflammatory cytokines and increased the body weight, the anti-inflammatory cytokines concentration, and the total platelet, WBC, neutrophil, lymphocyte, eosinophil, monocyte, and basophil counts, and RBC parameters as compared to the untreated mice. About the biochemical parameters, FeNPs significantly increased GPx, CAT, and SOD in serum, liver, and spleen, and also HDL, total protein, and albumin in serum, and decreased GR in serum, liver, and spleen, and also erythropoietin, ferritin, ferrous, creatinine, urea, LDL, triglyceride, cholesterol, GGT, ALT, AST, and ALP in serum as compared to the anemic mice. DPPH test revealed similar antioxidant potentials for FeNPs and Butylated hydroxytoluene. FeNPs had low cell viability dose-dependently against HUVEC cell line. It appears that FeNPs can be administrated as a hematoprotective and anti-hemolytic anemia drug or supplement for the treatment of hemolytic anemia in the clinical trial.     

含8-羟基喹啉侧基聚酯及其锌、铝配合物的合成和性能

合成了2种新型含8-羟基喹啉侧基聚酯(P5,P6),进一步与无水醋酸锌和六水氯化铝反应,得到4种聚酯锌、铝配合物(P5-Zn,P6-Zn,P5-Al,P6-Al)。采用元素分析仪、傅里叶变换红外光谱仪、紫外可见光谱仪、核磁共振氢谱仪、凝胶渗透色谱仪、热重分析仪和荧光光谱仪等技术手段对其结构和性能进行了表征。聚酯P5和P6易溶于四氢呋喃(THF)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)和N-甲基吡咯烷酮(NMP)等常用的有机溶剂,配合物P5-Zn、P6-Zn、P5-Al和P6-Al部分溶于DMF、DMAC、DMSO和NMP等溶剂。聚酯P5和P6的质均相对分子质量Mw为4.11×10~4和5.42×10~4,相对分子质量分布指数PDI为1.50和1.40。聚酯P5和P6的5%失重温度分别为261.4和291.1℃,配合物P5-Zn、P6-Zn、P5-Al和P6-Al的5%失重温度分别为307.7、306.2、286.3和297.8℃。聚酯P5和P6的DMF溶液(5×10-5 mol/L)在432和429nm处发射较弱紫色荧光,配合物P5-Zn、P6-Zn、P5-Al和P6-Al的DMF溶液(5×10~(-5) mol/L)分别在540、537、517和522nm处发强绿色荧光,固体分别在550、556、531和535nm处发射强绿色荧光。     

Synthesis,structure, and function of internally functionalized dendrimers

The past three decades have witnessed an exponential increase in the structural diversity and applications of dendrimers, spanning across drug delivery and diagnostics, protein, and enzyme mimicry, solubility enhancement, coatings, light harvesting, and catalysis. The dendrimer community has recently focused on internally functionalized dendrimers (IFDs) owing to their advanced design and functionality. The synthesis of IFDs relies on advanced orthogonal chemistries and/or (de)protection schemes, as well as careful purification to minimize polydispersity of composition and molecular weight. The studies published on IFDs, however, lay scattered across the chemical literature, and a comprehensive presentation of structural rationale, synthetic procedures, and technologically relevant applications is missing. To address this need, this review presents a comprehensive collection and discussion of all available studies on IFDs, detailing their methods of synthesis and their structure–function correlations. The wide variety of internal functionalities, including hydroxyl, amine, carboxylic acid, allyl, alkyne, and imidazole groups, enables myriad applications in biochemistry, chemical and biomedical engineering, and material science. Particular focus is given to IFDs that are amenable to modular synthetic strategies, which promote higher synthetic yield and scalability, and therefore possess stronger translational and commercial potential. As such, this review guides research groups pursuing the difficult task of IFD rational design and synthesis providing them a concise roadmap to their mission.     

A review on elastic graphene aerogels: Design,preparation, and applications

Graphene aerogels with unique properties, such as ultralow density, super-elasticity, high specific surface area, and excellent thermal stability, have undergone great progress in the past decades. Especially, super-elastic graphene aerogels provide a highly attention-catching platform for developing advanced energy devices, pressure sensors, contaminates adsorbents, and electromagnetic wave shielding and absorption materials, and so forth. In this review, we begin with the introduction and discussion of various fabrication techniques and compare their advantages and disadvantages, focusing on the template-free assembly process and template-assisted assembly process. Then, we summarize the factors influencing the compressibility and elasticity of graphene aerogels, including intrinsic properties of building blocks, constituent materials, and structure design, and their wide applications. At the end, we discuss the current challenges and future prospects of this field.     

Recent advances in thin-layer chromatography of pesticides

Advances in the applications of thin-layer chromatography (TLC) and high-performance thin-layer chromatography (HPTLC) for the separation, detection, and qualitative and quantitative determination of pesticides, other agrochemicals, and related compounds are reviewed for the period 1998-2000. Analyses are covered for a variety of samples, such as food, biological, and environmental, and for residues of pesticides of various types, including insecticides, herbicides, and fungicides, belonging to different chemical classes. References on formulation analysis, hydrophobicity studies, and the use of TLC and thin-layer radiochromatography (TLRC) for studies of pesticide metabolism, degradation, uptake, and related studies are also included.     

Density,viscosity, and surface tension of binary liquid systems: Ethanoic acid,propanoic acid,and butanoic acid with nitrobenzene

Density, viscosity, and surface tension of three binary liquid systems: ethanoic acid+nitrobenzene, propanoic acid+nitrobenzene, and butanoic acid+nitrobenzene have been determined at 25, 35, and 45°C, over the whole composition range. The excess molar volumes, viscosities, Gibbs energies for the activation of flow, and surface tension were evaluated and fitted to a Redlich-Kister type of equation. The Grunberg-Nissan parameter d was also calculated. Binary viscosity data were fitted to the models of McAllister, Heric, Krishnan, and Laddha, Auslander, and Teja and Rice. Surface tension data were fitted to the models of Zihao and Jufu, Rice, and Teja, and an empirical two-constant model.     

Polymer-surfactant and protein-surfactant interactions

The phase behavior and some physicochemical properties of homopolymers (HP) and hydrophobically modified (HMP) polymers, as well as of polyelectrolytes (PE) and proteins (PR), in the presence of aqueous surfactants, or their mixtures, are discussed. Mixing the above components gives rise to the formation of organized phases, whose properties are controlled by polymer and/or surfactant content, temperature, pH, and ionic strength. Depending on the nature, concentration, and net charge of both solutes, molecular solutions, polymer-surfactant complexes, adsorption onto micelles and vesicles, gels, liquid crystalline phases, and precipitates are observed. Such rich polymorphic behavior is the result of a complex balance between electrostatic, excluded volume, van der Waals, and other contributions to overall system stability. It is also modulated by the molecular details and architecture of both the polymer and the surfactant. Different experimental methods allow investigation of the above systems and getting information on the nature of polymer-surfactant interactions (PSI). Surface adsorption and thermodynamic methods, together with investigation of the phase diagrams, give information on the forces controlling PSI and on the existence of different phases. Conductivity, QELS and viscosity allow estimating the size and shape of polymer-surfactant (protein-surfactant) complexes. Optical microscopy, cryo-TEM, AFM, NMR, fluorescence, and relaxation methods give more information on the above systems. Use of the above mixtures in controlling gelation, surface covering, preparing dielectric layers, and drug release is suggested.