锰催化的碳碳键生成反应研究进展

迄今为止,贵金属(铑、钯、钌等)在过渡金属催化的碳碳键生成反应中发挥着主导作用,然而使用廉价金属催化剂更符合可持续发展的要求。锰是地壳中含量排第三位的过渡金属,价格便宜,环境危害性小,有潜力成为贵金属催化剂的替代品并发挥其自身独特的反应性。尽管锰参与的当量反应有大量文献报道,目前锰催化的反应尤其是碳碳键生成反应的发展还不成熟,如何实现高效的催化循环是锰催化领域面临的主要难题之一。本文对锰催化的付-克烷基化反应、格氏试剂的酰化反应、偶联反应、碳金属化反应、自由基反应和碳氢键活化反应进行了综述。     

钯催化惰性碳-氢键胺化反应研究进展

胺化反应是有机化学中最重要的反应之一,近年来,过渡金属催化的碳-氢键胺化反应已经成为合成有机胺化物的重要方法.本文综述了钯催化碳-氢键胺化反应的研究进展,按照底物类型和所活化碳-氢键的类型进行分类,并对该领域目前存在的局限性和未来发展进行了总结和展望.     

Fe和Co催化的碳-碳偶联反应的最新进展

作为廉价而且低毒的金属, Fe和Co是发展催化剂的理想元素. 同时由于Fe和Co有着多种氧化还原价态, 它们的催化化学应该具有极其丰富的内容. 然而由于种种原因, Fe和Co的催化剂很少得到有机化学家的关注. 直到最近几年, 人们才发现Fe和Co的催化剂可以很好地催化碳-碳偶联反应. 综述了Fe和Co催化碳-碳偶联反应的条件、产率和选择性; 探讨了这些新奇反应的可能机理; 并介绍了这些反应在复杂化合物合成中的应用.     

基于环己酮氧化脱氢构建碳-碳与碳-杂键

环己酮是一种廉价易得的大宗有机化工产品,被广泛用作有机合成反应的原料和中间体。脱氢芳构化是合成功能化芳烃的有效途径,使用环己酮作为反应底物,经过亲核加成、脱水和催化脱氢可以将非芳香的有机分子转化为芳香化合物。与传统的芳基化反应相比,该策略避免了苛刻的反应条件和含卤化合物的生产,克服了化学和区域选择性难以控制的难题,为功能化芳烃的合成提供了一条温和、环保的途径。本文就近年来以环己酮为原料,进行氧化脱氢、直接构建碳-碳和碳-杂键,及通过碳-杂键的形成合成杂环化合物的研究现状进行介绍。     

纳米碳材料非金属催化的研究进展

纳米碳材料直接作为催化剂的非金属碳催化是目前材料科学与催化领域的前沿方向之一.相对于传统金属催化剂,纳米碳材料催化剂具有高效环保、低能耗、耐腐蚀等优点.在烃类转化、化学品合成、能源催化等领域表现出优异的催化性能和发展潜力.综述了近年来纳米碳非金属催化研究的最新进展,主要包括新型纳米碳材料的表面性质、催化特性、反应机理和宏观制备等关键问题,并对纳米碳催化存在的挑战和前景进行了展望.     

碳碳双键催化加氢的研究进展

综述了近年来碳碳双键催化加氢的研究进展;分别针对以氢气为氢源的催化加氢反应和以非氢气为氢源的催化转移加氢反应进行了分析概括;指出其中催化转移加氢(包括光照下转移加氢)具有反应条件温和且操作安全简便的优势,应用前景广阔.     

碳点的设计合成、结构调控及应用

碳点是一类环境友好且性能独特的纳米粒子, 在光电转换、 生物医学、 催化及储能等领域的研究日益活跃. 碳点主要分为碳量子点(CQDs)、 石墨烯量子点(GQDs)和碳化聚合物点(CPDs), 其中CPDs作为一种新型碳点, 具有合成原料广泛、 碳化程度及共轭结构可调且材料相容性好等优点. 本文综合评述了近年来碳点尤其是CPDs的合成方法; 阐述了通过选择前驱体分子、 控制反应条件及掺杂原子等手段实现对其碳化和共轭程度、 晶格和能级结构的调控, 从而建立碳点及其杂化与复合材料微纳结构与性能之间的关系; 最后, 介绍了碳点在生物标记与成像、 光(电)催化、 光电转换及储能等领域的应用, 并对碳点领域的发展前景进行了展望.     

基于糖烯的碳苷合成方法研究进展

碳苷是一类具有多种生物活性的糖类天然产物,其独特的C—C糖苷键构筑是糖化学研究中的热点和难点.通过双键官能团构建新的C—C键是有机化学中的常用策略.随着烯化学的飞速发展,含1,2-位双键的糖烯供体在碳苷合成中也取得了显著进步.从FerrierI型碳苷化反应、Heck偶联型碳苷化反应、1-取代糖烯的过渡金属催化偶联碳苷化反应、2-取代糖烯的Michael加成型和自由基加成型碳苷化反应等方面,总结近年来基于糖烯的碳苷合成方法.     

手性磷酸催化α-全碳季碳醛的不对称烯丙基化动力学拆分

手性全碳季碳立体中心的高效构建一直是不对称催化领域的难点和热点.其中,α-全碳季碳非环状醛因具有立体环境拥挤和构象多变性等结构特点,相关不对称合成方法一直发展缓慢.本工作基于手性醛和高烯丙基醇化合物的合成应用重要性,通过Antilla烯丙基化反应,采用2,4,6-三异丙基苯基取代的联萘二酚型手性磷酸催化剂,以较好的产率、立体选择性和选择性系数(最高达到37.0),实现了外消旋α-全碳季碳非环状醛的动力学拆分,为含α-全碳季碳的醛和高烯丙基醇两类手性化合物的合成提供了新思路.     

亲核性氟源在碳碳不饱和键选择性氟化官能化反应中的应用

含氟化合物表现出的特殊理化和生物活性使得其在药物、农用化学品和材料科学等领域有着广泛而重要的应用,因此,含氟化合物的高效制备不仅成为了合成化学的研究热点之一,而且极大地推动了相关领域的蓬勃发展.其中,在有机分子内直接引入氟原子的方法主要有亲电氟化和亲核氟化.相较于亲电氟化,亲核氟化反应所用的氟化试剂通常廉价易得,所需的反应条件也比较温和.作者课题组借助过渡金属催化、可见光氧化还原催化和可见光促进策略,拓展了亲核性氟源在碳碳不饱和键选择性氟化官能化反应中的应用,合成了一系列结构新颖的含氟化合物.在该研究评论中将对此做出小结,并对该领域值得关注的研究方向进行简要的展望.     

电感耦合等离子体质谱法快速测定苦荞茶中铜、铅、镉、钴、镍

建立了用硝酸-高氯酸消解样品,电感耦合等离子体质谱法(ICP-MS)测定苦荞茶中铜、铅、镉、钴、镍的方法.方法具有灵敏度高、检出限低、精密度好、基体干扰少、准确可靠、快捷、简便的特点.各元素方法检出限(3SD,μg/L)分别为:铜0.009、铅0.023、镉0.015、钴0.022、镍0.035;方法精密度(RSD,n=12)分别为:铜2.5%～3.0%、铅2.1%～2.3%、镉3.0%～3.8%、钴2.5%～2.6%、镍1.5%～1.9%;各元素加标回收率分别为:铜95.0%～105.0%、铅95.0%～105.0%、镉98.0%～105.0%、钴95.0%～105.0%、镍95.0%～105.0%.在线用铑作为内标95.0%～105.0%.方法经国家一级标准物质验证,测定值与标准值吻合.应用于实际样品测定,结果满意.     

Analysis of urinary biomarkers for exposure to alkyl benzenes by isotope dilution gas chromatography-mass spectrometry

A validated GC-MS method for the analysis of urinary metabolites of alkyl benzenes is reported. Metabolites for exposure to toluene, xylene and ethylbenzene were analyzed simultaneously using stable isotope substituted internal standards. The method entailed acidic deconjugation of urine samples followed by extractive alkylation with pentafluorobenzyl bromide as alkylating agent. The resulting pentafluorobenzyl derivatives of ortho-, meta-, para-cresol, mandelic acid (MA), hippuric acid (HA) and ortho-, meta-, para-methylhippuric acid (MHA) were then quantified by SIM. Optimized reaction conditions for the extractive alkylation step are reported. The derivatives were found to be sufficiently stable for overnight batch analysis. The LODs were below 0.1 micromol/L for the cresols and below 1 micromol/L for MA and the HAs. Within-batch precision for o-MHA was 7%, for m-MHA 5%, for p-MHA 5.2% and below 5% for the rest of the analytes.     

Economic analysis of ethanol production in California using traditional and innovative feedstock supplies

In this article, we estimate the costs of using alternative feedstocks to produce ethanol in a 40 million-gal facility in California’s San Joaquin Valley. Feedstocks include corn imported from Midwestern states and locally grown agricultural products such as corn, grapes, raisins, oranges, and other tree fruits. The estimated feedstock costs per gallon of ethanol include $0.92 for Midwestern corn, $1.21 for locally grown corn, $6.79 for grapes, $3.36 for raisins, $3.92 for citrus, and $1.42 for other tree fruit. Adjusting for coproduct values lowers the estimated net feedstock costs to $0.67/gal of ethanol for Midwestern corn, $0.96 for locally grown corn, $6.53 for grapes, and $3.30 for raisins. We also examine the potential increases in net revenue to raisin producers, made possible by having an alternative outlet available for selling surplus raisins.     

Normal Coordinate Analysis for Polymer Systems: Capabilities and New Opportunities

Normal coordinate analysis is an important tool in studying the structure, dynamics, and physical properties of polymer systems. In this article the capabilities of normal coordinate analysis (NCA) are explored in some detail. The use of the eigenvalues and eigenvectors from NCA is catalogued for a wide variety of purposes: for assigning or interpreting polymer spectra, for structural determination, for constructing force fields, for computing heat capacity and other thermodynamic properties, and for computing other physical properties. Examples are given for crystals, melts, and amorphous systems. Also described are methods for characterizing the normal mode vectors that are especially useful for larger systems, in which a large amount of data must be analyzed or where visualization or animation fails. Finally, a recently developed method for eliminating negative eigenvalues in systems with tens of thousands of atoms, trajectory averaging, is presented. Also described are several advances in numerical linear algebra for speeding up the diagonalization phase and for computing physical properties without requiring full diagonalization of the Hessian matrix.     

Spectrophotometric and spectrofluorimetric methods for analysis of tramadol, acebutolol and dothiepin in pharmaceutical preparations

Sensitive spectrophotometric and spectrofluorimetric methods are described for the determination of tramadol, acebutolol and dothiepin (dosulepin) hydrochlorides. The two methods are based on the condensation of the cited drugs with the mixed anhydrides of malonic and acetic acids at 60 degrees C for 25-40 min. The coloured condensation products are suitable for the spectrophotometric and spectrofluorimetric determination at 329-333 and 431-434 nm (excitation at 389 nm), respectively. For the spectrophotometric method, Beer's law was obeyed from 0.5 to 2.5 microg ml(-1) for tramadol, dothiepin and 5-25 microg ml(-1) for acebutolol. Using the spectrofluorimetric method linearity ranged from 0.25 to 1.25 microg ml(-1) for tramadol, dothiepin and 1-5 microg ml(-1) for acebutolol. Mean percentage recoveries for the spectrophotometric method were 99.68+/-1.00, 99.95+/-1.11 and 99.72+/-1.01 for tramadol, acebutolol and dothiepin, respectively and for the spectrofluorimetric method, recoveries were 99.5+/-0.844, 100.32+/-0.969 and 99.82+/-1.15 for the three drugs, respectively. The optimum experimental parameters for the reaction has been studied. The validity of the described procedures was assessed. Statistical analysis of the results has been carried out revealing high accuracy and good precision. The proposed methods were successfully applied for the determination of the selected drugs in their pharmaceutical preparations with good recoveries. The procedures were accurate, simple and suitable for quality control application.     

傅里叶变换近红外光谱法同时定量分析水溶液中乙醇、果糖和葡萄糖

利用乙醇、果糖和葡萄糖在波数为14000-7500cm^-1范围内的吸收值,在近红外谱区用偏最小二乘法（PLS）对体系进行建模,并通过内部和外部样品校验确认最佳数据预处理方法。结果表明,乙醇在0.05-0.25L/L,果糖在0.01-0.05g/mL及葡萄糖在0.005-0.009g/mL的范围内外部校验模型较好的分别是在PLS中所用的一阶偏导（平滑点数是5）、二阶偏导（平滑点数是5）和直线消除法的数据预处理方法所建立的模型,其外部校验预测结果的相对误差在2%左右。此方法具有可同时测定不同样品,简便快速及成本低等优点。     

盐酸氯丙嗪作探针二级散射和倍频散射法测定环境水样中某些阴离子表面活性剂

在pH3.0~5.0的HAc-NaAc缓冲溶液中,盐酸氯丙嗪与十二烷基苯磺酸钠、十二烷基磺酸钠和十二烷基硫酸钠等阴离子表面活性剂反应形成离子缔合物时,仅能引起吸收光谱和荧光光谱的微小变化,但却能导致二级散射(SOS)和倍频散射(FDS)的显著增强。最大SOS峰均在552nm附近,最大FDS峰均在390nm附近。其中SOS法灵敏度更高,它对十二烷基苯磺酸钠、十二烷基硫酸钠和十二烷基磺酸钠的检出限分别为0.047、0.106和0.117mg/L,而其线性范围分别为0.2~12、0.4~15和0.4~20.0mg/L。研究了反应产物的吸收、荧光、SOS和FDS光谱特征、适宜的反应条件及分析化学性质,据此发展了一种用SOS技术灵敏、简便、快速测定阴离子表面活性剂的环境友好型新方法。     

高纯度树状大分子聚酰胺-胺的合成与表征

以乙二胺为核,通过Michael加成,与丙烯酸甲酯交替反应,合成了0.5代到5.0代聚酰胺 胺树状大分子。 利用傅里叶变换红外光谱、核磁共振氢谱、液相色谱和元素分析等对各代产品进行了表征,探索了反应温度、时间及反应物配比对产物的影响,确定生成聚酰胺-胺(PAMAM)的半代产物时反应温度为25 ℃,整代产物时反应温度为35 ℃;0.5G的反应时间为18 h,1.0G、1.5G的反应时间为24 h,2.0G、2.5G反应36 h,3.0G、3.5G反应48 h,4.0G、4.5G反应3 d,5.0G反应4 d。 分离提纯是树状大分子制备中遇到的最大困难,通过选择性溶剂萃取的方法对产品分离纯化,筛选出乙醚作萃取剂、甲醇作溶剂交换剂,大大提高了产品的纯度。     

Validated spectrophotometric method for quantitative determination of simvastatin in pharmaceutical formulations and human serum

A simple ultraviolet spectrophotometric method for the determination of simvastatin in methanol has been devised and compared with the existing pharmacopoeial RP-HPLC method for the estimation of the drug. Analytical parameters such as stability, selectivity, accuracy, and precision have been established for the method, using SIMS® tablets and human serum samples, and evaluated statistically to assess the application of the method. The method was validated under ICH and USP guidelines and was found to comprise the advantages for simplicity, stability, sensitivity, reproducibility, and accuracy for use as an alternative to existing nonspectrophotometric methods for the routine determination of the drug in pharmaceutical formulations and for pharmaceutical investigations involving simvastatin.     

Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

Dibenzomethanopentacene (DBMP) is shown to be a useful structural component for making Polymers of Intrinsic Microporosity (PIMs) with promise for making efficient membranes for gas separations. DBMP-based monomers for PIMs are readily prepared using a Diels–Alder reaction between 2,3-dimethoxyanthracene and norbornadiene as the key synthetic step. Compared to date for the archetypal PIM-1, the incorporation of DBMP simultaneously enhances both gas permeability and the ideal selectivity for one gas over another. Hence, both ideal and mixed gas permeability data for DBMP-rich co-polymers and an amidoxime modified PIM are close to the current Robeson upper bounds, which define the state-of-the-art for the trade-off between permeability and selectivity, for several important gas pairs. Furthermore, long-term studies (over ≈3 years) reveal that the reduction in gas permeabilities on ageing is less for DBMP-containing PIMs relative to that for other high performing PIMs, which is an attractive property for the fabrication of membranes for efficient gas separations.