(S)-1-苄基-3-羟基吡咯烷的合成及红外光谱研究

从L-苹果酸出发,经过与苄胺缩合反应得到(S)-1-苄基-3-羟基吡咯烷-2,5-二酮,再通过硼氢化钠-碘体系还原制得重要的医药中间体(S)-1-苄基-3-羟基吡咯烷。采用红外光谱法对原料、中间体及产物进行了测试并对硼氢化钠-碘体系还原酰亚胺的机理进行了研究。通过比较原料、中间体及产物相应特征吸收峰的消失或是出现,可知所得的产物为(S)-1-苄基-3-羟基吡咯烷;还原机理研究表明,硼氢化钠在碘催化下生成的硼烷与酰亚胺中的羰基形成四元环状过渡态,同时另外一分子硼烷与酰亚胺中的氮原子形成N-BH3复合物,然后羰基还原完全,得到(S)-1-苄基-3-羟基吡咯烷-硼烷复合物,最后在甲醇作用下脱去硼烷得到最终产物。     

α-苯甲胺基-β-(3-吲哚基)-丙酸甲酯的合成

以L-色氨酸为原料经过4步得到α-苯甲胺基-β-(3-吲哚基)-丙酸甲酯,它是一种具有潜在的抗肿瘤活性的吲哚二酮哌嗪化合物的中间体,首先通过“酰氯法”合成L-色氨酸甲酯盐酸盐,再脱去盐酸,与苯甲醛发生缩合反应形成希夫碱,最后选择性还原,得目的产物,得率54.9%.     

(2R,5S)-N-间氟苄基-2,5-二甲基哌嗪的合成

以(2R,5S)-2,5-二甲基哌嗪为原料,经过成盐,单取代反应,用D-酉石酸对光学异构体的手性拆分,用氢氧化钠游离,最终合成(2R,5S)-N-间氟苄基-2,5-二甲基哌嗪,反应总收率为83％.该物质的合成未见文献报道,目标化合物用1H NMR,IR进行结构表征.     

一种苯并二氢呋喃新木脂素苷的NMR研究

(7R, 8S)-脱氢双松柏醇-4, 9双-O-β-D吡喃葡萄糖苷是从中药北沙参(Glehnia littoralis Fr. Schmidt ex Miquel)醇提取物中分离得到的一种苯并二氢呋喃新木脂素苷类化通过化学方法和波谱分析鉴定了该化合物的结构．采用2D NMR技术对其1H和13C号进行了全归属．     

槲皮素-3-鼠李糖-(6-对羟基反式桂皮酰)葡萄糖甙1-2连接的NMR谱证据

用2D NMR技术研究了从银杏叶提取物中分离的一个黄酮双糖甙[槲皮素-3-鼠李糖-(6-对羟基反式桂皮酰)葡萄糖甙]的结构,对鼠李糖部分的¹H NMR,¹³C NMR化学位移进行了归属.¹³C化学位移和¹H NOE相关性都证明鼠李糖为1″-2″连接.     

氦原子(e,3-1e)反应中未探测电子屏蔽效应的理论研究

在DS3C模型的基础上,对氦原子(e,3-1e)反应的末态He+2场中未探测电子的屏蔽效应进行了研究.计算了(e,3-1e)过程中入射能为640 eV时,电子入射双电离He原子的四重微分截面(4DCS);讨论了非一级效应对截面结构的影响.所得结果与其他理论计算进行比较发现:文中结果与最新测量的实验数据较好地吻合.     

新试剂3-对氟苯基-5-(2′-胂酸基苯偶氮)绕丹宁的合成及荧光法测定铋的研究

合成了新型荧光试剂 3 对氟苯基 5 (2′ 胂酸基苯偶氮 )绕丹宁 ,并并经元素分析、IR确证了其结构。研究了其荧光性质 ,发现在 pH 5 4时试剂与痕量铋 (Ⅲ )形成的螯合物可使试剂的荧光强度大大减弱 ,在λex/λem =30 5 / 4 0 7nm处有最大峰 ,其荧光猝灭值与铋的浓度在 0～ 0 0 2 5 μg·mL-1范围内呈线性关系 ,检出限达 1 2× 10 -10 g·mL-1。建立了一种荧光光度法测定痕量铋的新方法     

单甲基酯亚磺酸帕珠沙星盐的波谱学研究

帕珠沙星(Pazufloxacin), (S)-7-(1′-氨基环丙基)[N,8-缩-(2″-甲基)乙氧基]-3-羧酸-6-氟-喹啉-[4]酮-(S)-7-(1′-Aminocyclopropy1)-[N,8-de]-(2″-methy1)-epoxyethane-3-Carbony1ic acid-6-fluoro-quino1-[4]-one,及其单甲基酯亚磺酸盐是一种可望用于抗革兰氏阳性菌和阴性菌的防治药物. 本文采用¹H NMR、¹³C NMR、DEPT及二维谱¹H-¹H COSY、HMQC、HMBC和IR、MS推证了单甲基酯亚磺酸帕珠沙星盐分子结构的正确性,并进行了¹H、¹³C NMR谱峰的全归属. 对其IR、MS各主要峰也进行了归属.     

海绵Callyspongia Fibrosa的化学成分研究(Ⅰ)

从中国南海海绵中分离鉴定出 5个化合物 ,其结构确定为对羟基苯甲酸 ( Ⅰ)、鲨肝醇 ( Ⅱ )、胸腺嘧啶( Ⅲ )、尿嘧啶 ( Ⅳ )、胸腺嘧啶脱氧核苷 (Ⅴ )。     

Heisenberg realization for U q (sl n ) on the flag manifold

We give the Heisenberg realization for the quantum algebra U _q (sl _n ), which is written by theq-difference operator on the flag manifold. We construct it from the action of U _q (sl _n ) on theq-symmetric algebraA _q (Mat _n ) by the Borel-Weil-like approach. Our realization is applicable to the construction of the free field realization for U _q [2].     

马骝卵挥发油的GC-MS分析

气相色谱 -质谱联用研究了中药马骝卵的挥发油化学成分 ,共鉴定出 17种成分 ,占色谱总溜出峰面积的 5 8.5 2 %。其中主要成分为十六酸乙酯、十六酸正丁酯、月桂酸乙酯、亚油酸乙酯、顺式 -油酸乙酯、9,12 -二烯 -十八酸丁酯、顺 - 9-烯 -硬脂酸丁酯、十二酸乙酯、雪松醇、2 ,3,4 ,7,8,8a-六氢化 1H- 3a,7-亚甲基奥。     

应用多核固体核磁共振光谱与量子化学计算的方法研究层状的过渡金属硫化物

层状的过渡金属硫化物及其衍生物在许多领域内有着广泛的应用前景. 具体应用包括催化、陶瓷、润滑、能量储存、半导体、电子与光学器件. 该文报道了作者最近用固体核磁共振光谱的方法来表征几种有代表性的过渡金属硫化物(MS₂: M=Zr, Ti, W, Mo和Ta)的结果. 并在不同的磁场强度下（21.1、14.1、9.4 T）成功地获取了³³S, ^47/49Ti,⁹¹Zr,⁹5Mo 在天然丰度下的固体核磁共振光谱. 为了帮助解释实验结果,同时还进行了量子化学计算. 实验及理论计算的结果都表明³³S, ^47/49Ti, ⁹¹Zr, ⁹⁵Mo 的固体核磁共振参数对于这些核的局部几何与电子环境非常敏感.     

柚子皮挥发油化学成分分析

使用水蒸气蒸馏法提取柚子皮中的挥发油,利用气相色谱-质谱联用技术对柚子皮化学成分进行分离鉴定,采用色谱峰面积归一化法确定各成分的相对含量。分析结果表明,共检测出62种组分,鉴定了其中的31种组分,占挥发油组分总量的50.0%。主要成分是β-蒎烯、4,4A,5,6,7,8-六氢-4,4A-二甲基-6-(1-甲基亚乙基)-(4R-顺)-2(3H)-萘酮、氧化芳樟醇、(E,E)-3,7,11,15-四甲基-1,6,10,14-十六碳四烯-3-醇。     

Surface‐enhanced resonance Raman spectroscopic characterization of cytochrome c immobilized on 2‐mercaptoethanesulfonate monolayers on silver

Single‐component self‐assembled monolayers (SAMs) of mercaptoethanesulfonate (MES) on Ag surfaces were studied with surface‐enhanced resonance Raman scattering (SERRS) spectroscopy with a view to their application to immobilize (ferro)cytochrome c (cyt c). SERS studies revealed that MES molecules adopt primarily trans (T) conformation even at early stages of the SAM growth and over wide range of pH values. High accessibility of the negatively charged groups for (bio)molecules in solution makes single‐component MES SAMs suitable linkage monolayers for electrostatic attachment of cyt c, which was verified with SERRS. Cyt c was successfully anchored to MES‐coated Ag at natural (∼5), neutral, and isoelectric point (10.6) pH. At pH = 7.0 and 10.6, SERRS bands characteristic of native six‐coordinated low‐spin (6cLS) heme iron configuration were detected. Lack of buffering resulted in additional appearance of five‐coordinated high‐spin (5cHS) SERRS markers and the presence of bands indicating ferric ion. An electrostatic attraction between protein and SAM was confirmed to exclude the hydrophobic interactions involved in cyt c binding. Cyt c attached to MES SAM on Ag was found to be electroactive at neutral pH, and protein oxidation was assisted with reversible conversion of 6cLS to the non‐native 5cHS state. Alteration of heme orientation deduced from SERRS spectra upon change of redox state allowed us to propose the protein dynamics as the electron transfer rate‐limiting step. Copyright © 2010 John Wiley & Sons, Ltd.     

Photolysis and E. S. R. Studies on Triphenylphosphinecarbethoxymethylene

Although several different groups have studied the photolysis of phosphorus ylides, none have utilized e. s. r. to support the postulated decomposition mechanisms. The fundamental question which awaits a definitive answer is which bond breaks first upon photolysis. Tschesche¹ and de Silva² utilizing the ylides (1) and (2) suggested that the carbon-phosphorus double bond was initially broken while Nagao³ using (3) proposed phenyl-phosphorus bond cleavage.     

Self‐assembled monolayers of mercaptosuccinic acid monolayers on silver and gold surfaces designed for protein binding. Part II: vibrational spectroscopy studies on cytochrome c immobilization

An attempt has been made for using MSA‐modified electrodes as linkage monolayers for electrostatic and covalent binding of cytochrome c (Cc). For MSA monolayers grown from an aqueous solution on Ag, attachment of Cc in its native state is proved in the case of covalent bonding. Electrostatic immobilization of Cc at pH 7 results in presence of at least some amount of Fe²⁺ high‐spin configuration and/or Fe³⁺ oxidation state. Native protein Fe²⁺ low‐spin state of Cc is observed after applying a negative potential to the Ag electrode. The influence of the solvent used for the preparation of the MSA monolayer and thiol surface coverage of the Ag surface was studied. It was shown that the key factor to obtain the native structure of Cc is the successful blocking of the metal surface by the MSA linking layer. IRRAS measurements of MSA on monocrystalline gold (111) at neutral pH confirm the successful electrostatic Cc immobilization, which preserves the Fe²⁺ oxidation state of the chromophore on this substrate. Copyright © 2007 John Wiley & Sons, Ltd.     

Adsorptive parameters and influence of hot geometries on the SER(R) S spectra of methylene blue molecules adsorbed on gold nanocolloidal particles

The vibrational signatures of methylene blue (MB) dye molecule have been reported. Complete vibrational assignments of the molecule are presented for the first time. Concentration‐dependent surface enhanced resonance Raman scattering [SER(R) S] spectra of the molecule have been investigated. Fluorescence spectroscopic technique has been applied to explore the concentration of the probe molecule actually adsorbed on the gold nanocolloidal (AuNC) surface. The free energy of adsorption and saturated concentration of MB molecules on AuNC surface are also estimated. Gigantic enhancements ~10⁵–10¹³ orders of magnitude have been recorded for the enhanced Raman bands in the SER(R) S spectra. The possible orientation of the molecule on the AuNC surface and their probable protrusions within the hot spots have been suggested. The hot geometries and correlation between the plasmonic behavior of the nanoparticles and enhancement efficiencies of the SER(R) S band have been mapped with the aid of three‐dimensional finite difference time domain (3D‐FDTD) simulations. Application of soft lithographic technique to engineer the pattern formation of hetero dimeric spherical aggregates will be an interesting field of study in future to enhance the detection limit of this and similar types of dye molecules. Copyright © 2015 John Wiley & Sons, Ltd.     

姜科植物化学成分的色谱／质谱研究

本文研究了姜科植物１１个样品，提取了挥发油，用色谱／质谱技术从挥发油中鉴定出１００多种成分。其中α－蒎烯，β－蒎烯，莰烯１，８－桉油素，β－水芹烯，柠檬酸，柠檬醛，香叶醇，丁子香酚，芳樟醇，α－姜烯，β－姜烯，α－姜黄烯，β－姜黄烯，石竹烯，姜酮，β－荜澄茄烯，香芹酮，乙酸香叶酯，乙酸芳樟酯等２０种化合物是多数姜科植物挥发油的共同成分。