氘代聚苯乙烯的合成及表征

在惯性约束聚变(ICF)靶材应用领域,氘代聚合物一直占据着重要位置。本文在氘代苯乙烯(D8,98%)中加入质量分数为其0.4%的引发剂,采用本体聚合方法聚合全氘代聚苯乙烯(D8,DPS),反应温度为70℃,反应时间为72 h,用傅里叶变换红外光谱仪、核磁共振仪对DPS的结构进行表征,综合测试结果表明产物为DPS。采用差式扫描量热仪和热重分析仪分析DPS的热性能,表明DPS的玻璃化转变温度为105℃,5%失重温度为380℃,热性能较好,满足ICF试验使用要求。     

新法氘代溴苯-d_5的合成与表征

以氘代苯（Ｃ６Ｄ６）及单质溴（Ｂｒ２）为原料,铁粉（Ｆｅ）及单质碘（Ｉ２）为催化剂,同时改进了常规溴苯合成中粗产物的后处理工序,最终合成出了产率达７２．５％ 、氘代率达９９．２％ 的氘代溴苯（Ｃ６Ｄ５Ｂｒ）。采用付立叶变换红外光谱仪及激光拉曼光谱仪对Ｃ６Ｄ５Ｂｒ的振动光谱特性进行了研究,此外亦采用相对重量校正因子１Ｈ－核磁共振波谱法对样品氘代率的测定进行了探讨。     

格林尼亚反应合成全氘代-α-苯乙醇

以重水 (D2 O)及电石 (CaC2 )为原料 ,先制得氘代乙醛 (CD3CDO) ;氘代苯则与溴和金属镁反应生成氘代苯基溴化镁 (C6D5MgBr)。CD3CDO再与C6D5MgBr进行格林尼亚反应 ,并用酸性重水溶液水解 ,最终制得氘代率xD≈ 99%的全氘代 α 苯乙醇 (C6D5—CDODCD3) ,产率 71.2 % (以氘代溴苯计 )。作者介绍了以D2 O、CaC2 及C6D6为原料制备C6D5—CDODCD3 的合成工艺及采用内标相对摩尔校正因子氢核磁共振波谱 (1HNMR)技术表征产物氘代率的方法     

临床试验的氘代药物及其氘代合成策略

综述了临床在研和已上市的20种氘代药物,分析了其氘代合成策略,结果表明氘代甲基CH3-d3是使用频率高和较成功的方法,展望了各种氘代策略的前景。     

全氘代聚苯乙烯的合成

以氘代苯（Ｃ６Ｄ６）、氘代醋酸（ＣＤ３ＣＯＯＤ）及重水（Ｄ２Ｏ）等市售试剂为原料,经酰化、镍铝合金碱性重水液相还原、脱水及自由基本体聚合等一系列反应,在国内首次合成出了全氘代聚苯乙烯（ＰＳＤ）。该ＰＳＤ材料氘代率达９８．３５％,可望在激光聚变热核靶、低损耗塑料光纤及聚合物相容性研究等领域得到广泛的应用。     

氘代氨基甲酸酯类化合物的合成与表征

设计了以有机酚为原料制备氘代氨基甲酸酯类化合物的合成路线。有机酚(Ⅰa~Ⅰc)在Na OH催化作用下,经与三光气(BTC)反应,合成了中间体氯甲酸酯(Ⅱa~Ⅱc),再与一甲胺-D3-盐酸盐缩合反应,制得目标化合物(Ⅲa'~Ⅲc')。设计的合成路线避免使用异氰酸酯,且操作简单,工艺流程短,副产物少,收率可达60%以上,氘同位素丰度没有降低。产物经HPLC、MS、1HNMR和13CNMR表征,结果表明,化学纯度99%,氘同位素丰度99 atom%。     

氘代对二乙烯基苯的合成

利用魏梯希-霍恩(Witting-Horne)反应合成了标题化合物,通过红外、核磁共振和质谱对产物结构及氘代率进行了表征和分析,结果表明产物氘代率为95%,产物结构符合预定结构.     

氘代药物进展

简要地介绍了氘的动力学同位素效应,以及将药物分子中特定的氢替换成氘得到的氘代药物,可以改变药物在体内的代谢速度甚至是代谢途径,达到增加药效和减少副作用的目的。同时还介绍了氘代药物的研究进展和临床情况。尽管到目前为止还没有一个氘代药物被批准上市,但是其临床中表现出的治疗效果还是显著的,相信在不久的未来氘代药物的上市会得到实现。     

无氘代核磁实验鉴别喹诺酮类抗生素

核磁共振技术是制药领域中一种重要的研究手段。在没有合适的氘代溶剂选择的情况下,可选择无氘代核磁共振技术。将无氘代核磁共振技术引入制药工程专业本科专业实验教学,充分发挥核磁共振波谱仪在制药专业实验教学中支撑作用。通过分组预先查阅资料、确立鉴别方案、进行无氘代核磁共振实验和图谱的对比分析,实现对6种喹诺酮类抗生物的鉴别,有利于提高学生的动手能力、自主学习、思考问题和解决问题的能力。     

钴催化氘代甲氧基化苯甲酰胺衍生物的合成研究

由于C-D键独特的稳定性和标记作用,在化合物中引入氘对于候选药物的合成以及反应机理的研究具有重要意义。芳基醚是一种在药物、溶剂和聚合物前体等方面具有应用前景与价值的化合物,广泛存在于药物中间体和农业生产中。本文根据C-D键和芳基醚类化合物的双重优势,以氘代甲醇为氘源,开发了一种钴(II)/水杨醛配体组成的催化体系,在氧化条件下高效合成了氘代甲氧基化芳烃化合物,该方法无需使用酸碱添加剂,反应条件温和,具有良好的官能团相容性和氘掺入量,各种不同取代的苯甲酰胺衍生物产率中等至良好。     

有机硫加氢转化催化剂的使用

介绍了有机硫加氢转化催化剂的化学组成、物理结构与活性关系，阐述了氢解反应及预硫化条件和催化剂选用原则，列举了工业应用实例。     

炸药晶体品质表征技术概述

从粒度、形貌、内部缺陷、晶型鉴定和纯度分析5个方面概述了炸药晶体品质表征技术。对其中主要方法的原理及优、缺点进行了分析,并介绍了一些具体应用。指出今后的研究方向及关键点,以期建立完善的炸药晶体品质表征技术体系,进而为提高含能材料的性能提供依据。     

有机生物环境分析中的新技术与新方法

综述了对食品中残留的有害物测定的新方法,环境水样中有害物质分析测定的新方法和中药材中有效成分测定的新方法,并对有机分析的发展进行了展望。     

Characterization of crosslinked starch materials with spectroscopic techniques

The structure, mobility, and properties of crosslinked starch materials of various compositions were investigated with FTIR and NMR spectroscopy, and relaxation time measurements were taken with cross‐polarization/magic‐angle‐spinning (CP–MAS) and magic‐angle‐spinning (MAS) spectroscopy. Characterization by Fourier transform infrared spectroscopy confirmed the crosslinking reaction. The CP–MAS and MAS spectra allowed the assignment of the principal ¹³C signals. The molecular mobility of these polysaccharides was analyzed in terms of the cross‐relaxation time between the protons and carbons, the ¹H spin–lattice relaxation time in the rotating frame, and the ¹H longitudinal spin–lattice relaxation time. Relaxation studies showed that increasing the crosslinking degree increased the amorphous content, and the material became rigid as an increasing number of covalent bonds in the polymer network reduced mobility. The values of the spin–lattice relaxation in the rotating frame reflected the homogeneous nature of the materials. The correlation between the crosslinking degree, structure, and mobility and the sorption properties of these sorbents was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2650–2663, 2004     

Synthesis of completely deuterated hydrocarbons

The possibility of synthesizing a new material—completely deuterated hydrocarbons—by the Fischer-Tropsch process has been demonstrated. This is the first step toward the formation of a research-and-production basis for the creation of a pilot plant. There was no isotope effect; consequently, the key characteristics of the synthesis and products were determined by the properties of the catalyst and reaction conditions, irrespective of whether hydrogen or deuterium was used in the starting mixture. Waxes were removed from the catalyst surface under mild conditions; this did not require any special equipment or the transfer of catalyst to another reactor. The chosen catalyst was highly stable and can be used in a pilot plant for the production of completely deuterated waxes. The first evaluation of the properties of the new materials showed that they were promising as solvents for NMR, radioactive labels, targets, neutron flux moderators, etc.     

Characterization techniques for thin and thick ferroelectric films

A few measurement techniques are presented for characterization of thin and thick ferroelectric films at microwave frequencies. Broadband reflection type measurements using a probe station are considered for on wafer characterization of thin films. The accuracy of the method is analyzed with respect to measurement residual systematic errors. A test structure is introduced allowing quick and accurate extraction of the film parameters based on the rigorous full-wave model. Two measurement techniques are reported for electrode-less characterization of thick ferroelectric films. The first method (X-band) is based on the reflection type measurement of a resonator established by a layered alumina/ferroelectric sample loaded in a cut-off waveguide. The second method (B-band) utilizes an open resonator (OR) technique. Theoretical and experimental results are presented.     

Characterization of microporous non-supported membrane top-layers using physisorption techniques

Gas physisorption is a generally used technique for the characterization of porous solids. Microporous solids, however, need a different approach compared to mesoporous solids due to enhanced adsorption in pores of molecular dimensions. Therefore, conventional theories and models can not be used. The application of physisorption for microporous solids, and the interpretation of the isotherms is elucidated. Some models presented in literature for pore size assessment in the micropore range are discussed. Based on a number of criteria, the Horváth-Kawazoe model, modified for cylindrical pore geometry, is selected. N₂ adsorption measurments on zeolites were performed to calibrate the method and to show the applicability and physical justification. Typical data obtained from experiments on non-supported microporous silica membrane top-layers show that the pore size distribution of these materials is bimodal, with a strong maximum at an effective diameter of 0.5 nm, and a weaker maximum at 0.75 nm.     

Mass spectra of TMS esters of deuterated decanoic acids and of TMS ethers of deuterated decanols

Mass spectra of trimethylsilyl esters of nine specifically deuterated decanoic acids and of trimethylsilyl ethers of the corresponding deuterated decanols and of tri[²H₃] methylsilyl derivatives of most of the acids and of decanol have been measured. The fragmentation patterns have been used to examine the formation of ions m/z 117, 129, 131, 132, 145, 159, 171, 185 and 201 in the spectrum of the TMS ester of decanoic acid. Mechanisms of breakdown of one ion to another have been proposed. Similarities and differences in ion formation between spectra of TMS esters and methyl esters have been examined. It has been shown that ion m/z 132 is produced by the McLafferty rearrangement and that ion m/z 117 is formed from it by loss of a silyl methyl group. Ion m/z 145 is formed by hydrogen transfer from C-5, C-6 or C-7 to the carbonyl oxygen and γ-cleavage. Ion m/z 129 is formed from ion m/z 145 by loss of the previously transferred hydrogen and a silyl methyl group. A mechanism of formation of ions m/z 115, 129, 143 and 157, which contained only one silyl methyl group, observed in the mass spectrum of the TMS ether of decanol, has been proposed. Ions in spectra of the derivatives can be used to locate the position of deuterium, or other substituents, at a number of the carbons of decanoic acid or decanol.     

Pyrolysis of deuterated and reduced coals

Samples of a coal and a lignite were boiled in pyridine, partially reduced and partially deuterated by modified Birch reductions. These samples were slowly pyrolysed in an inert atmosphere in a horizontal tube furnace to temperatures in the range 300–600 °C. The yields and the nature of the products are reported; in particular an attempt is made to characterize the various tars, and the pyrolyses are described in terms of a simplified mechanism. It was found that boiling the fuels in pyridine increased the subsequent yield of tar and increased the proportion of high-boiling material within the tar. Tar formation was diffusion-controlled. The role of hydrogen atoms from the hydroaromatic structure of the fuels in the formation of tar, liquor and gas was confirmed. Experiments with partially deuterated fuels established that during pyrolysis interchange of hydrogen atoms occurred amongst the molecules of the gas. Further pyrolyses of partially deuterated coals under wider conditions should be profitable.