疏水-亲脂相互作用对化学反应性的影响 7: 十四元和十八元环的邻基参与

本工作研究了不同链长的ω-取代羧酸对硝基苯酯p-NO2-C6H4OCO(CH2)n-1Y(简称n-Y,n=17,13,11;Y=SH,H,OH,Br和SCH3)在Me2SO-H2O溶剂体系(有机溶剂体积组成分数φ=0.40,0.45,0.50,0.55)中的水解动力学,观察到疏水-亲脂作用影响下,由于13-SH和17-SH长链分子自身绕曲,可以实现十四元环和十八元环的大环邻基参与,至于11-SH的水解,则观察不到十二元环的邻基参与.因此,这些受物的邻基助效确与链长有关.溶剂组成对此现象也有影响.     

4β-氮取代氨基酸的5-Fu酯-4′-去甲表鬼臼的合成

根据药物设计中的结合原理,考虑到氨基酸具有较好的水溶性,并具有降低药物毒性的作用,我们以氨基酸为载体将抗肿瘤药物5-Fu和4′-去甲表鬼臼结合. 以N-保护的氨基酸钾盐与1-(ω-溴丙基)-5-Fu反应制备得到氨基酸的ω-(N1-5-Fu基)-丙醇酯,再与4β-Br-4′-去甲表鬼臼反应,制备了四种4β-氮取代氨基酸的ω-(N1-5-Fu)酯-4′-去甲表鬼臼.合成路线如下:     

ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯的合成及其光性能研究

合成了9个新的双荧光团化合物ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯和3个模型化合物,讨论了这些化合物的结构与光性能之间的关系。     

双膦酸及其酯类化合物的合成研究进展

综述了双膦酸及其酯类化合物的最新合成研究进展:(1) α-羟基取代的双膦酸及其酯;(2) α-氨基酸取代的双膦酸及其酯;(3) α-卤素取代的双膦酸及其酯;(4)烷基取代的双膦酸及其酯;(5) α-杂原子取代的双膦酸及其酯.     

β—三氯化锡基丙烯酸甲酯与Schiff碱配合物分解反应及产物结构表征

将酯基锡 Me O2 CCH2 CH2 Sn Cl3( 1 )与 Schiff碱 ( 2 -HOC6 H4CH NC6 H5) ( 2 )反应合成配合物Me O2 CCH2 CH2 Sn Cl3· ( 2 -HOC6 H4CH NC6 H5) ( 3) ,在其反应混合液放置过程中发生分解生成酯基锡与无机氯离子形成的配合物 Me O2 CCH2 CH2 Sn Cl4- · H+ ( 4)和酯基锡与 Schiff碱的酚氧负离子取代生成的配合物Me O2 CCH2 CH2 Sn Cl2 · ( 2 -OC6 H4CH NC6 H5) ( 5 ) .用元素分析、IR及 NMR对配合物 3,4 ,5进行了表征 ,并对配合物 4的晶体结构进行了解析 .配合物 4为正交晶系 ,空间群 P2 cn,a=0 .785 2 ( 2 ) nm ,b=1 .2 2 36( 1 0 ) nm,c=1 .695 2 ( 4) nm,α=β=γ=90°,V=1 .62 87nm3,Z=4 ,Dc=1 .79g/ cm3,F ( 0 0 0 ) =860 ,μ=2 2 .2 cm- 1 ( Mo) ,R=0 .0 4 49,ωR=0 .0 382 .配合物 4的空间构型为畸变的八面体构型 ,中心锡原子的配位数为 6.配合物 5为 Schiff碱中的酚氧负离子取代配合物 1中的一个氯离子形成的配合物 ,锡原子的配位数为 5     

三组分反应高效合成螺[环戊烷-1,3'-吲哚啉]衍生物（英文）

烷基异氰酸酯、丁炔二酸二酯(丙炔酸酯)和3-苯甲酰亚甲基-2-吲哚酮在甲苯中回流反应,高产率地生成螺[环戊烷-1,3'-吲哚啉]衍生物.然而,含有游离氨基的3-苯甲酰亚甲基-2-吲哚酮参加反应时,未取代的氨基可与另一分子丁炔二酸二酯及烷基异氰酸酯继续反应形成含有氨基取代的氮杂-1,3-二烯支链的螺[环戊烷-1,3'-吲哚啉]衍生物.另一方面,3-芳亚甲基吲哚-2-酮参与三组分反应时,仅有游离氨基参与反应,生成2-(2-氧吲哚-1-基)-3-[(烷基亚氨基)亚甲基]丁酸酯.发现两种游离氨基参与多组分反应时,分别形成了含有C2-取代的1-氮杂-1,3-丁二烯(C=C—C=NR)和C4-取代的1-氮杂-1,2-丁二烯(C—C=C=NR)结构单元的吲哚酮衍生物.     

一种计算无机含氧酸pk1的新公式

提出了两个新的拓扑指数：Y＝（DR＋2）／n^0.5＋2N，Z＝[(8-DR)^N(n-1)(ω-1)]^0.05。将主族元素25种单中心无机含氧酸的pκ1实验值与其Y、Z相关联，使用最小二乘法进行线性回归，拟合得：pκ1=19.977-2.430Y-0.944Z(r=0.993）。     

全氟和多氟烷基磺酸的研究Ⅲ.1-氯-2-碘四氟乙烷与四氟乙烯的热调聚反应及其产物的化学转化

1-氯-2-碘四氟乙烷易与四氟乙烯进行热调聚反应,形成低分子量调聚物,Cl(CF₂CF₂)_nI(n=2～5),可以蒸馏分离.在低温下调聚物与普通格氏试剂反应得氯氟烷基卤化镁,再由它获得ω-氯代全氟烯烃-1Cl(CF₂CF₂)_nCF=CF₂(n=1,2,3)、ω-氯代全氟烷基醇Cl(CF₂CF₂)_nCR'R"OH(R'=CH₃,R"=H;R'=R"=CH₃;R'=R"=CF₃;n=2,3)及ω-氯代全氟烷基磺酰氯Cl(CF₂CF₂)_nSO₂Cl(n=2,3,4).通过ω-氯代全氟羧酸甲酯与甲基碘化镁的反应也得到ω-氯代全氟烷基醇Cl(CF₂CF₂).CF₂C(CH₃)₂OH(n=1,2).ω-氯代全氟烷基磺酸钾是稳定性很好的表面活性剂,可用作电镀镀铬中的铬雾抑制剂.     

乙酰丙酮-5,10,15,20-四-取代苯基卟啉钇的制备和表征

有机溶性乙酰丙酮-四-苯基卟啉希土配合物已有报告,但苯基上取代的钇的配合物的衍生物至今没见报道。本文首次制得乙酰丙酮-5,10,15,20-四邻氯苯基卟啉钇Y(o-Cl)Tppacac(H_2Tpp:四苯基卟啉:Hacac:乙酰丙酮;R_1:Cl,R_2=R_3:H),四间氯苯基卟啉钇Y(m-Cl)Tppacac(R_2:Cl,R_1=R_3:H),四对氯苯基卟啉钇Y(p-Cl)Tppacac(R_3:Cl,R_1=R_2:H),四邻甲氧基苯基卟啉钇Y(o-CH_3O)Tppacac(R_1:CH_3O,R_2=R_3:H)和四对甲氧苯基卟啉钇Y(p-CH_3O)Tppacac(R_3:CH_3O,R_1=R_2:H),并用元素分析、红外光谱、紫外光谱和热分析进行了表征。     

1,3-噻唑烷衍生物的合成、结构及生物活性

为了寻找新的含噻唑杂环的先导化合物, 利用2-取代-1,3-噻唑烷1与氯甲酸取代苯基酯2及取代苯基甲酰氯4在三乙胺存在下发生缩合反应, 合成了6个2-取代-1,3-噻唑烷-3-甲酸酯类化合物3和5个N-苯甲酰基-2-取代-1,3-噻唑烷类化合物5, 并利用¹H NMR, IR, MS, 元素分析对其结构进行了表征. 用X-ray单晶衍射测定了2-硫代-1,3-噻唑烷-3-甲酸苯酯(3d)和N-苯甲酰基-2-氧代-1,3-噻唑烷(5a)的晶体结构, 证实了氯甲酸酯与2-硫代-1,3-噻唑烷的反应产物为硫酮式结构, 而非硫酯式结构. 初步生物活性试验结果表明, 在试验浓度下部分目标化合物3和5具有一定的杀菌和杀虫活性.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Processing of non-isothermal TG data \par }

Decomposition of dichlorodifluoromethane in thermal plasma was investigated theoretically by computing the equilibrium composition of the gas mixtures involving carbon, chlorine and fluorine in presence of argon (which is assumed to be the main plasma gas) and/or in addition of hydrogen and calcium together with hydrogen. The calculations were carried out for the temperature range between 500 and 6000 K and for the total pressure of the system of 1 bar. Use is made of the fact that a thermal plasma is a plasma in (local) thermal equilibrium, which makes possible the theoretical determination of its equilibrium composition at definite temperature by employing Gibbs free energy data for the compounds present in the system and assuming that the equilibrium of the system corresponds to its minimum energy state. The results of calculations show that toxic molecules and radicals can be, under convenient conditions (appropriate temperature and amount of added substances), converted into stable non-toxic species like CaF₂ and CaCl₂.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Calorimetric study of transition phenomena in molecular solids \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Principle and technical development of low temperature calorimetry are described. Typical experimental results obtained by our group at Osaka University over the four decades are given. These include phase transitions in equilibrium crystals and glass transitions in non-equilibrium frozen-in disordered solids including crystals. It can be concluded that the glass transitions observed exclusively in liquids so far are just one example of transitions that must be of wide occurrence in solids arising from freezing of relevant degrees of freedom. Interplay between the phase and glass transitions in crystals is discussed in relation to useful dopant that may accelerate some molecular motions that had failed to maintain equilibrium at low temperatures. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 A pseudo-isothermal kinetic analysis of the recrystallisation of nickel sulphide measured by non-isothermal DSC \par }

Summary A pseudo-isothermal method for the kinetic analysis was applied to the recrystallisation of to nickel sulphide based on the Ozawa model for non-isothermal crystallisation in the presence of pre-existing nuclei. The aim of the analysis was to determine the number of steps involved in the recrystallisation and, hence, determine the applicability of the kinetic equation based on a single step mechanism, as is commonly applied in the kinetic analysis of solid-state processes using thermal methods. The kinetic analysis yielded evidence of at least two processes indicating that physical and mechanistic significance should not be drawn from the use of a single step approximation of the rate equation.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Saturation determination of micellar systems using isothermal titration calorimetry \par }

A novel method for the determination of the point of micellar saturation has been developed. To exemplify the theory a model system was considered, this being the saturation of two aqueous micellar solvents with dimethyl phthalate ester (DMP). Upon addition of a hydrophobic compound to an aqueous micellar system partitioning will occur. On further addition, the inner hydrophobic regions will eventually be unable to accommodate any more DMP and, at this specific concentration, the micelle is saturated. With a comparatively large enthalpy change upon partitioning the point of saturation can be determined by a corresponding significant reduction in enthalpy change.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Efficiency self-calibration of the HPGe detector for on-line assay of pebble bed reactor fuel \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Multi-pass pebble bed reactors are loaded with spherical fuel pebbles that are circulated through the core until they reach a proposed burnup limit (~100,000 MWD/MTU). An HPGe detector can be used to assay the fuel on-line to ensure that the burnup limit is not breached. The potential exists for using a relative burnup indicator, which would allow the use of a relative self-calibrating approach for efficiency determination. The utilization of several fission products as built-in on-line relative calibration standards is explored using the computer codes ORIGEN2.1, MCNP4C, and SYNTH to produce simulated gamma-ray spectra of the fuel pebbles at various levels of burnup. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Efficiency of germanium detectors as a function of energy and incident geometry: Comparison of measurements and calculations \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 The use of HPGe detectors in counting situations where the sample is not easily reproduced has increased the use of models to determine the counting efficiency for the specific geometry. The accuracy of these simulations of the germanium detector response relies on detailed knowledge of the performance of the detector. Several different types of detectors were measured at different energies using a pencil beam of gamma-rays. These measurements showed that the dead layer was not uniform from detector to detector. This and the construction details were used to calculate the efficiency for several detectors. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Neutron activation analysis using Excel files and Canberra Genie-2000 \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 We have developed a method for analyzing neutron activated sample data by using Microsoft Excel as the analysis engine. A simple technique for inputting data is based on report files generated by Canberra’s Genie-2000 spectroscopy system but could be easily modified to support other vendors having report formats with consistent text placement. A batch program handles operating an automatic sample changer, acquiring the data, and analyzing the spectrum to create a report of the peak locations and net area. The entire report is then transferred to within an Excel spreadsheet as the source data for neutron activation analysis. Unique Excel templates have been designed, for example, to accommodate short-lived and long-lived isotopes. This process provides us with a largely integrated solution to NAA while providing the results in an industry standard spreadsheet format. This software is ideally suited for teaching and training purposes. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Automated analysis of off-line measured gamma-spectra using \scaps UniSampo\scaps0 gamma-ray spectrum analysis software including criterias for alarming systems \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\lang2057\f0\fs24 In many laboratories the number of measured routine gamma-spectra can be significant and the labour work to review all the data is time consuming and expensive task. In many cases the routine sample does not normally contain radiation above a detectable level, and still the review of the spectra has to be performed. By introducing simple rules for emerging conditions, the review work can be significantly reduced. In one case the need to review the environmental measurement spectra was reduced to less than 1% compared to the original need, which in turn made the review personnel available for more useful functions. Using the \scaps UniSampo\scaps0 analysis system, the analysis results of spectra that are causing alarming conditions can be transmitted via e-mail to any address. Some systems are even equipped with the capability to forward these results to hand-portable telephones or pagers. This is a very practical solution for automated environmental monitoring, when the sample spectra are collected automatically and transmitted to central computer for further analysis. The paper describes how to set up an automatic analysis system, rules for the emerging conditions, technical solutions for an automated alarming system and a generic hypothesis test for the alarming system developed for \scaps UniSampo\scaps0 analysis software. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Digital signal processing in prompt-gamma activation analysis \par }

Summary The International Data Centre of the Comprehensive Nuclear-Test-Ban Treaty Organisation receives atmospheric radioactivity data from the monitoring stations of the International Monitoring System. The Centre is a processing hub through which raw data and analysis results flow to Treaty Member States. Data are processed automatically upon receipt, and then interactively reviewed and screened for detection of CTBT-relevant radionuclides. Atmospheric back-tracking for source location is included in the IDC functions. This paper describes the role of the IDC in this verification effort, the types of radionuclide monitoring data received, the automatic and interactive processing, and the products distributed to Member States.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Status of software for PGNAA bulk analysis by the Monte Carlo - Library Least-Squares (MCLLS) approach \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 The Center for Engineering Applications of Radioisotopes (CEAR) has been working for about ten years on the Monte Carlo - Library Least-Squares (MCLLS) approach for treating the nonlinear inverse analysis problem for PGNAA bulk analysis. This approach consists essentially of using Monte Carlo simulation to generate the libraries of all the elements to be analyzed plus any other required libraries. These libraries are then used in the linear Library Least-Squares (LLS) approach with unknown sample spectra to analyze for all elements in the sample. The other libraries include all sources of background which includes: (1) gamma-rays emitted by the neutron source, (2) prompt gamma-rays produced in the analyzer construction materials, (3) natural gamma-rays from K-40 and the uranium and thorium decay chains, and (4) prompt and decay gamma-rays produced in the NaI detector by neutron activation. A number of unforeseen problems have arisen in pursuing this approach including: (1) the neutron activation of the most common detector (NaI) used in bulk analysis PGNAA systems, (2) the nonlinearity of this detector, and (3) difficulties in obtaining detector response functions for this (and other) detectors. These problems have been addressed by CEAR recently and have either been solved or are almost solved at the present time. We have now finished the development of Monte Carlo simulation for all of the libraries except the prompt gamma-ray library from the activation of the NaI detector. We must first determine a treatment for the coincidence schemes for Na and particularly I to complete the Monte Carlo simulation of this last library. \par }