一类新的手性β-二酮铜(Ⅱ)配合物合成及性质 Ⅰ.( )双[1-对烷氧基苯基-3-对-(2′-甲基丁氧基)苯基-1,3-丙二酮]合铜(Ⅱ)

本文合成了一类新的含手性基团的β－二酮铜（Ⅱ）配合物，双［１－对烷氧基苯基－３－对－（２′甲基丁氧基）苯基－１，３－丙二酮］合铜（Ⅱ），经元素分析、红外光谱及比旋光度测定确定了结构。通过偏光显微镜下相变观察及ＤＳＣ图谱，证实这些配合物没有液晶性，其原因可能在于分子的对称性不好     

酰胺型冠醚液晶的合成及性质研究

冠醚液晶出现至今仅十几年，由于其具有冠醚和液晶的各种性质而受到人们的关注［‘－‘1．我们在已有工作的基础上，设计合成了5种酸胺型冠醚液晶分子（4—8），其中3种分子（4－6）具有液晶性．合成路线如下：1结果与讨论合成样品4－8经IR、MS、‘HNMR和元素分析确证其结构．用DSC和Texture图测定了4－6的液晶性质，其结果见图1．化合物7、8无液晶性，分子长径比分别为5．8：I，满足一般律状向列液晶分子长径比的要求．当在其分子链中增加1个苯环（5、6）时，分子的刚性链比例增大，整个分子的刚性增加，则具有液晶性．双臂型冠醚液…     

二(2,6-二叔丁基-4-个甲基苯氧基)钐催化丙交酯开环聚合

聚丙交酯（PLA）可以生物降解，产物无毒，可用于外科手术的缝合线、人造器官以及药物缓释等方面，因此引起了人们的广泛注意．丙交酯的开环聚合是合成聚丙交酯的一种方便方法，所用的催化剂主要是主族及副族金属的配合物，如双金属氧桥配合物［‘j，烷基金属有机化合物［‘j，异丙氧基铝［’‘以及叶琳铝「“等．最近，关于三价烷氧基稀土化合物作为单组份催化剂催化丙交酯开环聚会已有报道［’·’‘．我们发现两价芳氧基稀土化合物（ArO）。Sin（THF）。（ArO一2，已二叔丁基一个甲基苯氧基）也可以有效地催化丙文酯的开环聚合．本…     

可溶性醌胺聚合物的合成

酿胺聚合物（PAQ）是一类新型聚合物，适用于配制防水、防锈涂料，对金属有很大的亲和性［‘j．但溶解性较差［‘j．本文从分子设计出发，将一St一O一键、不对称多烷基取代脂环引人聚合物主链及侧基，增大PAQ分子内旋转自由度等提高其溶解度，合成了6种PAQ．对苯配（PBQ）按文献［3」制备，mP115～116’C；a，。二氨基丙基聚甲基硅氧烷（St—O重复次数n一8，胺值388，日本东丽化学公司）；异佛尔酮二胶（IPDA，AR，日本东京化成工业株式会社）；a，。一二氨基乙氧基聚甲基硅氧烷（St－O重复次数n二7），二缩三（1，2一丙二醇）双…     

一类新的手性β-二酮铜(Ⅱ)配合物合成及性质——Ⅰ. (+)双［1-对烷氧基苯基-3-对-(2′-甲基丁氧基)苯基-1，3-丙二酮］合铜(Ⅱ)

本文合成了一类新的含手性基团的β-二酮铜(Ⅱ)配合物，双［1-对烷氧基苯基-3-对-(2′甲基丁氧基)苯基-1，3-丙二酮］合铜(Ⅱ)，经元素分析、红外光谱及比旋光度测定确定了结构。通过偏光显微镜下相变观察及DSC图谱，证实这些配合物没有液晶性，其原因可能在于分子的对称性不好。     

（S）—α,α‘—二苯基—2—吡咯烷甲醇的简便合成

（S）－a，a’一二苯基一2一毗咯烷甲醇（1）是许多手性催化剂的合成前体’‘’，如手性呢隆硼试剂2，它能高度不对称地还原联基化合物［‘j．近年来有许多关于合成1的报道，但由于产率低，步骤多或者使用了高毒性光气［’j使大量制备方法受到限制．我们以L一脯氨酸为原料，采用不同的N一保护基因，高产率、简便地合成了化合物1．研究表明，不同N一保护基团对1的合成总产率有影响，其中PhCH。作保护基团时产率最低，但对光学纯度没有影响．陪叹烷酮是许多含毗咯环的天然产物的合成原料［‘j，在不对称合成中是一种功能较多的手性辅助基团…     

EXAFS研究合成甲醇催化剂Cu／ZnO／MxOy

有关CO。＋H。合成甲醇催化剂的研究已有许多报道［‘－’j，但目前对活性中心及反应机理的认识仍不～致，其中对活性中心的看法归纳起来有3种：（1）Cll为活性中心“‘；（2）Cll”为活性中心［’j；（3）Cll－CtJ”为活性中心［‘1．研究发现，第三组分（如AI刀。）的加入可防止Cu粒子的烧结［’］，使Cu产生无序及缺陷结构，有利于CO。的吸附、活化［‘j及起到高分散Cu／Zno的稳定剂的作用［’j．由于三组分催化剂结构的多相性和准非晶态性，通常的XRD方法难以明确了解其结构，而EXAFS方法对研究局部有序结构特别有效．本文以Z…     

含磺酸酯基液晶的合成

把硫原子引入液晶分子,取代液晶分子中的碳原子和氧原子可得到含硫代苯甲酸酯［１］、砜基［２］、亚砜基［３］和亚磺酸基［４］等结构的液晶化合物,性能独特．但含磺酸酯基的液晶化合物尚未见文献报道．本文应用Ｎ,Ｎ二环己基碳二亚胺（ＤＣＣ）和４Ｎ,Ｎ二甲...     

侧链液晶聚合物相转变点的分子动力学模拟

液晶基本上可分为３类：向列型液晶、近晶型液晶和胆甾型液晶［１］．液晶材料的相转变温度的预测对选择和设计液晶材料具有非常重要的作用．本文用分子动力学模拟法对聚［ω－（４′－甲氧基联苯－４－氧基）己基］甲基丙烯酸酯（ＰＭ６ＭＰＰ）单链分子进行了研究,模拟...     

含柔性链的液晶双马来酰亚胺／双烯丙基氧基联苯共聚物的合成

合成了含柔性链（Ｃ１０）的液晶双马来酰亚胺与双烯丙基氧基联苯的共聚物，经ＦＴＩＲ、ＤＳＣ、偏光显微镜表征了该共聚物的结构及液晶性，结果表明：二者发生共聚反应，且共聚反应快于均聚反应，形成的共聚物具有较好的热致液晶性。     

Identification of 4-sulfaminobutanoic acid in urine of a patient with nonketotic hyperglycinemia

4-Sulfaminobutanoic acid, a previously unknown 4-aminobutanoic acid conjugate, was found in urine of a nonketotic hyperglycinemia patient.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1313–1315, May, 1996.     

基于吡啶基苯甲酸盐的两个银(Ⅰ)配合物的合成、晶体结构及荧光性质

合成了2个含有吡啶基苯甲酸盐的银(Ⅰ)配合物,即[Ag₂(PPh₃)₂(4,4-pybz)₂(H₂O)₂]_n(1) 和[Ag₂(PPh₃)₂(4,3-pybz)₂]·2CH₃OH(2)(PPh₃=三苯基膦,4, 4-pybz=4-吡啶-4-基-苯甲酸根, 4,3-pybz=4-吡啶-3-基-苯甲酸根),并通过红外光谱、元素分析和荧光光谱进行分析和表征,它们的结构由X射线单晶衍射测定.在不同的溶剂下,2个配合物由AgBF₄、PPh₃和不同的吡啶苯甲酸在氨水作用下,以1:1:1的比例反应而成.在配合物1中,所有的银原子由吡啶基苯甲酸桥连形成一维链状结构.在配合物2中,2个银原子通过2个4-吡啶-3-基-苯甲酸根配体形成双核结构.在荧光光谱中,在发射状态下所有的峰均来源于配体的π-π*跃迁.     

基于吡啶基苯甲酸盐的两个银(Ⅰ)配合物的合成、晶体结构及荧光性质

合成了2个含有吡啶基苯甲酸盐的银(Ⅰ)配合物,即[Ag₂(PPh₃)₂(4,4-pybz)₂(H₂O)₂]_n(1)和[Ag₂(PPh₃)₂(4,3-pybz)₂]·2CH₃OH(2)(PPh₃=三苯基膦,4, 4-pybz=4-吡啶-4-基-苯甲酸根, 4,3-pybz=4-吡啶-3-基-苯甲酸根),并通过红外光谱、元素分析和荧光光谱进行分析和表征,它们的结构由X射线单晶衍射测定。在不同的溶剂下,2个配合物由AgBF₄、PPh₃和不同的吡啶苯甲酸在氨水作用下,以1:1:1的比例反应而成。在配合物1中,所有的银原子由吡啶基苯甲酸桥连形成一维链状结构。在配合物2中,2个银原子通过2个4-吡啶-3-基-苯甲酸根配体形成双核结构。在荧光光谱中,在发射状态下所有的峰均来源于配体的π-π*跃迁。     

对位取代苯甲酸与2,2'-联吡啶配体构筑的两种二价铅配合物的合成、晶体结构及性质

水热条件下,合成了2个含对位取代苯甲酸和2,2'-联吡啶配体的二价铅配合物[Pb(4-HOBA)2(2,2'-bipy)]·H2O(4-HOBAH=4-hydroxybenzoic acid,2,2'-bipy=2,2'-bipyridine)(1)及[Pb(4-MBA)2(2,2'-bipy)](4-MBAH=4-methylbenzoic acid)(2),并通过X-射线单晶结构分析、元素分析、红外光谱、紫外光谱、荧光光谱以及热重分析等手段对配合物进行了表征与研究.X-射线单晶结构测定表明,2种晶体的不对称单元中,六配位的二价铅离子分刖与来自1个2.2'-联吡啶的2个N原子和2个对位取代苯甲酸的4个O原子螫合.配合物1属单斜晶系,P21/c空间群,a=1.09483(4)nm,b=1.751 94(6)nm,c=1.20479(4)nm,β=100.334(2)°,V=2.27339(14)nm3,Z=4,final R1=0.0254,wR2=0.0674.广泛存在的分子间氢键和弱π…π堆积作用将配合物1组装成稳定的三维超分子结构.配合物2属三斜晶系,P-1空间群,a=0.955 10(11)nm,b=1.00805(12)am,c=1.324 83(15)nm,a=109.865(1)°,β=97.322(1)°,γ=90.643(1)°,V=1.1878(2)nm3,Z=2,final R1=0.0284,wR2=0.0508.配合物2经由一对Pb…O(0.3185(2)nm)弱相互作用被组装成二聚体结构.弱的Ph…O相互作用及与配合物1中类似的π…π堆积作用共同构筑了配合物2的三维结构.在配合物1和2中,铅的6s孤电子均显示了立体化学活性,使配位键分布于半球型区域.同时,两种配合物固体均具有光致发光特性,并在蓝光区有较强发射.     

对位取代苯甲酸与2，2′-联吡啶配体构筑的两种二价铅配合物的合成、晶体结构及性质

水热条件下,合成了2个含对位取代苯甲酸和2,2′-联吡啶配体的二价铅配合物[Pb(4-HOBA)₂(2,2′-bipy)]·H₂O (4-HOBAH =4-hydroxybenzoic acid,2,2′-bipy=2,2′-bipyridine) (1)及[Pb(4-MBA)₂(2,2′-bipy)](4-MBAH=4-methylbenzoic acid) (2),并通过X-射线单晶结构分析、元素分析、红外光谱、紫外光谱、荧光光谱以及热重分析等手段对配合物进行了表征与研究。X-射线单晶结构测定表明,2种晶体的不对称单元中,六配位的二价铅离子分别与来自1个2,2′-联吡啶的2个N原子和2个对位取代苯甲酸的4个O原子螯合。配合物1属单斜晶系,P2₁/c空间群,a=1.094 83(4) nm,b=1.751 94(6) nm,c=1.204 79(4) nm,β=100.334(2)°,V=2.273 39(14) nm³,Z=4,final R₁=0.025 4,wR₂=0.067 4。广泛存在的分子间氢键和弱π…π堆积作用将配合物1组装成稳定的三维超分子结构。配合物2属三斜晶系,P1 空间群,a=0.955 10(11) nm,b=1.008 05(12) nm,c=1.324 83(15) nm, α=109.865(1)°,β=97.322(1)°,γ=90.643(1)°,V=1.187 8(2) nm³,Z=2,final R₁=0.028 4,wR₂=0.050 8。配合物2经由一对Pb…O(0.318 5(2) nm)弱相互作用被组装成二聚体结构,弱的Pb…O相互作用及与配合物1中类似的π…π堆积作用共同构筑了配合物2的三维结构。在配合物1和2中,铅的6s孤电子均显示了立体化学活性,使配位键分布于半球型区域。同时,两种配合物固体均具有光致发光特性,并在蓝光区有较强发射。     

Synthesis and study of (2S,4S)-4-arylamino-2-carboxy-5-pyrrolidones

(2S,4S)-4-Arylamino-2-carboxy-5-pyrrolidones were prepared by hydrolysis of dimethyl (2S,4S)-4-arylamino-N-phthaloylglutamates. The protonation constants of the arylamino group in the synthesized compounds were determined. The pyrrolidone ring is stable in acidic or neutral solutions. The relative stability of the pyrrolidone ring in alkaline solutions was studied by IR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2087–2090, December, 1993.     

三苯甲醇-4,4′,4″-三羧酸及其氯化物的合成

以4-溴甲苯为原料,合成了几种三芳基甲烷衍生物:三甲苯甲醇(TTMO)、三苯甲醇-4,4′,4″-三羧酸(TOTA)、三苯基氯甲烷-4,4′,4″-三羧酸(TClTA);利用红外光谱仪、核磁共振谱仪及元素分析仪表征了合成产物的结构和组成.结果表明,将4-溴甲苯与镁条在四氢呋喃中反应,可得到对甲苯基溴化镁;对甲苯基溴化镁随后与碳酸二乙酯反应,可得到TTMO;TTMO经硝酸氧化得到TOTA;TOTA与乙酰氯反应得到TClTA.     

Biodegradation studies of 4-fluorobenzoic acid and 4-fluorocinnamic acid: an evaluation of membrane inlet mass spectrometry as an alternative to high performance liquid chromatography and ion chromatography

The biodegradation of 4-fluorobenzoic acid (4-FBA) and 4-fluorocinnamic acid (4-FCA) has been monitored by membrane inlet mass spectrometry (MIMS) using a hollow-fibre silicone membrane. A novel in-membrane pre-concentration/thermal desorption (IMP-MIMS) technique was employed for MIMS analysis using an oven temperature profile that allowed semi-volatile organic compounds to be accumulated in the membrane and then released by rapid heating. Air drying of the membrane between the analyte pre-concentration and thermal desorption stages improved mass spectrometric performance by removing residual water from the membrane. The concentrations of 4-FBA and 4-FCA determined by MIMS compare well with data obtained by high performance liquid chromatography (HPLC). Stoichiometric amounts of fluoride were monitored using ion chromatography (IC). Intermediates in the biodegradation pathway were identified by liquid chromatography/mass spectrometry (LC/MS). These data establish the potential of MIMS as an alternative to chromatographic methods for monitoring the biodegradation of semi-volatile organic compounds.     

Synthesis of azo derivatives of 4-aminosalicylic acid

For searching a better 4-aminosalicylic acid derivative with higher activity and less side effects against the inflammatory bowel disease, 4-aminosalicylic acid (4-ASA) was protected by benzyloxycarbonyl and acetyl, respectively. The resultant was hydrogenized to remove protective group of amino group, then the product was reacted with NaNO2 to give diazonium salt, which was conjugated with salicylic acid, hydroxybenzene, TV-salicyloyl glycine acid to get azo derivatives of 4-ASA. The azo derivatives were hydrolyzed under the alkaline condition to get the target products. All compounds were characterized by FT-IR, 1H NMR, 13C NMR spectra in details. New derivatives of 4-ASA were characterized. The synthetic route was reasonable and feasible.     

Titania immobilized polypropylene hollow fiber as a disposable coating for stir bar sorptive extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometry speciation of arsenic in chicken tissues

The bottleneck of applying stir bar sorptive extraction (SBSE) to elemental speciation analysis is lack of suitable extraction phases with good affinities to different elemental species. In this paper, a newly high polar extraction phase of titania immobilized polypropylene hollow fiber (TiO₂-PPHF) was prepared by sol–gel immersion and low temperature hydrothermal process and the obtained TiO₂-PPHF inherits the adsorption properties of TiO₂ and the toughness of PPHF. With a suitable size of stainless steel magnetic bar inserted into the prepared TiO₂-PPHF, a disposable TiO₂-PPHF coating stir bar was obtained. The prepared TiO₂-PPHF was characterized by X-ray diffraction spectrometry and scanning electron microscopy and the significant parameters affecting the extraction efficiency of different arsenic species were studied. Based on the above facts, a new method of SBSE combined with high performance liquid chromatography (HPLC)–inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of phenyl arsenic compounds and their possible transformation products in chicken tissues. Under the optimal conditions, limits of detection (LODs) of the developed method for eight target arsenic species were in the range of 11.4–64.6 ng L⁻¹ with enrichment factors of 8.5–22.3 (theory enrichment factor was 50), and the relative standard deviations (RSDs) were varying from 6.3 to 12.6% (c_AsIII/V = 5 μg L⁻¹, c_{MMA,DMA,p-ASA,4-OH,3-NHPAA,PA,4-NPAA} = 10 μg L⁻¹, n = 7). The proposed method was successfully applied to the speciation of arsenic in chicken meat/liver samples and the recoveries for the spiked samples were in the range of 78.5–120.4%. In order to validate the accuracy of the proposed method, a certified reference material of BCR-627 tuna fish tissue was analyzed and the determined values were in good agreement with the certified values. The TiO₂-PPHF was demonstrated to be a highly selective coating for the target arsenic species, and could be easily prepared in batches with low cost. In addition, with the disposable coating, the carry-over effect commonly encountered in conventional SBSE was avoided.