芳基膦（肿）酸及其盐的合成,结构与倍频效应研究

本文基于将无机非线性光学材料的有效基团（畸变阴离子基团）及有机共轭体系结合为一体的设想，用改进的Ｄｏａｋ－Ｆｒｅｅｄｍａｎ法合成了一系列芳基膦（胂）酸及其盐共２５个化合物，讨论了分子的电子性质及其在晶体中的排列方式。实验结果表明，在这类化合物的分子内存在着一定的电荷转移；对甲苯膦酸的晶体结构分析表明，分子间存在着氢键作用，使分子呈二聚的排列方式。在所合成的化合物中，有６种表现出宏观倍频效应。     

三苄基锡(Ⅳ)炔基(烯基)膦酸衍生物的合成及结构表征

烃基锡的膦(磷)酸衍生物具有较强的杀虫、杀菌及除草等生物活性, 受到人们的极大关注[1,2],尤其是三烃基锡(IV)二硫代磷酸酯的合成及应用研究已有较多报道[3,4],但三烃基锡(IV)膦酸衍生物的合成研究很少[5],而三烃基锡(IV)不饱和烃基膦酸衍生物R3SnOP(O)(OH)R'(R'为炔基或烯基)的研究尚未见文献报道.我们以三苄基氯化锡和炔基(烯基)膦酸单钠为原料,合成了6种三苄基锡(IV)炔基(烯基)膦酸类化合物.并用元素分析、红外光谱、核磁共振、氢谱和锡谱、质谱及热重分析等手段表征了这些化合物.     

S-烯丙基-O-取代苯基硫代磷(膦)酸衍生物的合成及杀菌活性研究

O,O-二烯丙基硫代磷(膦)酸酯(6)与三氯氧磷发生异构化氯化反应得到S-烯丙基硫代磷(膦)酰氯7和O-烯丙基磷酰二氯酯(8).7在碱性溶液中与取代酚反应,合成了18个新的标题化合物,生物活性测试表明,这些化合物均有一定的杀菌活性,有些化合物还具有较好的杀菌活性或杀虫活性.     

S-烷基-O-(2,6-二氯-4取代苯基)硫代磷(膦)酸酯的合成及杀菌活性的研究

O,O-二烷基硫酮代磷(膦)酸酯(3)与三氯氧磷发生异构化氨化反应得到S-烷基硫代磷(膦)酰氨(4),4与2,6-二氯-4-取代苯酚反应,合成了26种新的标题化合物.生物活性初步测定结果表明,这些化合物均有一定的杀菌活性.     

双膦酸化合物对基质金属蛋白酶的抑制效应及机理

根据基质金属蛋白酶(MMPs)的活性位点附近三维空间结构, 设计合成了4种双膦酸类化合物, 利用酶促反应动力学方法对比测试了双膦酸化合物及阿伦磷酸钠(Alendronate)对MMPs的抑制效果; 结合分子对接方法以及荧光滴定光谱研究了双膦酸化合物与MMPs的分子识别和作用机理, 并得到了二者的结合模型.     

甲基膦酸(濒)哪酯分子印迹聚合物的合成与识别特性研究

利用~(31)P{~1H}NMR谱和~1H NMR谱、FT-IR谱等技术手段,研究了化学毒剂梭曼的降解产物(甲基膦酸■哪酯)与甲基丙烯酸、丙烯酰胺功能单体的分子间作用力。通过预组装体系设计,合成了多孔性材料甲基膦酸■哪酯分子印迹聚合物。通过Scatchard模型分析,得到该聚合物对甲基膦酸■哪酯的最大表观结合量Q_(max)为661μg/g(AM为单体),在低吸附量(Q500μg/g)范围内,吸附量对模板浓度的比值与吸附量呈线性相关。通过静态吸附分配实验发现,该聚合物对同系的5种烷基膦酸单烷基酯存在选择性,对结构不同的其他化合物的识别因子显著降低。将该分子印迹聚合物制成固相萃取柱,用于含大量背景干扰的样品中痕量甲基膦酸■哪酯的萃取分离,取得显著效果。该研究为复杂基质中该类化合物的痕量分析鉴定提供了技术手段。     

一缺位杂多阴离子XW11O(12-n)-39(X=P5+,Si4+,B3+,Ga3+)含硫有机膦衍生物的合成及结构表征

杂多化合物的衍生物由于具有潜在的多功能催化性能,长期以来一直受到人们的关注[1～3].将有机或有机金属基团引入杂多化合物中以修饰杂多阴离子的部分外部骨架结构,对研究杂多化合物的性质和应用及新型催化剂的开发具有重要意义[4,5].在杂多化合物表面引入适当的有机基团还可改善其溶解性能及其它物理性质,从而拓宽其应用范围.研究结果表明,这类化合物还具有很好的抗病毒和抗肿瘤活性[6,7].Klemperer等[8]合成的[(η5-C5H5)TiPW11O39]4-将多酸与金属有机化合物有机地融为一体,从而开辟了多酸金属有机化学的新领域.此后,相继合成了许多多酸型金属有机化合物[9],然而缺位杂多阴离子的有机膦衍生物的研究却鲜见报道[10].     

烃基磷(膦)酸酯的化学结构及其液相色谱行为

本文研究了各种烷基或芳基磷(膦)酸酯和亚磷(膦)酸酯的化学结构对其在高效液相色谱(HPLC)柱上保留作用的影响. HPLC中容量因子与化合物的类型以及烷基碳原子数有密切关系. 我们讨论了这些化合物的化学结构和它们的容量因子的关系.     

三芳基膦配体的合成研究

从间溴苯酚出发, 利用新的合成方法经五步反应合成了一系列具有不同烷氧基的芳基膦配体. 改进后的方法可方便地通用于在苯环上具有各种不同基团基的膦配体衍生物的合成, 且有原料易得、操作简单、产率较高的优点.     

有机硫代磷(膦)酸铵盐与三氯氧磷的氯化反应──合成硫(酮)代磷(膦)酰氯的一种新的简便方法

O,O二烷基硫代磷(膦)酸衍生物与二甲胺水溶液发生去烷基反应后,生成的硫代磷(膦)酸铵盐与三氯氧磷发生氯化反应,得到硫(酮)代磷(膦)酰氯.本文还讨论了该反应可能的机理.     

Distribution and cycle of arsenic compounds in the ocean

In order to understand the distribution and the cycle of arsenic compounds in the marine environment, the horizontal distributions of arsenic(V) [As(V)], arsenic(III) [As(III)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) in the Indian Pacific Oceanic surface waters have been investigated. This took place during cruises of the boat Shirase from Tokyo to the Syowa Station (15 November–19 December 1990), of the tanker Japan Violet from Sakai to Fujayrah (28 July–17 August 1991) and of the boat Hakuho-maru from Tokyo to Auckland (19 September–27 October 1992). Vertical distributions of arsenic in the west Pacific Ocean have also been investigated. The concentration of As(V) was found to be relatively higher in the Antarctic than in the other areas. Its concentration varied from 340 ng dm^?3 (China Sea) to 1045 ng dm^?3 (Antarctic). On the other hand, the concentrations of the biologically produced species, MMAA and DMAA, were extremely low in the Antarctic and southwest Pacific waters. Their concentrations in Antarctic waters were 8 ng dm^?3 and 22 ng dm^?3 and those in the southwest Pacific were 12 ng dm^?3 and 25 ng dm^?3. In the other regions the concentration varied from 16 ng dm^?3 (China Sea) to 36 ng dm^?3 (north Indian Ocean) for MMAA and from 50 ng dm^?3 (east Indian Ocean) to 172 ng dm^?3 (north Indian Ocean) for DMAA. As a result, with the exception of Antarctic and southwest Pacific waters, the percentages of each arsenic species in the surface waters were very similar and varied from 52% (east Indian Ocean) to 63% (northwest Pacific Ocean) for As(V), from 22% (northwest Pacific Ocean) to 27% (east Indian Ocean) for As(III) and from 15% (northwest Pacific Ocean) to 21% (north and east Indian Oceans) for the methylated arsenics (MMAA+DMAA). These percentages in Antarctic waters were 97%, 0.2% and 2.8%, respectively, and those in the southwest Pacific Ocean were 97% for As(V)+As(III) and 3% for MMAA+DMAA. The very low concentrations of the biologically produced species in Antarctic waters and that of methylated arsenic in southwest Pacific waters indicated that the microorganism communities in these oceans was dominated by microorganisms having a low affinity towards arsenic. Furthermore, microorganism activity in the Antarctic was also limited due to the much lower temperature of the seawater there. The vertical profile of inorganic arsenic was 1350 ng dm^?3 in surface waters, 1500 ng dm^?3 in bottom waters with a maximum value of 1700 ng dm^?3 at a depth of about 2000 m in west Pacific waters. This fact suggested the uptake of arsenic by microorganisms in the surface waters and the co-precipitation of arsenic with hydrated heavy-metal oxides in bottom waters. The suggested uptake of inorganic arsenic and subsequent methylation was also supported by the profile of DMAA, with a high concentration of about 26 ng dm^?3 in surface water and a significant decrease to a value of 9 ng dm^?3 at a depth of 1000 m.     

The Distribution of Arsenic Compounds in the Ocean: Biological Activity in the Surface Zone and Removal Processes in the Deep Zone

The vertical profies of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were investigated at four sampling stations in the Pacific Ocean and a sampling station in the southern Tasman Sea. In addition, the concentrations of those compounds in surface waters of the Pacific Ocean and Tasman Sea have been determined. The vertical profiles of inorganic arsenic showed the low concentrations in both the surface and deep/bottom zones. The depleted concentrations in the surface zone varied from 1000 to 1700 ng dm⁻³ and that in the deep/bottom zone varied from 1300 to 2050 ng dm⁻³. The maximum concentrations that varied from 1500 to 2450 ng dm⁻³ were usually observed at a depth of about 2000 m. Both MMAA and DMAA were observed throughout the water column at sampling stations in the north-western and equatorial regions of the Pacific Ocean. At the sampling station in the central northern Pacific gyre, DMAA was the only methylated arsenic compound observed throughout the water column. On the contrary, at the sampling station in the southern Tasman Sea, the only detected methylated arsenic compound throughout the water column was MMAA. Their vertical profiles showed maximum concentrations in the surface water which abruptly dropped with depth from 0 to 200 m. The concentration in the surface water was close to 10 ng dm⁻³ for MMAA and varied from 27 to 185 ng dm⁻³ for DMAA. At depths greater than 100 m, MMAA and DMAA were at comparable concentrations which varied from 0.7 to 14 ng dm⁻³. The low inorganic arsenic concentration in the surface zone was due to biological activity. This activity resulted in the uptake of As(V) and subsequent reduction and methylation to MMAA and DMAA. DMAA was the main predominant arsenic compound resulting from biological activity in surface waters. The low inorganic arsenic concentrations in the deep and bottom zones were likely to be caused by the adsorption of dissolved inorganic arsenic onto sinking particulates rich in iron and manganese oxides.     

Two New Compounds from Hemsleya penxianensis var.gulinensis

Two new compounds,oleanolic acid 28-O- β-D-glucopyranosyl-3-O-α-L-arabinopyranosyl-(1→3)-(6′-butyl ester)-β-D-glucuropyranoside 1,oleanolic acid 28-O-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside 2 have been isolated from the roots of Hemsleya penxianensis var.gulinensis.Their structures were determined on the bases of the spectral and chemical evidences.     

Gd3+与RGD共修饰量子点用于胰腺癌细胞的荧光及MR双模态成像

结合磁共振成像(MRI)和荧光成像技术,以钆离子(Gd3+)、量子点及精氨酸(R)-甘氨酸(G)-天冬氨酸(D)(RGD)多肽等为功能单元,采用纳米载体组装技术构建了MRI弛豫率/荧光效率高和靶向性强的Gd3+与RGD共修饰的量子点双模态纳米探针(QDs@Gd3+-RGD),并将其用于胰腺癌细胞的双模态成像.实验结果表明,QDs@Gd3+-RGD双模态纳米探针具有较高的弛豫率,且能对胰腺癌patu8988细胞进行荧光和T1-weighted MR成像.     

新型热反应大分子单体的合成与表征

溶液法合成了一些低分子量的羟端基低聚苯醚砜,并由相转移催化剂将之转为热反应大分子单体——α,ω-双甲基丙烯酸聚苯醚砜酯;用FTIR、~1H-NMR对其结构进行了表征,GPC、VPO对其分子量进行了分析和测定;用DSC、DTA对聚苯醚砜双烯大分子单体的转变温度、热反应过程进行了测定和分析。     

Structural study of bis(triorganotin(IV)) esters of 4-ketopimelic acid

The set of six bis(triorganotin(IV)) esters of 4-ketopimelic acid was prepared. Their structures were studied using IR, NMR and X-ray crystallographic (cyclohexyl and ethyl derivatives) techniques both in solution and the solid state. Five of these compounds are polymeric in the solid state and depolymerise upon dissolving in non-coordinating and/or addition of coordinating solvent to monomeric species with four-coordinated tin atom or complexes with donor solvent with five-coordinated tin central atom. The tricyclohexyltin derivative is dimeric in the solid state and monomeric in solution.     

Luminol Chemiluminescence with Heteropoly Acids and its Application to the Determination of Arsenate,Germanate, Phosphate and Silicate by Ion Chromatography

A flow-injection chemiluminescence (CL) method has been proposed for sensitive determination of arsenate, germanate, phosphate and silicate, after separation by ion chromatography (IC). The post-column detection system involved formation of heteropoly acid in a H₂SO₄ medium before the CL reaction with luminol in an NaOH medium. For separation, heteropoly acid formation and the CL detection reaction, pH requirements were not compatible. When present as a heteropoly acid complex with molybdenum(VI), ger- manium(IV) and silicon(IV) caused CL emission from oxidation of luminol, and such a CL oxidation of luminol was observed analogously for arsenic(V) and phosphorus(V) but with the addition of metavanadate ion to the acid solution of molybdate. Good sensitivity for the three analytes arsenic(V), ger- manium(IV) and phosphorus(V) could be given by a single set of reagent conditions, chosen carefully. Another set was suitable for determining phosphorus(V) and silicon(IV). The minimum detectable concentrations of arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were 10, 50, 1 and 10 μg l⁻¹, respectively. Linear calibrations for arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were established over the respective concentration ranges of 10–1000, 50–25000, 1–1000 and 50–1 μg l⁻¹. The proposed IC–CL method was successfully applied to analyses of a seaweed reference material, rice wine and water samples.     

Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films

A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet–visible (UV–vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H₂O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329–1340, 1998     

Interpolymer Complexes of Poly(N,N-Dimethylacrylamide/Poly(Styrene-co-Acrylic Acid): Thermal Stability and FTIR Analysis

Summary: This contribution will focus on the elaboration and characterizations of new materials with optimal properties as interpolymer complexes, upon mixing poly (styrene-co-acrylic acid containing 18, 27 and 32 mol % of acrylic acid (SAA-x) and poly (N,N-dimethylacrylamide) (PDMA), through the control of the densities, strength, self-association and accessibility of the interacting species. These elaborated interpolymer complexes, of different structures, investigated by DSC and TGA, exhibited a significant improved thermal stability. Their DSC analysis showed that all these materials showed one composition-dependence glass transition temperature Tg, indicating the formation of a single homogeneous phase. The different behaviors of Tg-initial composition observed with these systems were analyzed by the approaches of Kwei and Brostow et al., recently developed. The specific interactions that occurred within the elaborated materials were evidenced qualitatively by ATR/FTIR spectroscopy, from the appearance of new bands in the 1800–1550 cm⁻¹ region.     

The Contrasting Behaviour of Arsenic and Germanium Species in Seawater

The vertical profiles of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), inorganic germanium and monomethylgermanium (MMGe) were investigated at three sampling stations in the Pacific Ocean. In addition, the concentrations of these species in various surface waters have also been determined. The vertical profile of both inorganic arsenic and germanium displayed low concentrations, 1100 to 1450 ng dm³ for inorganic arsenic and <0.7 to 2 ng dm³ for inorganic germanium, in the surface zone. The concentrations of inorganic arsenic increased with depth to maximum concentrations that varied from 1500 to 2200 ng dm³ at a depth of 2000 m and then slowly decreased to concentrations that varied from 1300 to 1900 ng dm³ at a depth of 5000 m. On the other hand, the vertical profiles of inorganic germanium displayed a relatively constant concentration (4 to 8 ng dm³) from a depth of 2000 m to 5000 m. These vertical profiles of inorganic germanium were linearly correlated with those of silicate with a Ge/Si molar ratio of 0.715×10⁶. Both MMAA and DMAA displayed maximum concentrations in surface water and abruptly dropped with depth from 0 to 200 m. The concentration in surface water was 12 ng dm³ for MMAA and varied from 48 to 185 ng dm³ for DMAA. At depths >200 m, MMAA and DMAA were generally at comparable concentrations of about 3 ng dm³. In the case of MMGe, it was uniformly distributed throughout the water column at a concentration of approximately 16 ng dm³, indicating that MMGe was not involved in the biogeochemical cycling of inorganic germanium. In deep waters (>200 m), the concentrations of both inorganic arsenic and germanium increased from the southern Tasman Sea to the north. The increase in inorganic arsenic concentration was linearly correlated with that of phosphate and the increase in inorganic germanium concentration was linearly correlated with that of silicate, with apparent δAs/δP and δGe/δSi molar ratios of 4.53×10³ and 0.73×10⁶, respectively. © 1997 by John Wiley & Sons, Ltd.