1,2-双(二叔丁基膦甲基)苯的合成

以氯代叔丁烷和亚磷酸二乙酯为原料制得二叔丁基氧化膦,用四氢铝锂还原得二叔丁基膦氢,经锂化后依次邻二氯苄反应合成了大位阻效应有机磷配体的1,2-双(二叔丁基膦甲基)苯.利用N MR核磁共振谱仪对其结构进行表征,并对反应收率的影响条件进行了优化.     

GC/MS法分析苯硫代膦酰二氯样品中的杂质

采用美国Finnigan公司最新型号的色质联用仪GC／DSQ，定性分析了苯硫代膦酰二氯合成产品。确定了其中杂质的主要成分二苯硫代膦酰氯，并用简单的面积归一化法算出了产品和杂质的大致含量，为下一步的研究工作指明了方向。     

α-二苯氧膦芳香醇的制备、重排及其核磁共振谱

本文介绍α-二苯氧膦苄醇(1)、α-二苯氧膦苯乙醇(2)和α-二苯氧磷二苯基甲醇(3)的制备及其~(13)C,~(31)P核磁共振谱,研究表明化合物1,2在室温下是稳定的,而化合物3在室温下自发重排为二苯基膦酸二苯甲酯(3a),对化合物3自发重排的键能因素和空间张力因素作了讨论.     

离子液体催化合成阻燃剂3-羟基苯膦酰丙酸

采用两步法合成3-羟基苯膦酰丙酸(CEPPA),即以三氯化磷与苯为原料,在离子液体三乙基苄基氯化铵氯化铝([BnEt3N]Cl-xAlCl3)催化下,合成苯膦二氯(DCPP),再用DCPP与丙烯酸合成3-羟基苯膦酰丙酸(CEPPA).确定第一步最佳反应条件为:n(三氯化磷)∶n(苯)∶n([BnEt3N]Cl-xAlCl3)=3∶1∶0.025,回流温度为72℃～76℃,反应时间为6 h,产率达81.1%;第二步通过改变反应物滴加顺序及调整反应温度,得到最佳反应条件为:n(丙烯酸)∶n(DCPP)=1.30∶1.00;滴加反应阶段,控制在70℃～80℃,反应1.5～2 h后,在90℃保温反应1 h;水解反应阶段,控制在92℃～95℃反应4 h,CEPPA的产率可达91%,并解决了反应中易结块问题.     

2-二烷基膦基-2′,4′,6′-三异丙基-3,6-二甲氧基-1,1′-联苯的合成工艺

以1,4-二甲氧基-2-氟苯和2,4,6-三异丙基溴苯为原料合成2-碘-3,6-二甲氧基-2′,4′,6′-三异丙基-1,1′-联苯.在四氢呋喃和甲苯混合溶液中将联基碘代物制成格式试剂,在溴化亚铜和溴化锂的催化下,与二环己基氯化膦或二叔丁基氯化膦进行反应,分别以82%和75%的产率生成2-二环己基膦基-2′,4′,6′-三异丙基-3,6-二甲氧基-1,1′-联苯和2-二叔丁基膦基-2′,4′,6′-三异丙基-3,6-二甲氧基-1,1′-联苯,并对其结构进行了表征.     

新化合物2,5-二氟苯膦酸二钠盐的合成及晶体结构

以2,5-二氟苯胺为原料,经重氮化反应生成2,5-二氟硼酸重氮盐,与三氯化磷反应后水解、中和得到新化合物2,5-二氟苯膦酸二钠盐,其结构经过1 H NMR,31P NMR,元素分析及单晶X-射线衍射确证.     

反应型阻燃剂3-羟基苯膦酰丙酸的合成

以苯、三氯化磷和丙烯酸等为原料合成了一种重要的磷系阻燃剂羟基苯膦酰丙酸。研究了反应温度、原料配比、置换剂等因素的影响。以苯、三氯化磷合成苯膦二氯的收率达到81％，以苯膦二氯和丙烯酸合成3-羟基苯膦酰丙酸的收率为88％。通过红外光谱和差示扫描量热分析确定了产品的结构。     

含二萘并膦杂环戊二烯结构的双膦配体的合成

在金属锂的作用下1,1'-联萘-2,2'-双二苯膦还原裂解后与二溴代烷烃反应,合成了双(二萘并膦杂环戊二烯基)乙烷和双(二萘并膦杂环戊二烯基)丙烷,并通过核磁共振和高分辨质谱等手段对它们的结构进行了表征.此外还利用核磁膦谱监测对反应进行了跟踪研究,去除了二苯基膦负离子对后续反应的影响,对反应过程进行了优化.     

1,2-二吡咯基-4,5-二(二苯基膦基)苯的合成与表征

含邻位芳基双膦配体的亚铜配合物因其高效发光应用于有机发光二极管。本文中设计将两个富电子单杂环吡咯引入到二(二苯基膦基)苯中,合成一种新的邻位芳基双膦配体1,2-二吡咯基-4,5-二(二苯基膦基)苯。首先将吡咯与1,2-二氟-4,5-二溴苯在碱性Cs₂CO₃、140℃下发生亲核取代反应,生成1,2-二吡咯基-4,5-二溴苯,然后在低温条件下继续与正丁基锂、氯代二苯基膦反应,生成目标产物1,2-二吡咯基-4,5-二(二苯基膦基)苯。用核磁共振谱(¹H、¹³C、³¹P NMR)、傅里叶变换红外光谱、高分辨电喷雾质谱等对目标化合物进行表征,确证了结构,为后续合成金属配合物发光材料提供了一种新的配体。该化合物目前鲜见报道。     

从生产盐酸氯洁霉素的废渣中制取三苯膦

制取盐酸氯霉素的废渣含有大量氧化三苯膦。经试验研究，将氧化三苯膦制成二氯化三苯膦，然后用电解铁粉末可将二氧化三苯膦还原为三苯膦。为制得数量多、质量高的产品，采用正交法选出的最佳生产条件为A1、B3、C3、D1，由T值还可看出，因素B对产率影响最大，其次是因素D，其它因此影响不大。     

醚链桥连氮杂环卡宾的合成及催化酯交换反应

合成了一种醚链桥连的氮杂环卡宾催化剂,通过元素分析、核磁共振表征了它们的结构.在酯交换反应中典型的催化剂是亲核性的叔胺和膦化合物.本文研究了氮杂环卡宾在酯交换反应中的催化作用,结果表明在室温下,氮杂环卡宾表现出良好的催化活性.     

手性膦配位钯化合物的电化学性质

手性膦（Ｌ）配位的钯化合物ＰｄＣｌ２Ｌ２，Ｌ＝２－ＭＢＰＡ（１）；Ｌ＝３－ＭＢＰＡ（２），在ＤＭＦ中的循环伏安法电化学研究表明，二个化合物的氧还性质相近，与膦在Ｄ－醣上的碳取代位置无关．化合物的氧还反应有一个还原峰和两个氧化峰．比较化合物（２）在乙氰和ＤＭＦ中的ＣＶ图，显示两个氧化峰系由溶剂配位后的还原产物［ＰｄＬ２（Ｓｏｌｖｅｎｔ）２］１－氧化而得     

共轭二烯烃调聚合反应研究(Ⅲ) Pd(acac)_2-PR_3体系催化丁二烯和甲醇调聚合

研究了用２．４－戊二酮钯－叔膦体系催化丁二烯和甲醇调聚合反应，结果表明： Ｐｄ（ａｃａｃ）２－ＰＲ３体系是有效的丁二烯和甲醇调聚合反应的催化剂．考察了四种有代 表性的叔膦 ＰＲ３（Ｐ＝Ｐｈ－，ＰｈＯ－，Ｐｒｉ－，Ｂｕｎ－）与 ２，４－戊二酮钯组成体系的催 化作用，发现丁二烯的转化率、调聚产物的选择及两个调聚产物的分配比例同催化剂 体系中 ＰＲ ３的碱性和空间角有关。     

Chemical remodelling of cell surfaces in living animals

Cell surfaces are endowed with biological functionality designed to mediate extracellular communication. The cell-surface repertoire can be expanded to include abiotic functionality through the biosynthetic introduction of unnatural sugars into cellular glycans, a process termed metabolic oligosaccharide engineering. This technique has been exploited in fundamental studies of glycan-dependent cell-cell and virus-cell interactions and also provides an avenue for the chemical remodelling of living cells. Unique chemical functional groups can be delivered to cell-surface glycans by metabolism of the corresponding unnatural precursor sugars. These functional groups can then undergo covalent reaction with exogenous agents bearing complementary functionality. The exquisite chemical selectivity required of this process is supplied by the Staudinger ligation of azides and phosphines, a reaction that has been performed on cultured cells without detriment to their physiology. Here we demonstrate that the Staudinger ligation can be executed in living animals, enabling the chemical modification of cells within their native environment. The ability to tag cell-surface glycans in vivo may enable therapeutic targeting and non-invasive imaging of changes in glycosylation during disease progression.     

Structural effects on the magnetic hyperthermia properties of iron oxide nanoparticles

Magnetic iron oxide nanoparticles(IONPs) are heavily explored as diagnostic and therapeutic agents due to their low cost, tunable properties, and biocompatibility. In particular, upon excitation with an alternating current(AC) magnetic field, the NPs generate localized heat that can be exploited for therapeutic hyperthermia treatment of diseased cells or pathogenic microbes. In this review, we focus on how structural changes and inter-particle interactions affect the heating efficiency of iron oxide-based magnetic NPs. Moreover, we present an overview of the different approaches to evaluate the heating performance of IONPs and introduce a new theranostic modality based on magnetic imaging guided–hyperthermia.     

A colorimetric sensor array for odour visualization

Array-based vapour-sensing devices are used to detect and differentiate between chemically diverse analytes. These systems--based on cross-responsive sensor elements--aim to mimic the mammalian olfactory system by producing composite responses unique to each odorant. Previous work has concentrated on a variety of non-specific chemical interactions to detect non-coordinating organic vapours. But the most odiferous, toxic compounds often bind readily to metal ions. Here we report a simple optical chemical sensing method that utilizes the colour change induced in an array of metalloporphyrin dyes upon ligand binding while minimizing the need for extensive signal transduction hardware. The chemoselective response of a library of immobilized vapour-sensing metalloporphyrin dyes permits the visual identification of a wide range of ligating (alcohols, amines, ethers, phosphines, phosphites, thioethers and thiols) and even weakly ligating (arenes, halocarbons and ketones) vapours. Water vapour does not affect the performance of the device, which shows a good linear response to single analytes, and interpretable responses to analyte mixtures. Unique colour fingerprints can be obtained at analyte concentrations below 2 parts per million, and responses to below 100 parts per billion have been observed. We expect that this type of sensing array will be of practical importance for general-purpose vapour dosimeters and analyte-specific detectors (for insecticides, drugs or neurotoxins, for example).     

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related nanomaterials.     

仿真方法在6自由度并联机器人运行中的应用

介绍一种6自由度并联机器人基本结构及当前仿真技术的应用,对其进行了运动分析,结合其结构特点对系统进行线性化并求出位置逆解,建立了系统的状态方程,分析讨论了仿真技术在该机器人控制中的适用性.     

Self - Crosslinking Behavior of Self - Emulsion Water - Based Polyure-thane Coating Agents

The relation between structures and properties of polyurethane are investigated by modern physical and chemical methods.The results obtained are as follows:the effects of the content of self-crosslinking agent on the properties of polyurethane,i.e.,dispersion stability,dynamical viscoelasticity and mechanical properties are discussed.It is found that the optimum molar ratio of epichlorohydrin and diethylenetriamine is 1:2.A mois-     

基于NASTRAN的现浇混凝土空心楼盖非线性数值模拟分析

运用大型通用有限元软件PATRAN—NASTRAN,建立了无梁空心板的三维有限元分析模型,并对其进行了竖向荷载作用下的非线性分析,给出了一些关键部位的荷载挠度曲线以及钢筋的应变曲线,最后将计算结果与试验结果作了对比,验证了有限元数值模拟的有效性及参数选取的合理性．