5H-苯基联苯膦磺化产物的薄层色谱分离

1 引 言5H－苯基联苯膦（5H-phenyl-dibenzophosphole, PDBP）的磺化产物是一种多组分的复杂混合物,在石油化学工业具有很好的应用前景。5H－苯基联苯膦是三苯基膦的衍生物,是三苯基膦经桥连反应生成。经与发烟硫酸/硼酸的无水混合物反应,氢氧化钠中和,生成PDBP磺酸钠的混合物。混合物中除了可能含有目标产物二磺化PDBP和三磺化PDBP外,还可能含有取代位置不同的一磺化产物的异构体,二磺化和三磺化PDBP的氧化物,以及Na2SO4等。有关PDBP磺化产物分离方法的研究,目前尚未见报道。作者尝试用薄层色谱法来分离该混合物,通过…     

新型水溶性膦配体PDBPDS的制备及在氢甲酰化反应中的应用

依据量子化学理论计算 ,设计并优化了 1-苯基二苯并膦 (1- phenydibenzophosphole,简称 PDBP)磺化制备二磺化 1-苯基二苯并膦 (5 H- phenyl- 3,13- disulfonatodibenophosphole,简称 PDBPDS)的工艺 ,重点探讨了 SO3/PDBP比、反应温度、反应时间以及硼膦比对磺化产物收率的影响 .实验结果表明 ,采用 5 0 %发烟硫酸作磺化剂、SO3/ PDBP摩尔比为 3,H3BO3/ PDBP比为 5 ,在 13～ 15℃及无水无氧条件下反应 5 0 h,磺化产物收率可达 85 % .此外 ,还将所得产物用作丙烯氢甲酰化两相反应催化剂的配体 ,大大提高了催化剂的活性和产物正异比 ,且有机相中铑含量仅为 3.6× 10 - 8,有效地控制了铑流失 .实验结果证明了新型水溶性配体 PDBPDS是一个能实现均相反应多相化的、很有开发前景的配体 .     

电导滴定法测定磺化聚苯醚的磺化度

用电导滴定法测定所制备的磺化聚苯醚的磺化度（被磺化结构单元的百分数），以元素分析及核磁共振分析法验证了电导滴定结果。深入探讨了几种类型滴定曲线。     

甲氧基萘的磺化反应

以三甲基硅氯磺酸酯为磺化剂，进行了单和双甲氧基萘的磺化反应研究。用１ＨＮＭＲ测定磺化产物的组成。比较了磺化剂种类和用量对磺化反应的影响。发现了磺化反应中的成酐现象，研究了１，６－二甲氧基萘进行反应时二磺化产物的生成动力学。     

磺化聚苯醚的制备与表征

磺化聚苯醚的制备与表征汪传清，黄玉惠，丛广民（中国科学院广州化学研究所广州５１０６５０）关键词聚苯醚，磺化，磺化度，磺化聚苯醚聚苯醚是一种优良的工程塑料，对它进行修饰改性以获得各种功能材料的研究近十多年来十分活跃’‘，’，‘’．磺化聚苯醚（ＳＰＰＯ）...     

联苯衍生物的磺化反应

研究了一系列联苯衍生物和ＳＯ３在二氯甲烷中进行的磺化反应。联苯的磺化产物为４－磺酸取代物，进一步反应得到４，４′－、２，４，４′－及少量的２，４，２′，４′－多取代物。甲氧基取代的联苯体现了较高的反应活性，３，３′－二甲氧基联苯的彻底磺化得到五磺酸取代产物，２－甲氧基联苯的单磺化主要发生在５位上，４－甲氧基联苯的单磺化先在３位上进行。     

磺化条件对SPEEK膜性能的影响

本文采用浓硫酸作为磺化剂,以聚醚醚酮(PEEK)为原料研究了在25℃、35℃、40℃、45℃、50℃和55℃以及2至24h磺化时间下所获得的SPEEK膜的物理化学性质,探讨了磺化温度、磺化时间对SPEEK膜的各项性能的影响.SPEEK膜的磺化度、离子交换容、含水率、导电率和钒离子渗透率等均随磺化温度和磺化时间的增加而呈...     

不同磺化度下的磺化聚醚醚酮对全钒储能液流电池性质影响的研究

本文报道了采用浓硫酸作为磺化剂,成功合成了不同磺化度下的聚醚醚酮(PEEK)膜,并深入研究了磺化条件包括磺化时间和磺化剂的用量对所获薄膜性能的影响,获得了在不同磺化度（DS）下SPPEK膜的离子交换容,含水率,机械性能,质子电导率等参数,特别测定了在全钒液流电池工作条件下钒离子(Ⅳ)渗透率,首次为该类液流储能电池使用价廉质优的质子交换膜提供了基础实验数据。室温条件下的实验结果如下：1）磺化12小时后,膜的磺化度46%,含水量为28%,钒离子(Ⅳ)选择性最佳（钒离子渗透率为1.2×10-7 cm2/min-1,是Nafion117 (2.9×10-6 cm2/min-1)的1/24）,其质子电导率只有0.02 S/cm;2）磺化96小时其磺化度达79%的膜,质子电导率达0.16 S/cm,是Nafion117 (0.10S/cm) 的1.6倍, 但其机械性能最差;3）与Nafion117膜相比,磺化在36到48小时的SPPEK膜其机械力学性能好,薄膜的钒离子渗透率、离子交换容IEC、质子导电率和含水率高,且对钒离子的选择性佳,尤其价格仅为Nafion膜的1/13,是理想的Nafion膜的代替物,可望直接应用于全钒氧化还原液流（VRB）电池中。本文还讨论了磺化时间和不同磺化剂量对膜的性质的影响。     

13C核磁共振研究磺化脲醛树脂的反应机理

利用^13CNMR数据证实了在低磺化剂用量下脲醛树脂的磺化改性仍可发生,并对磺化脲醛（SUF）树脂制备过程中的羟甲基化、缩合、磺化及缩聚等各步反应机理进行了探讨.明确了SUF树脂的^13CNMR谱图中各峰位所对应的结构单元,认为3个未知峰的出现与磺化改性得到的一些新结构单元有关,并对它们的结构进行了推测.通过对比不同磺化和缩聚反应程度下得到的SUF产物的^13CNMR数据,对磺化和缩聚反应后某些结构的出现和消失进行了解释.     

杂萘联苯共聚醚砜的非均相磺化

以杂萘联苯共聚醚砜(PPHES)为原料,氯仿为溶剂,浓硫酸为磺化试剂,采用非均相磺化法对PPHES进行了磺化改性,得到了一系列不同磺化度的磺化杂萘联苯共聚醚砜(SPPHES).考察了浓硫酸浓度、磺化反应温度和时间等工艺条件对产物磺化度的影响.利用FT-IR、1H-NMR对SPPHES进行了表征.结果表明,磺酸基已成功引...     

Synthesis and photopolymerization kinetics of benzophenone piperazine one‐component initiator

A one‐component type II photoinitiator (PDBP), based on 4‐hydroxybenzophenone (HBP), acryloyl chloride, and piperazine, was synthesized and its structure was confirmed by ¹H‐NMR. The photopolymerization kinetics of the photoinitiator was studied by real‐time Infrared spectroscopy (FT‐IR). It indicated that PDBP was a more effective photoinitiator than that of BP/triethylamine (TEA). The rate of polymerization, final conversion increased and the induction period shortened with increase in PDBP concentration, light intensity, and amine concentration. The kinetics of photopolymerization for TPGDA incorporating PDBP in the presence of different tertiary amines as the initiating system indicated that the PDBP/TEA combination exhibited the highest polymerization rates among the PDBP/amine combinations. Copyright © 2007 John Wiley & Sons, Ltd.     

有机化合物PDBP的合成及其在催人反应中的应用

用量子化学AM1方法优化了1－苯基二苯并膦（PDBP）和三苯基膦（TPP）的几何构型,比较了两种化合物的电子结构和空间结构,发现PDBP作为羧基合成铑膦催化剂的配体要优于三苯基膦（TPP）;系统研究了PDBP的合成方法,其最佳合成条件为：在无水无氧的条件下,采用二乙胺锂与溴化四苯基膦摩尔比为3,反应温度为22℃,反应5h,反应后酸化,pH值为1－2,产物收率可达到85％－88％,采用元素分析、红外、核磁等方法,对其结果进行了表征,并将PDBP用于丙烯氢甲酰化反应的催化剂配体。实验证明,在相同的反应条件下,以其为配体的催化剂活性约是目前工业上使用的以三苯基膦为配体的催化剂的1．2倍,选择性约为其1．7倍。     

Crystal Structure of the Sought-After Tetrameric [(PDBP)AgCl]4 Cluster (PDBP=5-Phenyldibenzophosphole)

The sought-after member of the [(PDBP) _n AgX] _m (n, m=1,4; 2,2; 3,1; PDBP=5-Phenyldibenzophosphole, X=halides) series, the tetrameric [(PDBP)AgCl]₄ cluster has been prepared and structurally characterized. The [P₄Ag₄Cl₄] cluster core of [(PDBP)AgCl]₄ bears striking similarity to that of [(Ph₃P)AgCl]₄.     

Separation of peroxidation products of diacyl-phosphatidylcholines by reversed-phase liquid chromatography-mass spectrometry

Lipid peroxidation process has attracted much attention due to the growing evidence of its involvement in the pathogenesis of age-related diseases. The monitoring of the lipid peroxidation products in phospholipids, formed under oxidative stress conditions, may provide new markers for oxidative stress signaling and for disease states, giving new insights in the pathogenesis process. Reversed-phase liquid chromatographic method coupled to mass spectrometry was developed for the separation of oxidized glycero-phosphatidylcholine (GPC) peroxidation products formed by the Fenton reaction that mimic in vivo oxidative stress conditions. The LC-MS conditions were applied for the separation of peroxidation products of oleoyl- (POPC), lineloyl- (PLPC) and arachidonoyl-palmitoyl phosphatidylcholine (PAPC). The peroxidation products separated included products resulting from the insertion of oxygen atoms in the sn-2 chain (long-chain), and products with the sn-2 chain shortened resulting from cleavage of oxygen-centered radicals (short-chain). Among long-chain products were the keto, hydroxy, hydroperoxide and poly-hydroxy derivatives, while short-chain products included dicarboxylic acids, aldehydes and hydroxy-aldehydes. Separation of long-chain products formed in each phosphatidylcholine was observed, and the reconstructed ion chromatogram of each ion showed an increase in the number of peaks with the increase in the number of oxygen atoms inserted into the phospholipid. Separation of short-chain products took place according to the functional group present at the sn-2 moiety that allowed the elution of dicarboxylic acids distinct from aldehydes. Separation between isomeric structures that were present in short- and long-chain products was also achieved.     

Promising Antimicrobial Properties of Bioactive Compounds from Different Honeybee Products

Bee products have been known for centuries for their versatile healing properties. In recent decades they have become the subject of documented scientific research. This review aims to present and compare the impact of bee products and their components as antimicrobial agents. Honey, propolis, royal jelly and bee venom are bee products that have antibacterial properties. Sensitivity of bacteria to these products varies considerably between products and varieties of the same product depending on their origin. According to the type of bee product, different degrees of activity were observed against Gram-positive and Gram-negative bacteria, yeasts, molds and dermatophytes, as well as biofilm-forming microorganisms. Pseudomonas aeruginosa turned out to be the most resistant to bee products. An analysis of average minimum inhibitory concentration values for bee products showed that bee venom has the strongest bacterial effectiveness, while royal jelly showed the weakest antibacterial activity. The most challenging problems associated with using bee products for medical purposes are dosage and safety. The complexity and variability in composition of these products raise the need for their standardization before safe and predictable clinical uses can be achieved.     

基于毛细管电泳的环介导恒温扩增技术检测方法研究

以大肠杆菌(E.coli)为对象,采用环介导恒温扩增技术(LAMP)对其扩增,在实验室自制的毛细管电泳-诱导荧光平台上建立了LAMP产物的检测新方法。引物F3,B3,FIP,BIP扩增的E.coli LAMP产物大小为240 bp。优化的毛细管电泳条件为:毛细管有效长度/总长度(10 cm/15 cm),筛分介质溶液为0.5%羟乙基纤维素(1 300 K),电场强度(100 V/cm),进样条件(100 V/cm,1.0 s)。毛细管电泳时,DNA长度在100~500 bp范围内与其迁移时间呈线性关系,相关系数为0.996。在相同毛细管电泳条件下对E.coli LAMP产物进行分析,并利用这种线性关系在电泳图中对E.coli LAMP产物与假阳性产物做区分,结果表明,毛细管电泳技术不仅可在15 min内实现LAMP产物及附加产物的快速检测,而且可快速区分LAMP阳性及假阳性实验产物。采用建立的毛细管电泳快速检测LAMP产物的方法,对AB0174 E.coli基因实施了LAMP,结果表明该方法适合DNA LAMP产物的快速检测。     

芳香类化合物异戊烯基化的研究进展

结构多样的芳香类化合物一直被用作新药发现的线索或主要来源。通过对类药物天然产物进行异戊烯基化结构修饰,能有效提高芳香类化合物生物活性及生物利用度,为新药研究与开发提供简便高效的方法。本文综述了近年来芳香类化合物异戊烯基化的各种方法,以为今后研究提供参考。     

Influence of photo-Fries reaction products on the photodegradation of bisphenol-A polycarbonate

The photodegradation of BPA polycarbonate (PC) can be described as an autoaccelerating process initiated by the formation of biphenol products arising from a formal photo-Fries reaction pathway. Evidence comes from spiking PC films with model compounds of photo-Fries reaction products, pre-exposure of films to generate photo-Fries products, and kinetic analysis. Published data on products formed during natural PC weathering are consistent with this pathway.     

Microbial‐induced synthesis of mineralization products based on the capture of carbon dioxide: Characteristics,reaction kinetics,interfacial adhesion properties,and mechanism of action

As a new type of green environment‐friendly cementitious material, microbial‐induced mineralization products have garnered more and more attention. In this paper, the synthesis of mineralization products under microbial inducement was conducted. The composition and microstructure of mineralization products were studied using energy‐dispersive spectrometer (EDS), X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The results showed that mineralization products were calcite, while the shape was similar to globular type, and particle size was about 5 μm. The effect of microbial culture solution, secretion solution, and concentration on the conductivity of the solution was compared and analyzed. During the formation of mineralization products, bacterial bodies not only played the role of nucleation sites but also accelerated the deposition of mineralization products. Thus, it could be seen that the bacterial bodies had a certain influence on the reaction kinetics. The adhesion force of mineralization products was evaluated by the interfacial adhesion properties between the mineralization products and glass slides. The results of the sonication test and scratch test indicated that the interfacial adhesion strength between mineralization products and glass slides was closely related to the mass of mineralization products deposited. The larger the mass of mineralization products deposited, the greater the interfacial adhesion strength. Based on the above research and analysis, the reaction process and mechanism model of microbial‐induced mineralization were defined.     

The Research of Sulfuric Acidic Recycling of Aluminum Industry Fluorine-containing Waste Products

The article presents the method of recycling aluminum industry fluorine-containing waste products to produce hydrogen fluoride. We carried out the estimate of the thermodynamic parameters of sulfuric acidic recycling of fluorine-containing waste products. We considered the necessity of waste products preliminary oxidizing roast stage to reduce carbonic constituent due to the interaction between carbonic constituent blocks of the sulfuric acid and waste products. We also carried out the researches for kinetic characteristics and to determine the optimal conditions for the to recycle sulfuric acidic in the fluorine-containing waste products.