乙二胺基乙磺酸钠的合成与表征

乙二胺基乙磺酸钠是水性聚氨酯合成中重要的亲水性扩链剂, 又可作为有机中间体、生化试剂应用于其它领域.采用乙二胺(EDA)和2-氯乙磺酸钠反应合成乙二胺基乙磺酸钠, 由红外光谱(FTIR)、核磁氢谱(1H NMR)和碳谱(13C NMR)、X射线衍射(XRD)、元素分析等手段表征了产物的结构与特性. 在EDA与2-氯乙磺酸钠物质的量比为6.5∶1时, 合成产物中乙二胺基乙磺酸钠含量高达94.4%. 产物极易溶于水, 微溶于甲醇, 乙醇, 不溶于丙酮, N,N-二甲基甲酰胺, 四氯化碳, 氯仿等有机溶剂.     

N-(2-氯乙基)-N'-2-(O~6-苄基-9-鸟嘌呤基)乙基-N-亚硝基脲的合成

以O~6-苄基鸟嘌呤为原料,经取代反应和盖布瑞尔反应制得N9-(2-胺基)乙基-O6-苄基鸟嘌呤(4);4与异氰酸酯经取代反应和经亚硝化反应合成了N-(2-氯乙基)-N'-2-(O6-苄基-9-鸟嘌呤基)乙基-N-亚硝基脲(6)。4和6为新化合物,其结构经UV-Vis,1H NMR,13C NMR,IR和HR-ESI-MS表征。     

铁羰基化合物的研究(η~5-C_5H_5)Fe(CO)_2CH_2COOR的合成

在我们实验室里采用环戊二烯基羰基铁的钠盐[(η~5-C_5H_5)Fe(CO)_2]Na和氯代乙酸酯ClCH_2COOR(R=C_2H_5,C_3H_7,C_4H_9,C_5H_(11))直接反应合成了铁羰基化合物(η~5-C_5H_5)Fe(CO)_2CH_2COOR(Ⅰ).并通过IR、~1H NMR、~(13)C NMR以及MS的分析,确定了(Ⅰ)的结构.η~5-环戊二烯基(2-烷氧基-2-氧代乙基)二羰基合铁(Ⅰ)的合成路线如下:     

O-炔丙基-N,N-二(2-氯乙基)-4-氨基苯酚的合成

以对氨基苯酚（1）为原料,经氨基的羟乙基化、酚羟基的苄基保护、氯代、脱保护制得N,N-二 (2-氯乙基) -对氨基苯酚（5）;在碳酸铯作用下,5与溴丙炔经O-烷基化反应合成了新化合物--O-炔丙基-N, N-二(2-氯乙基)-4-氨基苯酚,其结构经¹H NMR, ¹³C NMR和MS表征。     

5-乙基-2-吲哚酮的合成及其酰基化和N上烃基化反应研究

以4-乙基苯胺1为原料,经Sandmeyer反应得5-乙基靛红2;2经水合肼还原得到5-乙基-2-吲哚酮3;N,N-二甲基甲酰胺与三氯氧磷先形成Vilsmeier-Haack试剂,再与化合物3反应,合成2-氯-5-乙基-3-乙酰吲哚4;以丙酮为溶剂,对化合物4烃基化,以78.5%-95.6%的收率得到N-取代-2-氯-5-乙基-3-乙酰吲哚5a-5e。其中化合物4、5a-5e均未见文献报道,它们的结构均通过红外光谱、核磁共振氢谱(碳谱),质谱等确认。     

N,N-二(2-氯乙基)-磷酰基双硫脲的合成及除草活性研究

采用N，N-二(2-氯乙基)-磷酰基双异硫氰酸酯与不同的芳胺反应合成了7个N，N-二(2-氯乙基)-磷酰基双硫脲衍生物，它们的结构经1^H NMR、IR和元素分析证实。初步生测结果表明它们对单、双子叶植物根的生长具有较好的抑制活性。     

电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇

2-乙基己醇是一种增塑剂醇,可用于合成增塑剂、表面活性剂和溶剂等诸多化工领域.目前工业上2-乙基己醇的合成是以化石资源丙烯为原料,与氢气和一氧化碳通过氢甲酰化反应制备1-丁醛,后者经羟醛缩合和催化加氢反应生成2-乙基己醇.由生物质发酵产生的1-丁醇为原料,只需要经Guerbet反应可一步直接生成2-乙基己醇.比较而言,Guerbet反应路线步骤更少,且1-丁醇原位脱氢产生的氢为氢源,无需额外氢,因此比化石资源丙烯路线对环境友好.目前,文献报道的非均相催化1-丁醇Guerbet反应条件苛刻(如温度>170 oC),副产物多(如烯烃、醚和高碳醇等),且均相催化剂的活性低.本文报道了一类Cp*Ir(Cp*为1,2,3,4,5-五甲基环戊二烯基)配合物用于该Guerbet反应.当Cp*Ir配合物的配体上修饰给电子基N,N-二甲基氨基和邻羟基时,Cp*Ir配合物的催化活性增强,催化剂的转化数最高达到了14047.当氢氧化钾和Cp*Ir配合物(配体上修饰了N,N-二甲基氨基和邻羟基官能团)在1-丁醇中的浓度分别为1.7 mol％和0.04 wt％时,在130 oC反应48 h,产物2-乙基己醇收率为23.9％,选择性为89.5％.核磁(NMR)研究结果表明,Cp*Ir配合物配体上的邻羟基与氢氧化钾反应脱除质子,生成了羰基结构配体配位的Cp*Ir配合物,继续催化1-丁醇脱氢反应.机理研究表明,中间产物2-乙基己醛α-碳上乙基的位阻效应和2-乙基己烯醛本身的共轭效应抑制了其继续发生羟醛反应,从而提高了目标产物的选择性.     

新型1,4,5,8-萘酰亚胺类衍生物的合成

以1,4,5,8-萘四甲酸二酐(1)和2-乙基己胺(2)为原料,设计并合成了3种新型的1,4,5,8-萘酰亚胺类衍生物,其结构经1H NMR,IR和MS表征。中间体N-(2-乙基己基)-萘-1,8-二甲酸单酐-4,5-单甲酰亚胺的最佳反应条件为:19.7 mmol,n(1)∶n(2)=1.1∶1.0,以醋酸锌为催化剂,在DMF(20 mL)中于140℃反应15h,收率25%。     

以固体光气为原料合成氯代甲酸(2-乙基)己酯

氯代甲酸(2-乙基)己酯是一种化工中间体,主要用来制备过氧化二碳酸二(2-乙基)己酯(简称EHP),EHP是一种高活性聚合引发剂。由固体光气和2-乙基己醇为原料合成氯代甲酸(2-乙基)己酯的研究未见报道。本文以固体光气和2-乙基己醇为原料合成了氯代甲酸(2-乙基)己酯,研究了反应物加入顺序、反应时间、反应温度、催化剂种类及用量对氯代甲酸(2-乙基)己酯收率和纯度的影响,得到了优化的合成工艺,对产物结构进行了分析,进一步用其合成了常用的高活性聚合引发剂过氧化二碳酸二(2-乙基)己酯(EHP)。     

4-甲基-苯磺酸-2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯的合成及生物活性研究

合成了12个未见文献报道的4-甲基-苯磺酸2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯, 其结构经元素分析、¹H NMR和IR确证. 初步活性测试结果表明: 部分化合物有较好的杀菌活性.     

Hydrogels of sodium alginate based copolymers grafted with sodium-2-acrylamido-2-methyl-1-propane sulfonate and methacrylic acid for controlled drug delivery applications

Novel sodium alginate based hydrogels were prepared by grafting the binary mixture of methacrylic acid and sodium-2-acrylamido-2-methyl-1-propane sulfonate on to sodium alginate (SA) with N,N'-methylenebisacrylamide (MBA) and ammonium persulfate (APS) as crosslinker and initiator respectively. The resultant SA-g-poly(AMPSNa-co-MAA) hydrogels were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Thermo Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD). The results indicated that an increase in the amount of sodium-2-acrylamido-2-methyl-1-propane sulfonate, swelling capacity was found to increase. The effects of temperature, pH and inorganic salt on the swelling behavior of the hydrogels were investigated. The pH reversibility behavior at pH levels of 1.0 and 9.0 indicated great potential of this hydrogel as a candidate system for controlled drug delivery.     

Chemiluminescence determination of sodium 2-mercaptoethane sulfonate by flow injection analysis using cerium(IV) sensitized by quinine

A flow injection method with chemiluminescence (CL) detection is proposed for the determination of sodium 2-mercaptoethane sulfonate (MESNA), a drug often used to reduce the urotoxic effects of antineoplastic alkylating agents. The procedure is based on the reaction of the thiol with Ce(IV) in a sulfuric acid medium and measurement of the CL intensity produced by quinine used as a sensitizer. The optimum conditions for CL emission were investigated. Using the CL peak height as the analytical parameter, MESNA was determined over the concentration range 0.29–2.21 ng (1.97–9.85 μg·l⁻¹) with a detection limit of 0.21 ng (1.38 μg·l⁻¹) and a relative standard deviation (R.S.D.) of 4.1%. The method was applied satisfactorily to the determination of MESNA in pharmaceutical preparations with percentages of recovery between 94 and 105.     

TiO2纳米管的光催化作用

光催化降解;十二烷基苯磺酸钠;紫外可见光谱;TiO2纳米管的光催化作用     

2H NMR和DSC法研究十二烷基磺酸钠-正戊醇-水三元体系的溶致液晶

测定了十二烷基磺酸钠/正戊醇/水体系的相平衡,在相图中的液晶区选取样品点,采用²H NMR和差示扫描量热方法,并结合其液晶纹理,研究了该体系液晶相的结构特点。结果表明,在一定温度下,整个液晶区均为层状液晶,其相结构不随水含量和醇含量的变化而变化。在组成固定的情况下,该体系液晶的相结构随温度的升高而发生变化。     

用高效液相色谱法考察表面活性剂在油层中的色谱分离

强化采油中常用的表面活性剂石油磺酸盐在通过油层时会发生色谱分离作用,其完整性受到破坏,从而影响与原油界面的活性。采用高效液相色谱法（ＨＰＬＣ）,通过测定磺酸盐色谱分离因子,定量地描述石油磺酸盐在岩心多也介质的色谱分离程度。应用该方法可以考察影响色谱分离因子的因素,以优化化学驱油配方的设计。该方法具有灵敏度高、可靠、用量少等特点。     

One-step Synthesis and Gas Sensing Properties of Hierarchical SnO2 Materials

Hierarchical tin oxide(SnO₂) architectures were synthesized with a facile hydrothermal method. In the hydrothermal synthesis, sodium dodecyl benzene sulfonate(SDBS) surfactant plays an important role as structure-directing reagent. The synthesized samples were characterized by powder X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM) and high-resolution transmission electron microscopy(HRTEM). The results clearly reveal that the hierarchical architectures of SnO₂ were composed of aggregated nanosheets with a thickness of about 100 nm. A possible mechanism for the formation of the SnO₂ hierarchical architectures was proposed. In addition, the gas sensing properties of the as-prepared products were investigated and it was found that the sensor based on the special SnO₂ hierarchical architectures exhibited a high response and good selectivity to NO₂ at the optimal working temperature of 160 ℃.     

表面活性剂和聚乙烯吡咯烷酮在ZrO2上的吸附对其悬浮体稳定性的影响

研究了水溶液中十二烷基苯磺酸钠（ＳＤＢＳ）、溴代十四烷基吡啶（ＴＰＢ）和聚乙烯吡咯烷酮（ＰＶＰ）在ＺｒＯ２上的吸附及对ＺｒＯ２水悬浮体稳定性的影响。结果表明：ｐＨ＝２．４时ＳＤＢＳ在ＺｒＯ２上的吸附等湿线为ＬＳ型，ｐＨ＝７．０时ＴＰＢ的吸附等温线为Ｓ型，吸附等温线与ＺｒＯ２粒子ζ电势变化同线有大体一致的关系。在最大吸附量时ＺｒＯ２粒子ζ电势较大，且吸附的表面活性剂离子形成大部分亲水基朝向水相的表面     

Emulsifier-free emulsion copolymerization of styrene and sodium 1-allyloxy- 2-hydroxypropane sulfonate

Colloidal particles of poly(styrene-co-sodium 1-allyloxy- 2-hydroxypropane sulfonate) with diameters of 508 ∼ 596 nm were synthesized by emulsifier-free emulsion copolymerization, crosslinked with divinylbenzene, and initiated by potassium persulfate/sodium bisulfite in a mixed solvent of water and acetone. The diameters of the submicrometer-sized particles were measured by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The surface charge densities of the particles were determined by condutometric titration. The results showed that the highly surface charged monodispersed submicrometer-sized particles were obtained by two-stage shot growth polymerization. The particle diameters could be reduced and controlled by adding suitable amount of acetone.     

Determination of Pb in natural waters with 2-mercaptobenzimidazole-5-sulfonate (MBIS)chemically modified gold electrode

The preparation, characterization and analytical applications of gold electrodes modified with ω-mercapto alkyl/aryl sulfonates are described. The devices resulted effective for the determination of free and labile Pb(II) in water samples by anodic stripping voltammetry (E_dep = −600 mV) and in particular 2-mercaptobenzimidazole-5-sulfonate (MBIS) offered the best performances with detection limit of 0.4 μg L⁻¹.Quantitative stripping of Pb from the electrode surface during the anodic scan, is obtained using sodium citrate buffer (pH = 9.0) as supporting electrolyte. Natural waters were analysed by standard addition method with good recoveries (mean percentage = 97%); no fouling effects due to humic acids or other organic constituents were observed in the reported conditions.     

Laser Flash Photolysis Mechanism of Anthraquinone-2-Sodium Sulfonate in Pyridine Ionic Liquid/Water Mixed System

The photochemical reaction process of anthraquinone-2-sodium sulfonate (AQS) in the mixture of water (H₂O) and N-butylpyridinium tetrafluoroborate ([BPy][BF₄]) was studied using the laser flash photolysis technique. Experimental results show that the excited triplet of AQS (³AQS^*) could react rapidly with H₂O and the transient absorption spectra greatly changed by increasing the volume fraction of the ionic liquid (V_IL) in [BPy][BF₄]/H₂O mixtures. The absorbance at 510 nm increased gradually with increasing V_IL when 0< V_IL< 0.1. By contrast, the absorbance decreased gradually when V_IL>0.1. Otherwise, the absorbance of the band near 380 nm steadily increased. The apparent kinetic parameters of transient species B and ³AQS^* are obtained approximately. ³AQS^* abstracting hydrogen from [BPy]⁺ was also explored. It was deduced that the 350-420 nm band was the superposition of the peaks of ³AQS^* and AQSH^·. The two reactions of ³AQS^* with [BPy][BF₄] and H₂O are a pair of competitive reactions. We also concluded that the entire reaction processes slow down in the case of high [BPy][BF₄] concentrations.