两种Zn-饱和铵盐还原体系用于氢化偶氮苯的合成

采用Zn-饱和甲酸铵溶液、Zn-饱和苯甲酸铵溶液还原体系,从偶氮苯制备氢化偶氮苯。Zn-饱和甲酸铵溶液还原体系的优化反应条件为:偶氮苯/锌物质的量比为1∶3(偶氮苯2.5 mmol),饱和甲酸铵溶液1.0 mL,反应时间5 min,产率87.5%。Zn-饱和苯甲酸铵溶液还原体系的优化反应条件为:偶氮苯/锌物质的量比为1∶3(偶氮苯0.625 mmol),饱和苯甲酸铵溶液2.0 mL,反应时间3 min,产率86.4%。     

锌-丙酸铵还原体系用于氢化偶氮苯的合成

选用锌粉和镁粉与不同饱和铵盐（草酸铵、丙酸铵和苯甲酸铵）水溶液组成还原体系,由偶氮苯制备氢化偶氮苯,根据反应时间及结果选取锌一饱和丙酸铵水溶液为最佳还原体系。在反应温度25℃时,研究了锌一饱和丙酸铵水溶液还原体系还原偶氮苯反应,考察了偶氮苯与锌粉物质的量比、饱和丙酸铵水溶液的用量对氢化偶氮苯收率的影响。实验结果表明：偶...     

苦氨酸偶氮变色酸光度法测定对苯二甲酸中的微量钴

研究显色剂苦氨酸偶氮变色酸与钴的显色反应.在pH 10的柠檬酸铵一氨水溶液中,钴与苦氨酸偶氮变色酸反应生成绿色配合物,最大吸收波长为650 nm,表观摩尔吸光系数为2. 7×104.钴的含量在0～50μg/(25 mL)范围内符合比耳定律.该方法用于对苯二甲酸中微量钴的直接测定,测定结果的相对标准偏差小于5%(n=5),加标回收率为98%～102%.     

光度法测定锌钴镀液中钴

研究了显色剂二溴对甲偶氮二溴羧与钴(Ⅱ)的显色反应。在pH 10.2的柠檬酸铵-氨水缓冲溶液中,钴(Ⅱ)与二溴对甲偶氮二溴羧反应形成绿色配合物,最大吸收波长为650 nm,表观摩尔吸光率为2.59×104L.mol-1.cm-1。钴质量浓度在1.0 mg.L-1以内符合比耳定律。方法用于锌钴镀液中钴的直接测定,测得相对标准偏差(n=5)平均值为1.65%,平均回收率为100.5%。     

基于对环芳烷骨架的邻碘苯磺酸类催化剂的合成及其催化氧化性能

以对环芳烷为基本骨架结构,经磺化、上保护和脱氢上碘反应合成了新的邻碘苯磺酸类催化剂4-磺酸基-5-碘-[2.2]对环芳烃,其结构经¹H NMR, ¹³C NMR, IR, MS和元素分析表征。并以2,5-二甲基苯酚为底物,测试其催化效率。结果表明最佳反应条件为：催化剂用量为5 mmol%,在过硫酸氢钾复合盐（1 eq.）和10 mmol%四丁基硫酸氢铵存在下,在干燥碳酸二甲酯中于室温反应24 h,产物环化二聚体收率85%。     

钨过氧酸盐离子液体催化过氧化氢氧化苯甲醇制苯甲酸

用甲基三辛基氯化铵和钨酸钠一步法合成甲基三辛基季铵钨酸盐离子液体[(CH3)N(n-C8H17)3]2W2O11,以该离子液体为催化剂,在无反应溶剂条件下催化过氧化氢氧化苯甲醇生成苯甲酸。 考察了反应温度、催化剂用量以及氧化剂过氧化氢用量对苯甲酸产率的影响。 确定优化条件：反应温度70 ℃,苯甲醇用量5 mmol,催化剂用量是底物的0.4%(摩尔分数),30%过氧化氢用量2 mL,苯甲醇的转化率可达99%,苯甲酸选择性为98%。 该方法具有反应条件温和、产率高和选择性好的优点。     

新型可溶性偶氮聚酰亚胺及其作为液晶光定向层应用的初步研究

以 4 ,4′ 二 (1,2 苯二酸酐 4 羧酸酯 )偶氮苯为二酐单体 ,4 十六烷氧基 4′ ,4″ 二氨基三苯甲烷为二胺单体 ,通过缩聚反应合成了可溶性偶氮聚酰亚胺 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .在紫外光辐照下 ,上述聚合物表现出明显的光色效应 .经线性偏振紫外光 (LPUV)辐射后的上述偶氮聚酰亚胺定向层能诱导液晶盒中液晶分子发生定向沿面排列 ,且取向均匀 .上述实验表明 ,合成的偶氮聚酰亚胺是一类潜在的液晶光定向材料 .     

4，5-二甲氧基邻苯二甲醛在水中铵氮检测中的应用及测定方法

本发明公开了4,5-二甲氧基邻苯二甲醛在水中铵氮检测中的应用及测定方法。具体的测定方法包括：（1）在铵氮工作液中依次加入EDTA-4Na溶液、4,5-二甲氧基邻苯二甲醛溶液、亚硫酸钠溶液,然后用氢氧化钠溶液调节体系的pH值,反应平衡后,在λex=379 nm下,测定400～600 nm的荧光曲线,记录最大发射波长处的荧光强度,做出工作曲线;（2）将样品溶液在最大发射波长处的荧光强度根据工作曲线定量样品溶液中的铵氮含量。本发明所述方法中,4,5-二甲氧基邻苯二甲醛与铵氮的反应平衡时间缩短至50 min,且反应产物的最大激发波长红移至接近可见光区,为便携式铵氮在线荧光检测仪的研制奠定基础。     

浓硫酸催化合成叔丁基苯

利用浓硫酸催化叔丁醇和苯的反应,得到叔丁基苯;利用正交法优化了反应条件,利用气相色谱法测定了产物收率.结果表明,将叔丁醇滴加到苯-浓硫酸混合溶液中,控制叔丁醇与浓硫酸物料摩尔比为1:1、苯的用量为50 mL、浓硫酸用量为8.0 mL、反应温度为50℃、搅拌时间为4 h,目标产物的收率可达62.0%.     

锌-硫氰酸铵还原体系用于氢化偶氮苯的合成

氢化偶氮苯是重要的精细有机化工原料及中间体,染料工业用于制备联苯胺染料,医药工业用于生产解热镇痛药保泰松等[1]。传统的制备方法是在强碱性介质中用锌粉还原硝基苯,反应时间长,产率低[2]。用硫化铵快速还原偶氮苯生成氢化偶氮苯[3],则硫化铵用量大,刺激性气味对操作者及环境造成极大危害。我们采用ＮＨ4ＣＮＳ的饱和溶液与锌粉组成还原体系,在25℃时还原偶氮苯,反应条件温和,锌粉用量少,时间短,产率高,操作简单。反应方程式如下:ＰｈＮ=ＮｐＨ(橙红色)Ｚｎ-ＮＨ4ＣＮＳ25℃,ＥｔＯＨＰｈＮＨＮＨＰｈ(白色)1　实验部分在50ｍｌ圆底…     

Effect of the addition of diammonium citrate to <Emphasis Type="Italic">α</Emphasis>-cyano-4-hydroxycinnamic acid (CHCA) matrix for the detection of phosphorylated peptide in phosphorylation reactions using cell and tissue lysates

The ionization of phosphorylated peptides is usually suppressed by non-phosphorylated peptides when alpha-cyano-4-hydroxycinnamic acid (CHCA) is used as a matrix for matrix-assisted laser desorption/ionization-time-of-Flight (MALDI-TOF) mass spectrometry analysis. In the present study, we examined the effect of diammonium citrate addition to the CHCA matrix on the detection of phosphorylated peptides. Substrates for protein kinase C (PKC) and c-Src were synthesized and phosphorylated by reaction with cell and tissue lysate samples. The addition of diammonium citrate to the CHCA matrix increased the sensitivity for distinguishing phosphorylated peptides from background noise. However, the effect depended on substrate concentration.     

Contribution to the simultaneous determination of228Ra and226Ra by using 3M's EMPORETM radium rad disks

New method for simultaneous determination of²²⁸Ra and²²⁶Ra by using 3M's EMPORE^TM Radium Rad Disks in water has been developed. Both radionuclides²²⁶Ra and²²⁸Ra were counted through their daughter products,²²⁶Ra by conventional radon emanation techniques and²²⁸Ra through its daughter²²⁸Ac by using a proportional counter. Different molarity of diammonium hydrogen citrate were used for elution of²²⁸Ac and²²⁶Ra from EMPORE^TM Radium Rad Disks. 79% of²²⁸Ac was eluted in 10 ml of 0.0003M diammonium hydrogen citrate. The recovery of²²⁶Ra was 99% by using 40 ml of 0.2M diammonium hydrogen citrate adjusted by ammonium to pH 7.8.     

Simultaneous Analysis of Phosphorylated Peptides by MALDI-TOF-MS

Six peptides with various phosphorylation sensitivities for protein kinase A (PKA) were used for the simultaneous analysis of phosphorylated peptides using matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry. The mixture of six peptides was reacted with PKA and was analyzed by MALDI-TOF mass spectrometry. The intensity of all peaks except one phosphorylated peptide peak was very low (<20%). Moreover, we examined whether the addition of diammonium citrate to CHCA matrix at concentrations of 1–20 mg mL^?1 can increase the peak intensity of peptides and phosphorylated peptides. The addition of diammonium citrate increased the peak intensity of peptides and phosphorylated peptides, but an increase in the intensity was unsatisfactory. Our study strongly suggests that MALDI-TOF mass spectrometry is not suitable for the simultaneous analysis of phosphorylated peptides.     

有机分子偶氮苯在高岭石表面吸附研究

利用Gaussian 98软件,采用量子化学从头算计算方法,研究有机分子偶氮苯在高岭石表面的吸附作用.不同位置的吸附结果比较表明,吸附后体系稳定性强弱及电子发生转移的可能性大小依次是平行于硅氧烷表面、平行(010)面、平行[AlO4]八面体表面.芳香环上的π键和硅氧烷表面的O原子均相互作用,电子从偶氮苯上的C和N原子流向高岭石表面的O原子.对吸附复合物进行了X射线粉末衍射(XRD)、红外光谱(FTIR)测试及结构分析,结果表明,偶氮苯吸附到高岭石的硅氧烷表面.     

Complexometric determination of citric acid with copper

A method is presented in which citrate is determined by complexation with excess of copper(II), followed by back-titration with EDTA. Small amounts of citrate can be determined by this method in the presence of large amounts of most organic acids present in natural products. Interfering reductants are removed by treatment with permanganate, amino-acids with nitrous acid, and metal ions with a cation-exchange resin. The indicator used for end-point detection is Szechromotrope, 4,4'-sulphonyl-bis(azobenzene) dichromotropic acid.     

Preparation and characterization of magadiite grafted with an azobenzene derivative

A novel azobenzene derivative modified magadiite has been prepared by the reaction between the interlayer hydroxyl groups of magadiite and the azobenzene derivative using dodecyltrimethylammonium-exchanged magadiite as the intermediate. The formation of the silylated magadiite–azobenzene system was confirmed by X-ray diffraction, IR and MAS NMR spectroscopies. The organic groups of the azobenzene molecules are grafted onto the interlayer surface of magadiite by covalent bonding, affording compounds different from those derived by ion exchange. The orientation and reorientation of the azobenzene derivative in the magadiite have been examined through observing its photoinduced anisotropy behavior.     

十二烷基硫酸根复合物的制备及电子转移催化剂应用

制备了三种聚烷基紫精-十二烷基硫酸根复合物(PRV-LS),用紫外光谱、顺磁共振波谱研究了复合物的氧化、还原行为,将复合物用作电子转移催化剂于异相体系(CH_2Cl_2-H_2O;1:1,20mL)考察了其诱导的偶氮苯还原。结果表明:复合物在异相条件被还原时,聚烷基紫精自由基(PRV~ ·)在LS成份的作用下发生相转移,复合物具有良好的诱导偶氮苯还原的能力。     

十二烷基硫酸根复合物的制备及电子转移催化剂应用

制备了三种聚烷基紫精-十二烷基硫酸根复合物(PRV-LS), 用紫外光谱、顺磁共振波谱研究了复合物的氧化、还原行为, 将复合物用作电子转移催化剂于异相体系(CH2Cl2-H2O; 1:1, 20mL)考察了其透导的偶氮苯还原。结果表明: 复合物在异相条件被还原时, 聚烷基紫精自由基(PRV^+)在LS成份的作用下发生相转移, 复合物具有良好的诱导偶氮苯还原的能力。