5-碘[杯(4)芳烃偶氮]氨基喹啉光度法测钯

合成了新试剂5 碘[杯(4)芳烃偶氮]氨基喹啉(ICAQ),并研究了该试剂与钯显色反应条件。结果表明,在pH10.2～11.0的Na2CO3 NaHCO3缓冲介质中,在TritonX 100存在下,试剂与钯发生显色反应,生成1∶1稳定络合物。建立了测定钯的光度法新体系,λmax=625nm,ε=1.42×105L·mol-1·cm-1,钯质量浓度在0～0 80μg/mL内符合比尔定律。方法用于钯催化剂中钯的测定,结果与原子吸收法相符,平行6次测定的RSD在2.5%～3.0%。     

新显色剂8-[杯(4)芳烃偶氮]氨基喹啉的合成及其与金的显色反应

合成了一种新的杂环偶氮类显色试剂 8 [杯 ( 4 )芳烃偶氮 ]氨基喹啉(CAQ) 1。研究了该试剂与金的显色反应的适宜条件 ,在碱性介质中 ,在CTMAB存在下 ,试剂与金生成 1∶1稳定络合物 ,建立了测定金的光度法新体系 ,体系至少可稳定 8h ,λmax =640nm ,ε =2 .0 6× 1 0 5L·mol-1·cm-1,金含量在 0～ 2 2μg 2 5mL内符合比尔定律。方法已用于金矿石中微量金的测定。     

新显色剂5-磺酸基[杯(4)芳烃偶氮]氨基喹啉的合成及与钯显色反应的研究

合成了新试剂 5 磺酸基 [杯 (4)芳烃偶氮 ]氨基喹啉 (SCAQ) ,研究了该试剂与钯 (Ⅱ )显色反应的适宜条件 ,在pH 8.0的缓冲介质中 ,在非离子表面活性剂TritonX 10 0存在下 ,试剂与钯(Ⅱ )生成 1∶1稳定配合物 ,建立了测定钯 (Ⅱ )的光度法新体系 ,体系至少可稳定 6h ,λmax=6 6 0nm ,ε =7.88× 10 4 L·mol- 1·cm- 1,钯 (Ⅱ )浓度在 0～ 30 μg/ 2 5ml范围内服从比耳定律。方法已用于钯催化剂中钯 (Ⅱ )的测定 ,结果与原子吸收光谱法相符 ,RSD为 1.5 %～ 2 .6 %。     

显色剂5,7-二氯[杯(4)芳烃偶氮]氨基喹啉的合成及与镍显色反应的研究

合成了试剂5,7-二氯[杯(4)芳烃偶氮]氨基喹(CCAQ),研究了该试剂与镍(Ⅱ)的显色反应的适宜条件,在pH 10.8的缓冲介质中,在混合表面活性剂吐温40和CTMAB存在下,试剂与镍(Ⅱ)生成1∶1稳定配合物,体系至少可稳定8 h,λmax=620 nm,ε=1.83×105L.mol-1.cm-1,镍(Ⅱ)浓度在0.1~8μg/25 mL范围内服从比耳定律。方法已用于铝合金中镍(Ⅱ)的测定,RSD小于3.5%,回收率为98%~101%。     

2-(2-喹啉偶氮)-5-二乙氨基苯甲酸光度法测定生物样品中的钴

钴是人体必须的微量元素,大量研究工作表明,钴对铁的代谢,血红蛋白的合成,细胞的发育成熟及成熟细胞的释放等均有重要的生理功能。缺钴将产生严重的低色素小细胞,而过量的钴却能产生严重的中毒现象,因而生物样品中痕量钴的测定具有重要意义。     

2-(2-喹啉偶氮)-1,5-二氨基苯固相萃取光度法测定钴

合成了新试剂2 (2 喹啉偶氮) 1,5 二氨基苯(QADAB),研究了其与钴的显色反应及C18固相萃取小柱对显色络合物的固相萃取,在pH3.5磷酸盐缓冲介质中,CTMAB存在下,QADAB与钴反应生成2∶1稳定络合物,该络合物可用C18固相萃取小柱富集,小柱上富集的络合物用乙醇(内含2%乙酸)洗脱后用光度法测定,λmax=590nm,ε=8.36×104L·mol-1·cm-1。钴含量在0.01～0.80mg·L-1内符合比耳定律,方法用于环境样品中钴含量的测定,结果满意。     

2-(2-喹啉偶氮)-5-二乙氨基苯胺光度法测定钴

合成了新试剂 2 (2 喹啉偶氮 ) 5 二乙氨基苯胺 (QADEAA) ,并研究了其与钴的显色反应 ,在pH为5 .5的磷酸盐缓冲介质中 ,在CTMAB存在下 ,QADEAA与钴反应生成 2∶1稳定络合物 ;用磷酸酸化后 ,在酸介质中 ,体系λmax=6 2 5nm ,ε =1 .4 6× 1 0 5L·mol-1 ·cm-1 。钴含量在 0 .0 1～ 0 .30mg/L内符合比尔定律。方法用于大米、猪肝及水样中钴含量的测定 ,结果令人满意     

2-[2-(4-甲基喹啉)-偶氮]-5-二乙氨基苯酚固相萃取光度法测定水和食品中的镉

研究了新试剂2[2(4甲基喹啉)偶氮]5二乙氨基苯酚(QADP)与镉的显色反应。在pH为8.0的硼酸氢氧化钠缓冲介质中,TritonX100存在下,QADP与镉反应生成2∶1稳定络合物。体系最大吸收波长λmax=590nm,摩尔吸光系数ε=1.56×105L·mol-1·cm-1。样品中的镉用强阴离子交换固相萃取柱固相萃取预分离和富集后用该方法测定,结果令人满意。     

8-氨基喹啉-5-偶氮苯和8-氨基喹啉-5-偶氮对氯苯荧光光度法测定微量铬(V1)

8-氨基喹啉-5-偶氮苯(AQAP)是钯(Ⅱ),氰的显色剂,也是金(Ⅲ)和铜(Ⅱ)的荧光试剂。我们合成了AQAP及其氯代衍生物8-氨基喹啉-5-偶氮—对氯苯(AQAPC1)。发现它们均是优良的铬(Ⅵ)的荧光试剂,可以在上千倍Cr(Ⅲ)存在下测定微量铬(Ⅵ)。     

5-(5-硝基-2-吡啶偶氮)-2,4-二氨基甲苯光度法同时测定钴和钯

在3.0mol·L-1H2SO4介质中,钯(Ⅱ)与试剂可形成稳定的配合物,而钴(Ⅱ)与试剂在pH 5.5的HOAc-NaOAc介质中才能定量配合,配合物形成后,用硫酸酸化至一定酸度时则转变为另一稳定的深色配合物。同时两者的吸光度于586nm波长处具有良好的加和性。据此,建立了钴、钯同时测定的方法,已用于合成样中微量钴、钯的同时测定。     

Synthesis and Conformational Properties of Bis（calix [4] arene）

The bis(calix [4] arene)3 was synthesized in moderate yield by the reaction of p-tert-butylcalix [4] arene (1) with 1,4-bis(chloromethyl) benzene (2). The conformation of all alkylated product 4 was investigated by the variable-temperature ^1H-NMR.     

(硫杂)杯[4]芳烃缩氨基(硫)脲(桥联)衍生物的合成

对叔丁基(硫杂)杯[4]芳烃-1,3-二醛基衍生物4a和4b与苯基氨基硫脲进行“1＋2”缩合反应, 合成了杯[4]芳烃缩氨基硫脲衍生物5a和5b, 产率为84%和85%. 化合物4a和4b与1,6-己基双氨基脲发生“1＋1”缩合反应, 合成了杯[4]芳烃双缩氨基脲桥联衍生物6a和6b, 产率为83%和80%. 新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

New preorganized calix[4]arenes. Part I. A doubly-crowned calix and a double-calixcrown derived from 4,6,10,12,16,18,22,24,25,26,27,28-Dodecamethyl-5,11,17,23-tetrahydroxycalix[4] arene

A doubly-crowned calix and a double-calixcrown derived from 4,6,10,12,16,18,22,24,25,26,27, 28-dodecamethyl-5,11,17, 23-tetrahydroxycalix[4]arene (1) have been prepared by reaction of appropriate oligoethylene glycol ditosylates with (1) in acetonitrile in the presence of potassium carbonate. A potassium template effect is observed during one of the double cyclizations.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

Isolation and X-ray crystal structure of a stable calix[4]arene monohemiketal

The formation of a stable calix[4]arene monohemiketal is described. X-ray crystallographic data provide conclusive evidence for the presence of a stabilizing hydrogen bond. Supplementary Data. Lists of H-atom parameters and bond lengths and angles involving hydrogens have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 82159 (5 pp.).     

Evidence of Hydrogen Bonding in Stabilizing the Cone Conformation of a Monoalkylated Calix[4]arene. X-ray Structure of 25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene

The synthesis of25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene3 as a byproduct of the preparation of 1,3-dialkylated25,27-di-[2-(ethoxy-1p-toluene-sulfonate)phenyl]-26,28-dihydroxy calix[4]arene 2 is reported. Compound 3 is a monoalkylatedcalix[4]arene in the cone conformation. The X-ray structure of 3 showed that this conformation is stabilized by intramolecular hydrogen bonding.     

Controlled solvothermal synthesis of PbS quasi-nanorods by calix[4]arene

A new idea of the nanorods preparation and a novel application of calixarenes are presented. Calix[4]arene was introduced into solvothermal system to produce one-dimensional inorganic nanomaterial. The obtained product was characterized by XRD and TEM. Results of the XRD analysis showed that the product was pure cubic phase of PbS with high crystallinity. TEM images revealed that the diameter and length of the PbS nanorods were about 200 nm and up to 3.5 μm, respectively. Optical properties of the product were also studied. PL emission image showed that the product exhibited an emission peak at 308 nm in ultraviolet region showing a blue shift of 14 nm compared to the bulk material. The formation mechanism of PbS nanorods in the presence of calix[4]arene is discussed.