1-(4-磺酸基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯与季铵盐型阳离子表面活性剂的显色反应及应用

合成了１－（４－磺酸基苯基）－３－［４－（苯基偶氮）苯基］－三氮烯（ＳＰＡＰＴ）,研究了该试剂在强碱性介质中与季铵盐型阳离子表面活性剂溴化十六烷基吡啶（ＣＰＢ）和溴化十六烷基三甲铵（ＣＴＭＡＢ）的显色反应体系,试剂与表面活性剂形成１∶３的紫红色离子缔合物,其表观摩尔吸光系数分别为１．６７×１０４和１．０６×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。测定了显色体系中ＣＰＢ和ＣＴＭＡＢ的临界胶束浓度（ＣＭＣ）,证明在比尔定律范围内,ＣＰＢ和ＣＴＭＡＢ均以单分子缔合显色。确定了显色体系最佳实验条件     

1-(2-苯并噻唑)-3-(4-偶氮苯基)-三氮烯与汞的显色反应研究及应用

研究了新试剂１－（２－苯并噻唑）－３－（４－偶氮苯基）－三氮烯（ＢＴＰＡＰＴ）与汞的显色反应．在Ｔｗｅｎ－８０存在下，ｐＨ为１１．２０时，Ｈｇ（Ⅱ）与试剂生成红色的１∶１型配合物，最大吸收峰位于５１０ｎｍ，表观摩尔吸光系数为１．１０×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，线性范围０－１４μｇ／２５ｍＬ．建立了可用于饮用水、生活用水和工业废水汞含量测定的方法．     

用Cadion-CPB光度法测定水中痕量阴离子表面活性剂

研究了用于直接测定水相中痕量阴离子表面活性剂的新体系。在ＮａＯＨ介质中,１－（４－硝基苯基）－３－［４－（苯基偶氮）苯基］－三氮烯（Ｃａｄｉｏｎ）与溴化十六烷基吡啶（ＣＰＢ）形成离子缔合物（Ｃａｄｉｏｎ－ＣＰＢ）,当加入阴离子表面活性剂（ＡＳ）时,ＡＳ能定量置换出离子缔合物中的Ｃａｄｉｏｎ,而使吸光度下降。阴离子表面活性剂十二烷基苯磺酸钠（ＤＢＯＳＯ３Ｎａ）、十二烷基磺酸钠（ＤＯＳＯ３Ｎａ）、十二烷基硫酸钠（ＤＳＯ４Ｎａ）的表观摩尔吸光系数εｍａｘ分别为２．７４×１０４、１．１１×１０４、１．５０×１０４Ｌ·ｍｏｌ－１·ｃｍ－１,服从比尔定律的范围分别为０～４．１８、０～６．５４、０～５．７７ｍｇ·Ｌ－１。方法操作简便,用于测定合成水样及环境水样中痕量阴离子表面活性剂,结果满意。     

新试剂1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯与锌的显色反应研究及应用

研究了新显色剂１－（６－硝基－２－苯并噻唑）－３－（４－硝基苯）－三氮烯（ＮＢＴＮＰＴ）与锌的显色反应，在非离子表面活性剂ＴｒｉｔｏｎＸ－１００存在下，ｐＨ１０．１～１０．８的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ缓冲溶液中，Ｚｎ２＋与试剂能形成１∶２的橙黄色配合物，最大吸收波长为４４６ｎｍ，同时在５２８ｎｍ处配合物表现有最大负吸收，其表观摩尔吸光系数分别为ε＝７．０３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１和ε＝１．０６×１０５Ｌ·ｍｏｌ－１·ｃｍ－１．用拟定的方法测定了人发和婴儿奶粉中的微量锌，结果令人满意．     

新试剂二溴对硝基苯基重氮氨基-4-苯基-2-噻唑的合成及其与钯显色反应的研究

报道了新试剂二溴对硝基苯基重氮氨基－４－苯基－２－噻唑的合成方法，并研究了在表面活性剂ＣＰＣ存在下，该试剂与钯（Ⅱ）的显色反应。结果表明，在ｐＨ６．４～７．８范围内，钯（Ⅱ）与该试剂可形成１∶２灰紫色的配合物，其最大吸收波长位于６５０ｎｍ，表观摩尔吸光系数为７．０２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，钯量在０～２２μｇ／２５ｍＬ范围内符合比尔定律，该方法已用于Ｐｄ－Ｃ催化剂中微量钯的测定，结果满意。     

新试剂N-间甲苯基-N′-(氨基对苯磺酸钠)硫脲(MMPT)的合成及其在分析化学中的应用

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ），经红外、紫外、核磁、元素分析等测试，确定其结构。研究测定了试剂与４０多种离子的反应及其配合物的表观摩尔吸光系数，它可作为Ｃｕ２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ）、Ａｇ＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ２＋（ε３０９．７＝６．３２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）、Ｐｔ（Ⅳ）（ε７５４．４＝８．５８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）等的显色剂，方法灵敏度高、选择性好，用于阳极泥、人发、矿石及催化剂中上述元素的鉴定或测定，均获满意结果。     

新显色剂1-(2.4-二硝基苯)-3-(2-噻唑)-三氮烯的合成及与汞的显色反应研究

报道了新显色剂１－（２．４－二硝基苯）－３－（２－噻唑）－三氮烯的合成及其与Ｈｇ（Ⅱ）的显色反应。实验表明，在非离子表面活性剂ＴｒｉｔｏｎＸ－１００存在下，于ｐＨ１１．７５的三酸缓冲介质中，试剂与Ｈｇ（Ⅱ）能生成蓝绿色配合物，最大吸收波长位于６９０ｎｍ处，试剂的最大吸收波长位于４１０ｎｍ处，对比度高达２８０ｎｍ，其配合比为１∶２，表观摩尔吸光系数为１．１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，Ｈｇ（Ⅱ）含量在０～１８μｇ／２５ｍＬ范围内符合比耳定律。测定了废水中汞的含量，结果令人满意。     

2-羟基-3-羧基-5-磺酸基苯基重氮氨基偶氮苯与铊反应的分光光度法研究

于ｐＨ１０．０～１１．０的ＮＨ３－ＮＨ４Ｃｌ缓冲介质中，在ＴｒｉｔｏｎＸ－１００存在下，铊（Ⅲ）与２－羟基－３－羧基－５－磺酸基苯基重氮氨基偶氮苯（ＨＣＳ－ＤＡＡ）形成组成比为１∶３的红色配合物，其最大吸收波长和对比度分别为５１０ｎｍ和８０ｎｍ，表观摩尔吸光系数为１．５２×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，线性范围为０～０．７０ｍｇ／Ｌ，室温下显色反应立即完成，配合物至少稳定２ｈ。方法用于水样、烟叶和煤灰中痕量铊的分析，回收率为９０．０％～１０１．４％，５次测定的相对标准偏差不大于４．６％。     

5，10，15，20－四（3－溴－4－磺酸苯基）卟啉光度法测定痕量铜的研究

本文研究了新水溶性卟啉试剂５，１０，１５，２０－四（３－溴－４－磺酸苯基）卟啉［Ｔ（３－ＢｒＰ）ＰＳ＿４与铜的显色反应。在ｐＨ３，铜与５，１０，１５，２０－四（３－溴－４－磺酸苯基）卟啉形成１：１的稳定配合物。此配合物的最大吸收波长位于４１２．８ｎｍ，摩尔吸光系数为２．６１×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。铜量在０～３．０μｇ／２５ｍＬ范围内符合比尔定律，工作曲线回归方程为ｙ＝０．００９４３、＋０．１６７ｘ，相关系数为ｒ＝０．９９９７。方法有较高的灵敏度和较好的选择性，直接用于大米和茶叶中痕量铜的测定，结果与ＡＡＳ法一致。     

钼(Ⅵ)-4-(5-溴-2-噻唑偶氮)邻苯二酚-二苯胍三元离子缔合物的萃取分光光度研究

在ｐＨ４．０的介质中，Ｍｏ（Ⅵ）与新试剂４－（５－溴－２－噻唑偶氮）邻苯二酚（５－Ｂｒ－ＴＡＰＣ）和二苯胍（ＤＰＧ）反应形成稳定的三元离子缔合物，其组成比Ｍｏ（Ⅵ）：５－Ｂｒ－ＴＡＰＣ∶ＤＰＧ为１∶３∶２。该三元缔合物氯仿萃取液的λｍａｘ为５３６ｎｍ，对比度为１１９ｎｍ，表观ε为６．３３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。钼（Ⅵ）含量在０～０．８０ｍｇ／Ｌ范围内遵从比耳定律，并探讨了离子缔合物的结构。将在最佳显色条件下拟定的分析方法用于合金钢中小量或痕量钼的测定，取得了满意的结果。     

盐酸氯丙嗪作探针二级散射和倍频散射法测定环境水样中某些阴离子表面活性剂

在pH3.0~5.0的HAc-NaAc缓冲溶液中,盐酸氯丙嗪与十二烷基苯磺酸钠、十二烷基磺酸钠和十二烷基硫酸钠等阴离子表面活性剂反应形成离子缔合物时,仅能引起吸收光谱和荧光光谱的微小变化,但却能导致二级散射(SOS)和倍频散射(FDS)的显著增强。最大SOS峰均在552nm附近,最大FDS峰均在390nm附近。其中SOS法灵敏度更高,它对十二烷基苯磺酸钠、十二烷基硫酸钠和十二烷基磺酸钠的检出限分别为0.047、0.106和0.117mg/L,而其线性范围分别为0.2~12、0.4~15和0.4~20.0mg/L。研究了反应产物的吸收、荧光、SOS和FDS光谱特征、适宜的反应条件及分析化学性质,据此发展了一种用SOS技术灵敏、简便、快速测定阴离子表面活性剂的环境友好型新方法。     

溴酚蓝-氯化十六烷基吡啶光度法测定水中痕量阴离子表面活性剂

本文研究了溴酚蓝(BPB)与氯化十六烷基吡啶(CPC),阴离子表面活性剂(AS)与CPC形成缔合物的反应.发现在pH=8.0的NH_3·H_2O-NH_4Cl缓冲溶液中,AS能定量置换出CPC-BPB缔合物中的BPB而显色,其最大吸收在590nm处.阴离子表面活性剂十二烷基本磺酸钠(DBSNa)和十二烷基磺酸钠(DSNa)的ε值分别为2.9 ×10_4和3.2×10~4L·mol~(-1)·cm~(-1).在80μg CPC存在下,DBSNa和DSNa浓度分别在0～80μg/25 ml和0～60μg/25ml范围内符合比耳定律.应用此法测定环境水样中的痕量阴离子表面活性剂,结果满意.     

Sensitive determination of anionic surfactants in water with trans-4-[4'-(N-methyl-N-hydroxylethylamino)-cinnamyl-N-9-(4'-(2,2':6',2''-terpyridine))-phenylmethylene]pyridine bromide by the light-absorption ratio variation approach

The light-absorption ratio variation approach was described and applied to the determination of anionic surfactants (AS) in water with a novel chromophore, trans 4-[4'-(N-methyl-N-hydroxylethylamino)-cinnamyl-N-9-(4'-(2,2':6',2'-terpyridine))-phenylmethylene]pyridine bromide (BTMHCTPP). The complexations between BTMHCTPP and sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS) at pH 3.85 were characterized by the break point approach. Results have shown that both 1BTMHCTPP:1SDS and 1BTMHCTPP:1SDBS complexes were formed, and that deltaA(r) (deltaA(r) = light-absorption ratio variation) is linear for the range of AS between 0.05 and 1.00 mg/L. The limits of detection (3sigma) are 0.045 mg/L for SDS and 0.040 mg/L for SDBS. The complexation is selective in the presence of EDTA, and it has been applied to the analysis of water samples with satisfactory results.     

Flow injection spectrophotometric determination of anionic surfactants using methyl orange as chromogenic reagent

A flow injection(FI) spectrophotometric method for the determination of anionic surfactants was developed on the basis of the competition for the cationic surfactant cetyl pyridine (CP+) chloride between the acidic dye methyl orange (MO) and anionic surfactants. In a pH 5.0 medium the cation of cetyl pyridine (CP+) reacts with dissociated methyl orange (MO-) to form an ion-associate complex, causing a blue shift of lambda(max) from 465 nm for MO- to 358 nm for the CP+ x MO- associate. The MO- in the ion-associate complex can be quantitatively substituted by such anionic surfactants as sodium dodecyl benzene sulfonate (DBS) or sodium lauryl sulfate (LS), leading to an increase in the absorbance measured at 465 nm. This increased absorbance value is proportional to the concentration of anionic surfactants. Various chemical and physical parameters for the FI spectrophotometric method were optimized, and interference-free levels were examined. At the optimized conditions, Beer's law was obeyed in the range 1.4 approximately 25 mg/L sodium DBS for an injected sample volume of 180 microL, and a detection limit of 0.22 mg/L for sodium DBS was achieved at a sampling rate of 90 h(-1). Eleven determinations of a 16 mg/L sodium DBS solution gave a RSD of 0.4%. The proposed method has successfully been applied to the determination of anionic surfactant concentration in waste water and in detergents.     

1-偶氮苯-3-(5-氰-2-吡啶)-三氮烯的合成及其与锌的显色反应

报道了新显色剂1-偶氮苯-3-(5-氰-2-吡啶)-三氮烯的合成。在pH 10~12的硼砂-氢氧化钠缓冲溶液中,NP-40表面活性剂存在下,该试剂与锌发生显色反应,生成3∶1的红色配合物。配合物的最大吸收峰位于530 nm,表观摩尔吸光系数为1.52×105L.mol-1.cm-1。Zn2+质量浓度在0~0.48 mg/L范围内遵守比尔定律。用该法测定人发中微量锌,结果令人满意。     

Interfacial molecular array behaviors of mixed surfactant systems based on sodium laurylglutamate and the effect on the foam properties

The foam properties of mixtures of an eco-friendly amino-acid derived surfactant sodium lauroylglutamate (LGS) interacting with cationic surfactant dodecyl trimethyl ammonium bromide (DTAB), nonionic surfactant laurel alkanolamide (LAA) and anionic surfactant sodium dodecyl sulfonate (SDS), were investigated, respectively. It was amazing that the three investigated binary-mixed systems all showed obviously synergism effect on foaming, though LGS/DTAB catanionic mixture showed remarkable synergistic effect with no surprise. The equilibrium and dynamic surface activity, along with the interfacial molecular array behaviors of binary-mixed systems with different molar ratios at air/water surface were also studied. Moreover, the theoretical simulation was employed to investigate how the interfacial behaviors of surfactants at air/water surface affected the foam properties. The study might provide the meaningful guidance for utilizing the LGS-based systems, especially in constructing eco-friendly foam systems in the application areas of cosmetics, medicine and detergent.     

Spectrophotometric determination of silver with 2-(2-quinolylazo)-5-diethylaminophenol as chromogenic reagent

A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminophenol (QADEAP) was synthesized. A highly sensitive, selective and rapid method for the determination of silver based on the rapid reaction of silver(I) with QADEAP has been developed. In the presence of citric acid-sodium hydroxide buffer solution (pH=5.0) and sodium dodecyl sulfonate (SDS) medium, QADEAP reacts with silver to form a violet complex of a molar ratio 1:2 (silver to QADEAP). The molar absorptivity of the complex is 1.33x10(5) L mol(-1) cm(-1)at 590 nm. Beer' s law is obeyed in the range of 0.01-0.6 micro g mL(-1). The relative standard deviations for eleven replicate samples of 0.2 microg mL(-1) is 1.38%. This method was applied to the determination of silver in water with satisfactory results.     

Study on the Color Reaction of Silver with 2‐(2‐Quinolylazo)‐5‐Dimethylaminoaniline and its Application

A new chromogenic reagent, 2‐(2‐quinolylazo)‐5‐dimethylaminoaniline (QADMAA) was synthesized. A highly sensitive, selective and rapid method for the determination of silver based on the rapid reaction of silver(I) with QADMAA was developed. In the presence of pH = 6.5 sodium citrate‐sodium hydroxide buffer solution and sodium dodecyl sulfonate (SDS) medium, QADMAA reacts with silver to form a violet complex of a molar ratio 1:2 (silver to QADMAA). The molar absorptivity of the complex is 1.26 × 10⁵ L. mol^?1.cm^?1 at 570 nm. Beer's law is obeyed in the range of 0.01–0.6 μg/mL. The relative standard deviation for eleven replicate samples of 0.2 μg/mL silver is 1.76%. This method was applied to the determination of silver in water with good results.     

Resonance Rayleigh scattering spectra of ion-association nanoparticles of [Co(4-[(5-Chloro-2-pyridyl) azo]-1, 3-diaminobenzene)2]-sodium dodecyl benzene sulfonate system and its analytical application

In pH 1.8-3.0 Britton-Robinson (BR) buffer solution, cobalt (II) reacts with 4-[(5-Chloro-2-pyridyl) azo]-1, 3-diaminobenzene (5-Cl-PADAB, L) to form a cationic chelate [CoL₂]²⁺. When interacting with anionic surfactants (AS) such as sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfate (SDS) or sodium dodecyl sulfonate (SLS), the chelate can only react with SDBS to form ternary ion-association complexes ([CoL₂][SDBS]₂). By virtue of the extrusion action of water and Van der Waals force, the hydrophobic ion-association complexes draw close to each other and further aggregate to form {[CoL₂][SDBS]₂}_n nanoparticles with an average diameter of 30 nm. As a result, resonance Rayleigh scattering (RRS) is enhanced greatly and new RRS spectra appear. Under the same conditions, both SDS and SLS exhibit no similar reactions and do not result in obvious change of RRS. Therefore, SDBS can be determined selectively by RRS method in the presence of SDS or SLS. The wavelength of 516 nm was chosen as a detection wavelength, the linear range and the detection limit (3σ) are 0.05-6.0 μg mL⁻¹ and 0.015 μg mL⁻¹ for the determination of SDBS, respectively. The characteristics of RRS spectra of the [CoL₂]²⁺-SDBS system, the optimum conditions of the reaction and the influencing factors have been investigated. The effects of coexisting substances have been examined too, indicating a good selectivity of the method for the determination of SDBS. The method can be used for the determination of SDBS in waste water and river water samples, and the results are satisfactory compared with those of standard samples of SDBS. Based on the formation of {[CoL₂][SDBS]₂}_n nanoparticles, a sensitive, simple and rapid method has been developed for the determination of SDBS in environmental water samples using a RRS technique. Moreover, the reaction mechanism was discussed.     

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.