IO3--I--丁基罗丹明B体系测定面粉中痕量溴酸根

在磷酸介质中,BrO3-氧化I-形成I3-络阴离子,I3-络阴离子可进一步与丁基罗丹明B阳离子形成离子缔合物,在聚乙烯醇存在下,缔合物呈清亮的紫色溶液,以试剂空白为参比,最大吸收波长位于587nm,吸光度A与BrO3-浓度呈线性关系。线性范围0.20～3.50μg/10mL,表观摩尔吸光系数为9.79×104L·mol-1.cm-1,检出限为0.012μg·mL-1,样品回收率94.0%～100.3%,RSD为2.81%。该方法用于面粉中痕量溴酸根测定,结果令人满意。     

AR-Ag(I)体系的共振散射光谱法测定痕量银

在pH=4.4的NaAc-HAc缓冲介质和2.0×10-3mol/L十二烷基苯磺酸钠(SDBS)溶液中,Ag(I)与茜素红(AR)可形成较稳定的离子缔合物微粒,其在324、360和500nm处分别产生3个较强的共振散射峰。在最佳实验条件下,浓度在0.022～2.160μg/mL之间的Ag(I)与共振散射强度ΔI324nm呈较好的线性关系,检测限为0.139ng/mL。据此,建立了一种测定痕量银的共振散射新方法,并将该方法用于废胶片中痕量银的测定。     

Fe(Ⅲ)-磺基水杨酸体系共振散射法测定肝素钠

在pH=4.5的B-R缓冲溶液中,Fe(Ⅲ)与5-磺基水杨酸配位生成紫红色配合物,使得体系在257nm和342nm处产生2个共振散射峰。在该体系中加入肝素钠后,在静电引力作用下其与配合物结合形成离子缔合物,从而使得体系在257nm和342nm处的共振散射信号减弱。在优化实验条件下,在0.05~15.0μg/mL质量浓度范围内,体系的共振散射信号△I与肝素钠的浓度之间有较好的线性关系(相关系数r=0.9976),其检出限为39.9ng/mL。该方法可直接用于测定肝素钠注射液中肝素钠的含量,回收率为98.9%~102.2%。     

Bi(Ⅲ)-茜素红-CTMAB体系共振散射光谱法测定环境水样中痕量铋

在pH=4.1的HCl溶液中,Bi(Ⅲ)与茜素红和十六烷基三甲基溴化铵（CTMAB）缔合形成粒径较大的疏水性三元离子缔合物（结合比为n(Bi(Ⅲ))∶n(AR)∶n(CTMAB)=1∶3∶3）,该反应导致共振光散射显著增强,最大散射峰位于364 nm。 研究了反应介质、pH值、共振探针浓度等对散射体系的影响,考察了该散射反应的稳定性及共存物质的影响,并对该三元离子缔合物的反应机理进行了探讨。 在2.5 mL 1.0×10-4 mol/L茜素红和2.0 mL 1.0×10-4 mol/L CTMAB最优试验条件下,Bi(Ⅲ)质量浓度与共振光散射强度ΔI364 nm在0～0.384 mg/L范围内呈良好线性关系,检测限为5.898×10-8 g/L,对含量为0.18 mg/L Bi(Ⅲ)溶液进行11次平行测定,其相对标准偏差为2.2%。 将该方法用于环境水样中痕量铋(质量浓度为0.552～0.831 μg/L)的测定,加标回收率为99.5%～100.2%,测定偏差小于2.7%。 基于Bi(Ⅲ)-AR-CTMAB三元离子缔合物的共振光散射光谱,建立了以茜素红染料为光谱探针的痕量Bi(Ⅲ)共振光散射检测新方法。     

硒(Ⅳ)-硫氰酸钾-甲基紫萃取光度法测定痕量硒

研究了硒(Ⅳ)与硫氰酸钾和甲基紫(MV)的显色反应,发现在pH=1.85的HCl介质中,[Se(SCN)_6)~(2-)与MV形成不溶解于水的三元离子缔合物,该缔合物可溶解于苯等有机溶剂,在苯溶液中,该缔合物的最大吸收峰位于600nm处,其摩尔吸光系数为1.18×10~5L/(mol·cm),硒(Ⅳ)浓度在0.0～6.0μg/25mL范围内符合比耳定律。该方法应用于合成水样和环境水样中硒的测定,结果准确、可靠。     

Zn~(2+)-邻菲啰啉-亮黄缔合体系双波长光度法测定锌

在pH5.7的NaAc-HAc缓冲溶液中,Zn2+与邻菲啰啉(phen)和亮黄(BY)反应生成稳定的离子缔合物[Zn(phen)3]BY,使BY褪色,492 nm处出现正吸收峰,379 nm处出现负吸收峰。选定测量波长为492 nm,参比波长为379 nm,建立了双波长光度法测定微量锌的新方法。表观摩尔吸光系数为3.01×104L.mol-1.cm-1,线性范围为0~1.5μg/mL,检出限为18.5μg/L。方法用于测定锌强化营养盐和健康平衡盐中锌,相对标准偏差为0.69%~0.87%(n=5),回收率为98.4%~99.3%。     

AR-Ag(Ⅰ)体系的共振散射光谱法测定痕量银

在pH=4.4的NaAc-HAc缓冲介质和2.0×10-3mol/L十二烷基苯磺酸钠(SDBS)溶液中,Ag(Ⅰ)与茜素红(AR)可形成较稳定的离子缔合物微粒,其在324、360和500nm处分别产生3个较强的共振散射峰.在最佳实验条件下,浓度在0.022～2.160μg/mL之间的Ag(Ⅰ)与共振散射强度△I324nm呈较好的线性关系,检测限为0.139 ng/mL.据此,建立了一种测定痕量银的共振散射新方法,并将该方法用于废胶片中痕量银的测定.     

Bi(Ⅲ)-茜素红-十六烷基三甲基溴化铵体系共振散射光谱法测定环境水样中痕量铋

在pH=4.1的HCl溶液中,Bi(Ⅲ)与茜素红和十六烷基三甲基溴化铵(CTMAB)缔合形成粒径较大的疏水性三元离子缔合物(结合比为n(Bi(Ⅲ))∶n(AR)∶n(CTMAB)=1∶3∶3),该反应导致共振光散射显著增强,最大散射峰位于364nm。研究了反应介质、pH值、共振探针浓度等对散射体系的影响,考察了该散射反应的稳定性及共存物质的影响,并对该三元离子缔合物的反应机理进行了探讨。在2.5mL1.0×10-4mol/L茜素红和2.0mL1.0×10-4mol/LCTMAB最优试验条件下,Bi(Ⅲ)质量浓度与共振光散射强度ΔI364nm在0～0.384mg/L范围内呈良好线性关系,检测限为5.898×10-8g/L,对含量为0.18mg/LBi(Ⅲ)溶液进行11次平行测定,其相对标准偏差为2.2%。将该方法用于环境水样中痕量铋(质量浓度为0.552～0.831μg/L)的测定,加标回收率为99.5%～100.2%,测定偏差小于2.7%。基于Bi(Ⅲ)-AR-CTMAB三元离子缔合物的共振光散射光谱,建立了以茜素红染料为光谱探针的痕量Bi(Ⅲ)共振光散射检测新方法。     

锌(Ⅱ)-硫氰酸盐-中性红体系共振瑞利散射法测定痕量锌

在pH 5.1的HAc-NaAc缓冲溶液中,聚乙烯醇存在下,Zn(Ⅱ)和硫氰酸盐形成的配阴离子[Zn(SCN)4]2-与中性红阳离子结合形成的离子缔合物具有共振瑞利散射光谱,其最强共振瑞利散射峰位于594.5 nm处。基于共振瑞利散射峰的增强,建立了测定痕量Zn(Ⅱ)的共振瑞利散射方法。Zn2+质量浓度在0~0.5μg/mL范围内呈良好的线性关系,检出限为1.9×10-5μg/mL。方法已用于水样中Zn2+的测定。     

四溴汞(Ⅱ)酸钾-异辛基苯二聚乙二醇醚二甲基苄基氯化铵的共振散射光谱及其分析应用

在pH2～8的溶液中,四溴汞（Ⅱ）酸钾和异辛基苯二聚乙二醇醚二甲基苄基氯化铵（BTC）反应生成离子缔合物,在390nm处有一共振散射峰,峰强度随汞（Ⅱ）质量浓度的增加而增大,据此建立了测定痕量汞的新方法。在实验条件下,此法测定汞（Ⅱ）的线性范围是14～240μg/L,检出限为μg/L,已用于合成水样和环境水样中汞（Ⅱ）的测定。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.