双缓血氨二乙三胺五乙酸酰胺钆,镱螯合物的合成及其弛豫性能

缓血氨（Ｔｒｉｓ，三羟甲基氨基甲烷）修饰多氨多羧酸（二乙三胺五乙酸，ＤＴＰＡ和乙二胺四乙酸，ＥＤＴＡ）得到两种新的双酰胺型氨羧衍生物配体ＤＴＰＡВＴｒｉｓ和ＥＤＴＡＢＴｒｉｓ，并合成了它们的Ｇｄ３＋，Ｙｂ３＋，Ｍｎ２＋，Ｆｅ３＋等顺磁性金属螯合物，研究了Ｇｄ３＋，Ｍｎ２＋和Ｆｅ３＋螯合物作为磁共振成像造影剂的主要性能。结果表明，ＧｄＤＴＰＡＢＴｒｉｓ，ＭｎＥＤＴＡＢＴｒｉｓ和ＦｅＥＤＴＡＢＴｒｉｓ在体外水溶液中对水质子的纵向弛豫率Ｒ１分别为５４，３．１和１．９Ｌ·ｍｍｏｌ－１·ｓ－１，均高于其相应母体螯合物在相同条件下的弛豫率。此外，这些螯合物还具有医用磁共振成像造影剂所要求的高水溶性和化学稳定性。     

CORRELATION BETWEEN THE CATALYTC PROPERTY AND Zr~（3＋） ION FOR ZrO_2 IN CO HYDROGENATION

ＣＯＲＲＥＬＡＴＩＯＮＢＥＴＷＥＥＮＴＨＥＣＡＴＡＬＹＴＣＰＲＯＰＥＲＴＹＡＮＤＺｒ~（３＋）ＩＯＮＦＯＲＺｒＯ_２ＩＮＣＯＨＹＤＲＯＧＥＮＡＴＩＯＮ￥ＷｅｎＬＩ；ＬｉａｎｇＢｏＦＥＮＧ；ＹｕａｎＱｉＹＩＮ（ＬａｎｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍ...     

TOLUENE HYDROXYLATION WITH H_2O_2 CATALYZED BY TITANIUM SILICALITE(TS-1)

ＴＯＬＵＥＮＥＨＹＤＲＯＸＹＬＡＴＩＯＮＷＩＴＨＨ２Ｏ２ＣＡＴＡＬＹＺＥＤＢＹＴＩＴＡＮＩＵＭＳＩＬＩＣＡＬＩＴＥ（ＴＳ１）ＹａｎｇＷｕｂｉｎ，ＬｉｕＸｉｙａｏ（ＲｅｓｅａｒｃｈＩｎｓｔｉｔｕｔｅｏｆＹａｎｓｈａｎＰｅｔｒｏｃｈｅｍｉｃａｌＣｏｒ...     

锆—7—碘—8—羟基喹啉—5—磺酸—EDTA—表面活性剂体系的荧光光度法研究

在ｐＨ６．２的ＨＡｃ－ＮａＡｃ缓冲溶液中，在溴化十六烷基三甲基胺（ＣＴＭＡＢ）存在下，Ｚｒ（Ⅳ）与７－碘－８－羟基喹啉－５－磺酸（Ｈ２ＱＳＩ）及ＥＤＴＡ形成了四元荧光配合物，其组成为：Ｚｒ：Ｈ２ＱＳＩ：ＥＤＴＡ：ＣＴＭＡＢ＝１：１：１：３。据此建立了锆的选择性好，灵敏度高的荧光测定方法，方法检测限为１．２ｎｇ／ｍＬ。锆的线性范围为１．６ｎｇ～１．０μｇ／ｍＬ。用于铜合金中微量锆的测定，结果令人满意     

二溴苯羟基荧光酮荧光光度法测定微量锆

本文提出了一个锆－二溴苯羟基荧光酮（ＤＢＨＰＦ）－乳化剂ＯＰ荧光光度法测定微量锆的新体系，在０．５～１．２ｍｏｌ／Ｌ的ＨＣｌ介质中，锆与ＤＢＨＰＦ生成组化比为１：４的红色荧光性络合物，荧光强度与锆（Ⅳ）的浓度在０～１００μｇ／Ｌ呈线性关系，检出限为２．０μｇ／Ｌ。灵敏度高，高选择性好，用于瓷釉等样品中ＺｒＯ２的测定，获得满意的结果。     

CATALYTIC BEHAVIOR OF HYDROTALCITE-LIKE COMPOUND IN NITROGEN MONOXIDE REDUCTION BY CO

ＣＡＴＡＬＹＴＩＣＢＥＨＡＶＩＯＲＯＦＨＹＤＲＯＴＡＬＣＩＴＥＬＩＫＥＣＯＭＰＯＵＮＤＩＮＮＩＴＲＯＧＥＮＭＯＮＯＸＩＤＥＲＥＤＵＣＴＩＯＮＢＹＣＯＷａｎｇＸｕｅｚｈｏｎｇ１，ＬｉｕＹｕｍｉｎ２，ＷｕＹｕｅ１（１ＣｈａｎｇｃｈｕｎＩｎｓｔｉｔｕｔ...     

锆—氟—7—碘—8—羟基喹—5—磺酸—EDTA—表面活性剂体系的荧光光度研究

在ＰＨ５．５－７．０的ＨＡｃ－ＮａＡｃ缓冲溶液中，锆与氟、７－碘－８－羟基喹啉－５磺酸、ＥＤＴＡ及十六烷基溴化铵形成五元荧光络合物，其组成为Ｚｒ（Ⅳ）：Ｆ：Ｈ２ＱＳＩ：ＥＤＴＡ：ＣＴＭＡＢ＝１：２：１：１：４。络合物的最大激发波长（λｅｘ）为３６５ｎｍ，最大发射波长为５００ｎｍ。     

锆－7－碘－8－羟基喹啉－5－磺酸－EDTA－表面活性剂体系的荧光光度法研究

在ｐＨ６．２的ＨＡｃ－ＮａＡｃ缓冲溶液中，有溴化十六烷基三甲基铵（ＣＴＭＡ８）存在下，Ｚｒ（Ⅳ）与７－碘－８－羟基喹啉－５－磺酸（Ｈ＿２ＱＳＩ）及ＥＤＴＡ形成了四元荧光配合物。其组成为：Ｚｒ：Ｈ＿ＱＳＩ：ＥＤＴＡ：ＣＴＭＡＢ＝１：１：１：３。据此建立了错的选择性好、灵敏度高的荧光测定方法。方法检测限为１．２ｎｇ／ｍＬ。锆的线性范围为１．６ｎｇ～１．０μｇ／ｍＬ。用于铜合金中微量锆的测定，结果令人满意。     

ESR STUDY OF ZrO_2 CATALYST

ＥＳＲＳＴＵＤＹＯＦＺｒＯ＿２ＣＡＴＡＬＹＳＴ￥ＷｅｎＬＩ；ＬｉａｎｇＢｏＦＥＮＧ；ＹｕａｎＱｉＹＩＮ（ＬａｎｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅｓ，Ｌａｎｚｈｏｕ７３００００）...     

CO_2 HYDROGENATION OVER SiO_2－SUPPORTED HETEROBINUCLEAR METAL COMPLEX CATALYSTS

ＣＯ_２　ＨＹＤＲＯＧＥＮＡＴＩＯＮ　ＯＶＥＲ　ＳｉＯ_２－ＳＵＰＰＯＲＴＥＤ　ＨＥＴＥＲＯＢＩＮＵＣＬＥＡＲ　ＭＥＴＡＬ　ＣＯＭＰＬＥＸ　ＣＡＴＡＬＹＳＴＳＣｈａｎｇＰｉｎｇＳＨＡＯ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，...     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.