钴硫氰酸根离子缔合—萃取光度法测定盐酸布比卡因

本文提出了在Ｎ，Ｎ－二甲基酰胺（ＤＭＦ）存在下，用萃取光度法研究了盐酸布比卡因与钴硫氰酸根络阴离子生成的离子缔合物的实验条件及反应机理，并用于实际样品的测定，获得了良好的效果。实验结果表明，由于ＤＦＭ对二氯甲烷的协同作用，使反应体系较之单一溶萃取更稳定、更灵敏。     

气相法苯胺N-烷基化反应研究Ⅲ.苯胺和甲醇催化合成N,N-二甲基苯胺研究

本文报导了在系列复合氧化物催化剂上苯胺和甲醇反应合成Ｎ，Ｎ－二甲苯胺（ＤＭＡ）研究，并从中选择了活性和选择性都良好的ＬＨＰ催化剂，在常压气相反应条件下详细地考察了反应温度，液时空速（ＬＨＳＶ），苯胺和甲醇摩尔比变化等对催化剂活性和选择性的影响，提出了两段转化的新工艺流程。并经扩大试验，证明两段转化工艺过程优于一段转化法。第一段反应时苯胺转化率大于９５％，ＤＭＡ选择性大于７０％，第二段转化后，产物中几乎不含苯胺，ＤＭＡ选择性大于９４％，并在工业固定床催化反应装置中常压气相反应条件下试生产成功。     

DECOMPOSITION OF KNO_3/γ-Al_2O_3 AND THE FORMATION OF SURFACE BASE SITES

ＤＥＣＯＭＰＯＳＩＴＩＯＮＯＦＫＮＯ３／γ┐Ａｌ２Ｏ３ＡＮＤＴＨＥＦＯＲＭＡＴＩＯＮＯＦＳＵＲＦＡＣＥＢＡＳＥＳＩＴＥＳ＊ＴｕＭａｉ，ＬｉＤａｔａｎｇ，ＺｈｕＪｉａｎｈｕａ，ＳｈｅｎＪｉａｎｙｉ＊＊（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｉｎｓ...     

铂对硫芴加氢脱硫钼催化剂的促进作用

铂对硫芴加氢脱硫钼催化剂的促进作用王军李文钊张盈珍ＴＨＥＰＲＯＭＯＴＩＯＮＥＦＦＥＣＴＯＦＰＬＡＴＩＮＵＭＯＮＭＯＬＹＢＤＥＮＵＭＣＡＴＡＬＹＳＴＦＯＲＨＹＤＲＯＤＥＳＵＬＦＵＲＩＺＡＴＩＯＮＯＦＤＩＢＥＮＺＯＴＨＩＯＰＨＥＮＥＷａｎｇＪｕｎ，ＬｉＷ...     

PARAMAGNETIC AND DIAMAGNETIC DICOPPER（Ⅱ） COMPLEXES WITH DI－SCHIFF BASE DERIVED FROM 2－HYDROXY－1－NAPHTHALDEHYDE AND1，3－DIANINO－2－PROPANOL

ＰＡＲＡＭＡＧＮＥＴＩＣＡＮＤＤＩＡＭＡＧＮＥＴＩＣＤＩＣＯＰＰＥＲ（Ⅱ）ＣＯＭＰＬＥＸＥＳＷＩＴＨＤＩ－ＳＣＨＩＦＦＢＡＳＥＤＥＲＩＶＥＤＦＲＯＭ２－ＨＹＤＲＯＸＹ－１－ＮＡＰＨＴＨＡＬＤＥＨＹＤＥＡＮＤ１，３－ＤＩＡＮＩＮＯ－２－ＰＲＯＰＡＮＯＬ...     

SWINANINE C＆D，TWO NEW DITERPENE ALKALOIDS FROM DELPHINIUM SWINANENSE VAR LEPTOPOGON

ＳＷＩＮＡＮＩＮＥＣ＆Ｄ，ＴＷＯＮＥＷＤＩＴＥＲＰＥＮＥＡＬＫＡＬＯＩＤＳＦＲＯＭＤＥＬＰＨＩＮＩＵＭＳＷＩＮＡＮＥＮＳＥＶＡＲＬＥＰＴＯＰＯＧＯＮＳＷＩＮＡＮＩＮＥＣ＆Ｄ，ＴＷＯＮＥＷＤＩＴＥＲＰＥＮＥＡＬＫＡＬＯＩＤＳＦＲＯＭＤＥＬＰＨＩＮＩＵＭ...     

ENHANCEMENT OF EXCIMER FORMATION AND PHOTODIMERIZATIONON OF 9－ANTHRYLMETHYL DODECANOATE VIA AGGREGATION

ＥＮＨＡＮＣＥＭＥＮＴ　ＯＦ　ＥＸＣＩＭＥＲ　ＦＯＲＭＡＴＩＯＮ　ＡＮＤ　ＰＨＯＴＯＤＩＭＥＲＩＺＡＴＩＯＮＯＮ　ＯＦ　９－ＡＮＴＨＲＹＬＭＥＴＨＹＬ　ＤＯＤＥＣＡＮＯＡＴＥ　ＶＩＡ　ＡＧＧＲＥＧＡＴＩＯＮＥＮＨＡＮＣＥＭＥＮＴＯＦＥＸＣＩＭＥＲＦＯ...     

ANEW CHIRAL SCHIFF BASE FAMILY DERIVED FROM 2,4-DIHYDROXYBENZALDEHYDE

ＡＮＥＷＣＨＩＲＡＬＳＣＨＩＦＦＢＡＳＥＦＡＭＩＬＹＤＥＲＩＶＥＤＦＲＯＭ２，４－ＤＩＨＹＤＲＯＸＹＢＥＮＺＡＬＤＥＨＹＤＥＹａｎＱｉｎｇＴＩＡＮ；ＹｉｎｇＹｉｎｇＺＨＡＯ；ＦｅｎｇＹｕＳＵ；ＸｉｎＹｉＴＡＮＧ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔ...     

A MICROCALORIMETRIC ADSORPTION STUDY ONSURFACEACIDITYANDBASICITYOFFe┐MgBINARYOXIDES

ＡＭＩＣＲＯＣＡＬＯＲＩＭＥＴＲＩＣＡＤＳＯＲＰＴＩＯＮＳＴＵＤＹＯＮＳＵＲＦＡＣＥＡＣＩＤＩＴＹＡＮＤＢＡＳＩＣＩＴＹＯＦＦｅ┐ＭｇＢＩＮＡＲＹＯＸＩＤＥＳ＊ＳｈｅｎＪｉａｎｙｉ，ＴｕＭａｉ，ＣｈｅｎＹｉ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ...     

A NEW N－FORMYL C_（19）－DITERPENOID ALKALOID， ALDOHYPACONITINE， FROM CULTIVATED ACONITUM CARMICHAELI， DEBX．

ＡＮＥＷＮ－ＦＯＲＭＹＬＣ_（１９）－ＤＩＴＥＲＰＥＮＯＩＤＡＬＫＡＬＯＩＤ，ＡＬＤＯＨＹＰＡＣＯＮＩＴＩＮＥ，ＦＲＯＭＣＵＬＴＩＶＡＴＥＤＡＣＯＮＩＴＵＭＣＡＲＭＩＣＨＡＥＬＩ，ＤＥＢＸ．￥ＸｉａｎＫａｉＷＡＮＧ；ＴｏｎｇＦａｎｇＺＨＡＯａｎｄＳｈ?..     

原子吸收光谱法间接测定盐酸布比卡因

提出了在Ｎ，Ｎ－二甲基甲酰胺（ＤＭＦ）存在下，用二氯乙烷萃取盐酸布比尔因与钴硫氰酸根生成的离子对缔合物，经反萃取后，用原子吸收光谱法测定反萃取液中的Ｃｏ＾２＋量间接确定盐酸布比卡因含量的新方法，本法在０．０５～１．３０ｇ／Ｌ范围内呈线良好线性关系（ｒ＝０．９９９９），回收率在９８％～１０３％的范围内，用于实际样品测定获得良好效果。     

Thermal characterization of poly(lactide-co-glycolide) microspheres containing bupivacaine base polymorphs

Solid-state chemistry of bupivacaine base, obtained by precipitation from bupivacaine hydrochloride solutions with ammonia, was investigated. Two bupivacaine base polymorphs (Form I: T _m=105.6±0.0°C; Form II: T _m=97.6±0.2°C) were isolated depending on the precipitation conditions and characterised by thermal analysis and FTIR spectroscopy. No weight loss was evidenced by TG confirming that no solvate formation had occurred. Biodegradable poly(lactide-co-glycolides) microspheres containing bupivacaine base were prepared by spray-drying. In the microspheres bupivacaine base was present as the metastable low melting crystal form independently of the bupivacaine base / poly(lactide-co-glycolides) ratio.     

Poly(acrylonitrile) ultrafiltration membranes. I. Polymer‐salt‐solvent interactions

Fourier transform infrared spectroscopy was used to study the interactions among LiCl, ZnCl₂, and AlCl₃ with N,N‐dimethylformamide (DMF) and poly(acrylonitrile) (PAN). It was observed that all three salts complex with DMF as well as PAN. The strength of the cation interaction with the >C?O oxygen of DMF was found to be higher than that with the ? CN group of PAN. The >C?O stretching frequency of DMF with ZnCl₂ was red shifted, indicating stronger complex formation compared with other two cations. With the addition of salt, the salt–DMF pseudo solvent was found to become a θ solvent for PAN compared with neat DMF. This change in PAN solvation power was primarily the result of DMF–salt complexation. As a result of the complexation, Mark‐Houwink constant a, was found to reduce from 0.75 (for pure DMF) to ～0.6 for DMF–salt solvents, indicating decreased PAN chain expansion. Comparison of intrinsic viscosity [η] values indicated that addition of salts to PAN–DMF solutions resulted in: (i) decrease in the DMF solvation power, which causes less expanded polymer coils, and (ii) increased interpolymer chain entanglements via salt‐promoted chain association. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2061–2073, 2005     

Experimental FTIR and simulation studies on H-bonds of model polyurethane in solutions. I: In dimethylformamide (DMF)

Polyurethane (PU) hard segment is one of the key factors determining the final PU properties whereas dimethylformamide (DMF), with the simplest tertiary amide, is one of the good solvents for PU. In the present paper, both FTIR and molecular simulation (QM/B3LYP) were used to study the hydrogen bonds (H-bonds) of PU model hard segment (PUMHS) in DMF. The FTIR characteristics and the H-bonding interaction between DMF and PUMHS, as well as in DMF and PUMHS themselves have been investigated. The results showed that the H-bonds not only exist in DMF and in PUMHS themselves, but also exist between PUMHS and DMF. Among them, seven H-bonding complexes between DMF and PUMHS were found based on different conformations. The H-bonding properties and the forming probabilities have been obtained and compared. The evolution of H-bonds of PUMHS in DMF with different concentration was qualitatively analyzed.     

Proton bound homodimers and heterodimers of amides and amines in the gas phase. Equilibrium studies by Fourier transform ion cyclotron resonance spectrometry

By injection of the proton bound homodimer [DMF.H+.DMF] of N,N-dimethylformamide (DMF) generated in an external ion source into a mixture of DMF and a second base within the cell of a Fourier transform ion cyclotron resonance (FT-ICR) spectrometer the equilibria between [DMF.H+.DMF] and the other possible proton bound dimers [DMF.H+.base] and [base.H+.base] have been studied for 13 different bases. Strongly polar bases like aliphatic amides and dimethyl sulfoxide (DMSO) exchange both DMF in [DMF.H+.DMF] by a two step process, while the almost non-polar amines exchange only one DMF. If the base is a primary or secondary amine, the proton bound heterodimer [DMF.H+.amine] reacts further by the addition of one DMF to create a proton bound trimer [(DMF)2.H+.amine]. The affinity deltaG(DMFH+) of the bases towards protonated DMF relative to neutral DMF depends linearly on the difference deltaGB of the gas phase basicity of DMF and the other base, but different correlation lines are obtained for polar and non-polar ligands (deltaGDMFH+ = 0.44GB(base)-375 [kJ/mol] (r = 0.97) and deltaGDMFH+ = 0.46GB(base)-397 [kJ/mol] (r = 0.99), respectively). This different behavior is explained by a different character of the proton bridge in the heterodimers containing only polar ligands and those incorporating a non-polar ligand besides DMF. The former dimers contain a more or less symmetric proton bridge while the latter can be viewed as a protonated base solvated by DMF. The available data have been used to calculate the molecular pair gas phase basicity of DMF and the 13 bases used and to estimate the dissociation energies of the bonds of the proton bridge in various proton bound heterodimers.     

DMF竞争性抑制大豆脂氧酶好氧催化及其松弛底物抑制的综合作用

在大豆脂氧酶催化亚油酸的氧化反应中加入溶剂二甲基甲酰胺DMF(lgP为-1.01)可将底物亚油酸浓度提升到232 mmol/L而不产生底物抑制作用, 并使平衡产率从38.93%提高到66.09%. 在有底物存在时, 质量分数为5%的DMF基本不影响酶活; 此时体系具有最大的Kss与Ki值, 表明5%DMF对底物抑制作用的松弛效应最强, 而对酶的抑制作用最小.     

Comparative study of mono- and dinuclear complexes of late 3d-metal chlorides with N,N-dimethylformamide in the gas phase

Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)(n)MCl](+) almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu(II) to Cu(I) concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl(2) with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)(n)ZnCl](+) and [(DMF)(n)Zn(2)Cl(3)](+), ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)(2)Zn(2)Cl(3)](+) which corroborates parallel theoretical predictions.     

Competitive complexation in the copper(II) chloride-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylformamide-Aerosil system

Competitive complexation in the copper(II) chloride-N,N-dimethylformamide (DMF)-Aerosil system was studied by IR spectroscopy. It was found that adsorption from organic solutions containing copper(II) chloride and DMF resulted in the formation of the following three types of DMF complexes: self-associates of DMF, DMF complexes with surface hydroxyl groups, and DMF complexes with Cu(II) ions. The removal of DMF resulted in the sequential degradation of, initially, self-associates; next, complexes with silanol groups; and, finally, complexes with copper ions.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 917–920.Original Russian Text Copyright © 2004 by Golubeva, Zubareva.     

Processes of molecular association and excimeric emission in protonated N,N-dimethylformamide

Formation of associates of N,N-dimethylformamide (DMF) molecules was studied to clarify their role in photoluminescent activity of protonated DMF solutions. The association of DMF molecules was observed in dilute aqueous solutions at concentrations of DMF above approximately 4x10(-2) M. The association is enhanced when the CO bond of the DMF molecule is activated by protonation with hydrochloric acid, which leads to appearance of an excimeric emission at approximately 530 nm. The excitation spectrum of the excimeric emission showed the excitation maximum in the region of the absorption of DMF associates, which is a first evidence of a more complex mechanism of excimer formation originating from excitation of associated rather than monomeric molecules in the ground state. A simple approach was provided to evaluate a number of molecules in the excimer structure. An original theory has been developed, and it was calculated that the DMF excimer has a dimeric nature. A model of the excimer formation was proposed, which suggests that a hydrogen-bonded associate is an intermediate form leading to the excimeric structure upon excitation. It was observed that DMF possesses also a monomeric emission with the emission maximum at approximately 385 nm, which was attributed to the intramolecular charge-transfer process. It has been found that the change in structure of the DMF associates via the liquid-solid phase transition affects both excitation and emission bands of excimers, so that the excimeric emission shifts to the blue region and intermixes with the emission of DMF monomers.     

Li＋在PC＋DMF混合溶剂中优先溶剂化的13C NMR研究

利用¹³C NMR光谱技术研究了Li^＋在碳酸丙烯酯(PC)＋N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li^＋发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO₄＋PC＋DMF混合物中, DMF分子对Li^＋的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)＝1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li^＋第一溶剂化层中的比率为0.12, 说明Li^＋优先被DMF分子溶剂化.