FT-Raman Spectra of o-, m-, and p-Nitrophenol Included in Cyclodextrins

FT-Raman spectra of o-, m-, and p-nitrophenol included in -cyclodextrin (CD), -CD, hydroxypropyl (HP) -CD, andsulfated -CD were recorded. The phenyl (C=C) band of o- and p-nitrophenol in the CD inclusion complexes was shifted to higher wavenumber thanthat of pure o- and p-nitrophenol,whereas the phenyl (C=C) band of m-nitrophenol in the CD inclusion complexes was shifted to lower wavenumber than that of pure m-nitrophenol. The ring CH peak of o-nitrophenol in the CD complexes was shifted to higher wavenumber than that of pure o-nitrophenol, whereas the ring CH peak of m- and p-nitrophenol in the CD complexes was shifted to lower wavenumber than that of pure m- and p-nitrophenol.     

Fast Atom Bombardment Mass Spectroscopic Investigation of Inclusion Complexes of Cyclodextrins with 4-Nitrophenol and Benzoic Acid

Mixtures of -, -, and -cyclodextrins and 4-nitrophenol (or benzoic acid) were investigated by means of fast atom bombardment mass spectroscopy. In the gas phase, inclusion complexes of -, , and -cyclodextrins with 4-nitrophenolate and benzoate, which have a 1 : 1 cyclodextrin–guest stoichiometry, were observed in negative-ion mode. In addition, guest anions, clusters of two and three guest molecules, and guest–matrix complexes were observed.     

Complexation of Ketoconazole by Native and Modified Cyclodextrins

Complexation of ketoconazole (KET), a broad-spectrum antifungal drug, with β- and γ-cyclodextrins (CDs), heptakis (2,6-di-O-methyl)-β-CD (2,6-DM-β-CD), heptakis (2,3,6-tri-O-methyl)-β-CD (TM-β-CD), 2-hydroxypropyl-β-CD (2HP-β-CD) and carboxymethyl-β-CD (CM-β-CD) was studied. The stability constants were determined by the solubility method at pH = 6 and for 2,6-DM-β-CD and CM-β-CD at pH = 5. At pH = 6, the stability constants increased in the order: TM-β-D < γ-CD < 2HP-β-CD < β-CD < CM-β-CD < 2,6-DM-β-CD. At pH = 5, due to the increased ionization of KET, the stability constant with CM-β-CD increased and with 2,6-DM-β-CD decreased. For complexes of KET with 2HP-β-CD and 2,6-DM-β-CD, the thermodynamic parameters of complexation were determined from the temperature dependence of the corresponding stability constants. For β–γ and TM-β-CD complexes, calculations using HyperChem 6 software by the Amber force field were carried out to gain some insight into the host–guest geometry.     

Spectroscopic Study of the Inclusion Complexes of Phenylbutazone and Oxyphenbutazone with Cyclodextrins in Polar Reaction Media

The formation of inclusion complexes of -, -, hydroxypropyl-- (HP--) and -cyclodextrins with phenylbutazone and oxyphenbutazone has been studied in aqueous buffer solution (pH 7.5 and 0.1 mol dm^-3 NaCl), dimethylsulfoxide, and 25, 50 and 75% dimethylsulfoxide/water mixtures. These complexation reactions have been followed by UV electronic absorption spectroscopy. In addition, 1D and 2D ¹H NMR spectra were recorded to obtain structural information about the inclusion complexes formed in solution; 136 binding constant values were determined at five different temperatures (288, 293, 298, 303 and 310 K) from the electronic absorption data and, from these H_binding and S_binding values were obtained. At the studied cyclodextrin and guest concentration ranges, 1 : 1 inclusion complexes were detected. Only in three cases were 1 : 2 complexes detected, those of phenylbutazone and oxyphenbutazone with -cyclodextrin in aqueous, and oxyphenbutazone with hydroxypropyl--cyclodextrin in 75% dimethylsulfoxide/water solutions.     

Inclusion Complexes of Cyclodextrins with Tetrakis(4-carboxyphenyl)porphyrin and Tetrakis(4-sulfonatophenyl)porphyrin in Aqueous Solutions

In neutral and alkaline solutions, tetrakis(4-carboxyphenyl)porphyrin (TCPP) and tetrakis(4-sulfonatophenyl)porphyrin (TSPP) form 1:1 and 2:1 host–guest inclusion complexes with -cyclodextrin (-CD), -cyclodextrin (-CD), and 6-deoxy-6-diethylamino--CD (DEA--CD), except for DEA--CD in alkaline solution. On the other hand, TCPP and TSPP form only 1:1 inclusion complexes with 6-deoxy-6-dihexylamino--CD (DHA--CD). The limited solubilities of DEA--CD in alkaline solution and DHA--CD are likely responsible for no observation of the 2:1 inclusion complex containing DEA--CD in alkaline solution and that containing DHA--CD. The equilibrium constants (Ks) of TCPP and TSPP for the formation of the inclusion complexes have been estimated from the absorption and/or fluorescence intensity changes in neutral and alkaline solutions. The K₂ values, which are the equilibrium constants for the formation of the 2:1 host–guest inclusion complex from the 1:1 inclusion complex, are about one tenth the corresponding K₁ values, except for the -CD–TSPP system in alkaline solution. In neutral solution, where DEA--CD and DHA--CD are in protonated forms, the electrostatic force operates between DEA--CD (DHA--CD) and TCPP (TSPP), leading to the greater K values than those in alkaline solution, where DEA--CD and DHA--CD exist as neutral species.     

Theoretical Study on the Structure and Vibrational Spectra for4-methyl-3-penten-2-one

The4-methyl-3-penten-2-oneisanimportanta,0-unsaturedketonemoleculeandanimportantligandoftheorganometalliccompounds.Untilnow,somepropertiesofphoto-chemistryandexcitedstateshavebeenexperimentallystudied'-#andconformationofthemoleculewerealsostudiedinexperiments"'.Standardinfraredgratingspectrumwasalsoobtainedin1970'.However,therearenodensityfunctionaltheory(DFT)calculationsofthismoleculeintheliterature.Recently,densityfunctionaltheoryhasbeenacceptedbytheahinitioquantumchemistrycommunityasacost…     

Er2O3的光致发光光谱,吸收光谱和Raman光谱

在可见激光的激发下,Ｅｒ２Ｏ３粉晶样品的Ｒａｍａｎ光谱易受Ｅｒ＾３＋光致发光光谱的干扰。本文利用同一Ｒａｍａｎ光谱仪测得Ｅｒ２Ｏ３的高分辨可见光吸收光谱和激发光谱。     

Synthesis,characterization, NLO study,and antimicrobial activities of metal complexes derived from 3-(3-(2-hydroxyphenyl)-3-oxoprop-1-enyl)-4H-chromen-4-one and sulfanilamide

A series of metal(II) complexes ML (where M?=?Cu(II), Co(II), Ni(II), Zn(II), Mn(II), Cd(II), and VO(II)) have been prepared from 3-(3-(2-hydroxyphenyl)-3-oxoprop-1-enyl)-4H-chromen-4-one and sulfanilamide. The structures of the complexes have been investigated by elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, NMR, mass, and ESR spectral studies. Conductivity measurements reveal that the complexes are non-electrolytes, except the oxovanadium complex. Spectral and other data show square pyramidal geometry for oxovanadium and octahedral for the other complexes. The redox behaviors of the copper and vanadyl complexes have been studied through cyclic voltammetry. Antimicrobial activities of the compounds against several microorganisms indicate that some complexes have higher activity than free ligand. The compounds may serve as photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation efficiency of the ligand was found to be higher than that of urea and KDP.     

Crystal structure,spectroscopic and thermal studies of 3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid sodium salt

The crystal structure, infrared spectrum and thermal stability of 3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid sodium salt have been studied. The compound of general formula {[Na₂L₂?·?3H₂O]?·?H₂O} _n is a two-dimensional polymer, in which Na ions are bridged by one or two water molecules and additionally coordinated to oxygen atoms of carboxylate, hydroxy and methoxy groups. The structure is stabilized by a hydrogen bond network. The compound dehydrates at 75°C and then decomposes at 150°C. The IR spectra of the salt and free acid are discussed.     

3-(2'-苯基-1', 2', 3'-连三唑-4'-基)-6-烷基/芳基-均三唑并[3, 4-b]-1, 3, 4-噻二唑的合成

研究了3-(2'-苯基-1', 2', 3'-连三唑-4'-基)-4-氨基-5-巯基-1, 2, 4-三唑(1)与取代苯甲酸和脂肪酸(2a-r)在POCl3催化下的反应, 共合成得到18个新的3-(2'-苯基-1', 2', 3'-连三唑-4'-基)-6-烷基/芳基-均三唑并[3, 4-b]-1, 3, 4-噻二唑(3a-r), 经元素分析,IR, 1H NMR和MS进行了结构确证。     

Synthesis,Crystal Structure and Anti-tumor Activity of 2-（2-Chloro-4-nitrophenyl）-4- （4-chlorophenyl）-3a,4-diethoxy-2,3,3a, 4-tetrahydrochromeno[3,4-d] [ 1,2,3]diazaphosphole

The title compound 2-（2-chloro-4-nitrophenyl）-4-（4-chlorophenyl）-3a,4- diethoxy- 2,3,3a, 4-tetrahydrochromeno[3,4-d][1,2,3]diazaphosphole 2 （C29H30Cl2N3O7P, Mr = 633.44） was synthesized and its structure was characterized by IR, MS, ^1H NMR, ^13C NMR, ^31p NMR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1^-, a = 9.1549（3）, b = 10.7168（4）, c = 17.6272（6）A, α = 102.9363（12）, β = 90.2713（9）, γ = 117.4265（10）°, V= 1484.41（9）A^3, Z= 2,μ（MoKa） = 0.323, F（000） = 658, Z= 2, De= 1.417 g/cm^3, the final R = 0.0687 and wR = 0.2066 for 4943 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the diazaphospholine ring is almost planar and the two ethoxy groups bonded on the 3a- and 4-positions are in trans configurations. Its antiproliferative activity was also tested in vitro against four human tumor cell lines.     

3-烷基/芳基-6-(2', 4'-二氯苯基)-7H-1, 2, 4-三唑[3, 4-b]- 1, 3, 4-噻二 嗪的合成及波谱性质

以间二氯苯与氯乙酰氯反应,生成ω-氯代-2,4-二氯苯乙酮(1),再使之分别与3-烷基/芳基-4-氨基-5-巯基-1,2,4-三唑(2a～2l)反应,合成了12种新的3-烷基/芳基-6-(2',4'-二氯苯基)-7H-1,2,4-三唑并[3,4-b]1,3,4-噻二嗪(4a～4l)。利用EA,IR,^1HNMR确定了其结构,并提出该反应的可能机制。     

Synthesis and Bioactivity of Novel Aminomethyl-2-（1, 2,4-triazol）-4, 4-dimethyl-3-pentanone （ol）

3, 3-Dimethyl-1-(1,2,4-triazol)-2-butanone was treated with aqueous formaldehyde to give an additional product, and subsequent elimination by acetic anhydride yielded 4,4-dimethyl-2-(1,2,4-triazol)-1-penten-3-one. Further addition with substituted amines provideda series of (1,2,4-triazol)-4,4-dimethyl-3-pentanone, which were then reduced by KBH4 to obtaina series of (1,2,4-triazol)-4,4-dimethyl-3-pentanol. Their structures were confirmed by ^1HNMR and elemental analysis. The results of bioassay showed that the title products possess good fungicidal activities.     

二[1-(2-噻吩基)-4,4,4-三氟丁二酮-1,3]合铜(Ⅱ)及其某些溶剂加合物的热分析研究

Thermoanalysis study has been carried out on the complex of bis[1-(2-thienyl)-4,4,4-trifluoro-butanedione- 1,3]copper(Ⅱ) and its adducts with pyridine, 2,2′-bipyridine, quinoline and dimethyl sulfoxide in a dynamic ni-trogen atmosphere by simultaneous TG-DTG-DSC technique. The experimental results showed that the decomposi-tion modes of the solvent molecules were various according to the different structures of the complex, in general, the decomposition of them was ahead of the decomposition of the ligand 1-(2-thienyl)-4,4,4-triflurobu- tanedione-1,3. Among them the adduct with 2,2-bipyridine showed a quite unique thermal behavior. Several methods have been jointly used to study the kinetics of all the thermal decomposition stages for title compounds, which showed that the evolution of the solvent molecules was controlled mainly by Rn mechanism (or Am mechanism for 2,2-bipyridine adduct) with lower activation energy; while the release of 1-(2-thienyl)-4,4,4-trifluro-butane- dione-1,3 was gove- rned by D2 or D3 mode with higher activation energy.     

固体超强酸催化剂SO2-4/TiO2-WO3的制备及其催化性能研究

制备了固体超强酸催化剂SO2-4/TiO2-WO3,并以丁酸丁酯的合成作为探针反应,系统考察了WO3的含量、硫酸浸渍浓度、焙烧温度等制备条件对SO2-4/TiO2-WO3催化活性的影响.实验表明:制备催化剂的适宜条件为m(H2WO4)=12.5%,硫酸浸渍浓度为1.0 mol·L-1,焙烧温度为580℃,活化时间3 h.利用优化条件下制备的催化剂SO2-4/TiO2-WO3催化合成缩醛(酮),在醛/酮与二元醇(乙二醇,1,2-丙二醇)的投料摩尔比为1:1.5,催化剂的用量占反应物总投料质量的0.5%,反应时间为l h条件下,2-甲基-2-乙氧羰甲基-1,3-二氧环戊烷的收率为78.7%,2,4-二甲基-2-乙氧羰甲基-1,3-二氧环戊烷的收率为83.0%,环己酮-乙二醇缩酮的收率为85.9%,环己酮-1,2-丙二醇缩酮的收率为84.6%,丁酮-乙二醇缩酮的收率为70.7%,丁酮-1,2-丙二醇缩酮的收率为88.3%,2-丙基-1,3-二氧环戊烷的收率为80.6%,4-甲基-2-丙基-1,3-二氧环戊烷的收率为79.6%,2-异丙基-1,3-二氧环戊烷的收率为64.2%,4-甲基-2-异丙基-1,3-二氧环戊烷的收率为83.3%,2-苯基-l,3-二氧环戊烷的收率为75.3%,4-甲基-2-苯基-1,3-二氧环戊烷的收率为95.1%.     

新试剂6-(2,4-二羟基苯基偶氮)-2,3-二氢-1,4酞嗪二酮的电致化学发光研究

本文研究了6-(2,4-二羟基苯基偶氮)-2,3-二氢-1,4酞嗪二酮(新试剂DHDHD)的电致化学发光的条件及产生电化学发光的机理。     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.     

The Effect of Cyclodextrins on the Photochemical Stability of 7-Amino-4-methylcoumarin in Aqueous Solution

The effect of -, - and -cyclodextrin onthe photochemical stability of 7-amino-4-methylcoumarin (C120)was studied. Using spectroscopic techniques (UV/Vis absorption spectroscopy, fluorescence, fluorescence anisotropy and circular dichroism) combined with HPLC/MS and MS analysis it was demonstrated that addition of -cyclodextrin to the aqueoussolution of C120 markedly inhibits the photodegradation of that dye. This results from theformation of an inclusion complex between C120 and -cyclodextrin.     

1,2-和1,4-萘醌248 nm激光光解的瞬态吸收光谱研究

利用纳秒级激光光解动态吸收光谱装置,研究了1,2-和1,4-萘醌中性水溶液的瞬态吸收光谱.发现1,2-萘醌及1,4-萘醌被光电离后形成的阳离子自由基在380nm均有最大吸收,但1,4-萘醌阳离子自由基在衰变过程中又形成了两种新的活性粒子,它们的最大吸收分别位于410和580nm,分析表明:410nm属于1,4-萘醌脱氢自由基的吸收,而580nm很可能归属由于电子转移而形成的瞬态产物.进一步研究发现,1,2-萘醌在中性水溶液中能被248nm激光单光子电离.     

Novel 3d-metal complexes with 1,2-diamino-3-(2-benzothiazolyl)-4(5H)-ketopyrrole: Synthesis,spectroscopic and structural investigations

A series of new 3d-metal complexes have been prepared by the reaction of M(CH₃COO)₂ (M = Zn(II), Co(II), Ni(II)) and 1,2-diamino-3-(2-benzothiazolyl)-4(5H)-ketopyrrole (HL) in a methanol (3) or a methanol/dmf (1, 2) medium. All the complexes have been studied by elemental analyses, electronic and IR spectroscopies. The zinc(II) complex 1 and the ligand HL have been investigated using the method of ¹H NMR-spectroscopy at various temperatures. The disappearance of the signal from one proton of the amino group H(5) in the spectrum of complex 1 confirmed the existence of the ligand in the deprotonated form. According to the data of the ¹H NMR-spectroscopy, the ligand HL is coordinated to zinc(II) through the nitrogen atom of the deprotonated amino group and the nitrogen atom of the benzothiazole substituent. These data are in agreement with X-ray structural studies for the ligand HL and the zinc(II) complex 1.