3－烷基-4-羟基-2-噻唑烷硫酮-4-羧酸乙酯的一锅煮合成

Ethyl 3-alkyl-4-hydroxy-2-thioxothiazolidine-4-carboxylates were prepared in excellent yields from the reaction of corresponding primary amines with carbon disulfide and ethyl 3-bromo-2-oxopropanoate in the presence of anhydrous potassium phosphate in DMF at room temperature within 1 h. The structures of the highly functionalized products were corroborated spectroscopically （IR, ^1H NMR, ^13C NMR, EI-MS） and by elemental analyses. A plausible mechanism for such type of cyclization was proposed.     

Studies on Amidothiosemicarbazides and Related Hcterocyclic Derivatives ( XIII) --Synthetic Studies on 2-(3-Pyridyl)-5-Arylamino- 1,3, 4-Thiadiazoles and Oxadiazoles

By ring-closure of 1-nicotinyl-4-arylthiosemicarbazides under the catalysis of concentrated sulfuric acid or mercuric acetate, a series of 2-(3-pyridyl)-5-arylarnino-1,3,4-thiadiazoles and 2-(3-pyridyl)-5-ary-lamino-1,3,4-oxadiazoles were synthesized, respectively. All the products were subjected to testing of biological activity. Furthermore, the IR, 1H NMR and MS spectral properties of these new compounds were studied in details and some significant conclusions were drawn.     

高活性离子液体-铑膦络合物体系催化1-己烯氢甲酰化反应

 The hydroformylation of 1-hexene catalyzed by rhodium-TPPTS complexes in the ionic liquid [bmim]BF4 was studied. The activity and selectivity of the rhodium-TPPTS complexes in [bmim]BF4 were much higher than those reported in other ionic liquids. The TOF of 1-hexene and selectivity for aldehyde were 1508 h-1 and 92%, respectively, under the optimum conditions. The high activity of the catalyst is ascribed to the absence of halide ions as well as the much higher solubility of hydrogen and rhodium-TPPTS complexes in [bmim]BF4 than in [bmim]PF6.     

Synthesis and Crystal Structure of 3-（ 2- Hydroxybenzly ）-4-（ 4- Hydro xybenzylideneamino ）-（1H） - 1,2,4- Triazole-5-Thione and Its Antibacterial Activities

1 INTRODUCTION 2. 1 Physical measurements Azole derivatives, such as pyrazole, imidazole, All solvent and chemicals were commercial rea- triazole(including benzotriazole), tetrazole and indole, gents and used without further purification. Ele- have extensive biological activities. They have be- mental analyses were performed on a PE 1700 CHN come the central focus of studies for agricultural che- auto elemental analyzer. IR spectra were recorded on micals, medicines, plant growth regul…     

新的手性[2-(1-羟基烷基)吡咯]甲基二茂铁配体的合成及其在催化不对称加成二乙基锌到芳香醛中的应用

A series of new optically active [2-（1-hydroxyalkyl）pyrrolidino]methylferrocenes were conveniently prepared from commercially available L-proline and ferrocenecarboxylic acid. The crystal structure of key intermediate was obtained. They were then applied to catalyze enantioselective addition of diethylzinc to arylaldehydes with enantioselectivity up to 99%. The effects of the ligand structures on the enantioselectivity were also studied.     

1-萘甲酰苯胺和2-萘甲酰苯胺的分子内电荷转移研究

A series of 1-naphthanilides (1) and 2-naphthanilides (2) with varied substituents at the para- or meta-position of anilino phenyl ring were prepared and their absorption and fluorescence spectra in a nonpolar solvent cyclohexane were investigated. An abnormal long wavelength emission assigned to the charge transfer (CT) state was found for all of the prepared naphthanilides in cyclohexane. A linear free energy correlation between the CT emission energies and the Hammett constants of the substituent was found within series 1 and 2. The value of the linear slope with 1 (0.42 eV) was higher than that with 2 (0.32 eV) being close to that of the substituted benzanilides 3 (0.31 eV) The higher slope value suggested higher charge separation extent in the CT state of 1 than that of 2. It was found that the corresponding linear slope of anilino-substituted benzanilides remained unchanged when para-, meta-, ortho-, or ortho, ortho-methyls were introduced into the anilino moiety, which ruled out the possible contribution of the difference in the steric effect and the electron accepting ability of the naphthoyl acceptor in 1 and 2. Compared with the early reported N-substituted-benzoyl-aminonaphthalene derivatives 4 and 5, it was considered that 1-naphthoyl enhanced the charge transfer in 1 and the proximity of its ^1La and ^1Lb states was suggested to be responsible. It was shown that 1- and/or 2-substituted naphthalene cores acting as either electron acceptor (naphthoyl) or electron donor (aminonaphthalene) were different in not only electron accepting (donating) ability but also shaping the charge transfer pathway.     

羟丙基-β-环糊精对双苯氟嗪包合作用的热力学研究

The inclusion complexes formation of dipfluzine(DF)with hydroxpropy -β-cyclodextrin(HP-β-CD)in aqueous solution was investigated by the phase-solubility method.With the increase of HP-β-CD concentration in aqueous sloutions,the solubility of DF increased linearly,which showed typical AL-type phase solubility diagram.The molar ratio of the DF-HP-β-CD complex was 1: 1.The effect of temperature on the reaction was studied through thermodynamics.The apparent stability constants of inclusion reation were determined.Thermodynamic parameters during the inclusion process were as follows: △_rH=30.58 kJ·mol~(-1),△_rS=158.8 J·mol~(-1)·K~(-1),△_rG＜0.The complex process was endothermic and spontaneous.With the increase of temperature,the tendency of spontaneous reaction increased.     

甲硫氨酸-脑啡肽的分子动力学模拟

The conformational properties of Met-enkephalin (Tyr-Gly-Gly-Phe-Met) were investigated by high temperature quenched molecular dynamics simulations in vapor. Each of these selected structures were then analyzed according to their backbone(φ,Ψ) conformational distributions and sorted into 13 families by computing the rms difference between the Cα-C backbone fragments of each residue over all the structures. Selected lowest energy conformations from each of 13 families were thoroughly energy minimized. The results of simulations show that Met-enkephalin is a flexible molecule. It shows a type Ⅰβ-turn, with the Gly2 carbonyl forming a hydrogen bond with the Met5 amino proton and a type Ⅱβ turn, with the Tyr1 amino proton forming a hydrogen bond with the Phe4 carbonyl. The multiple fit were carried out for all of the 13 conformers with morphine(9 atoms on the pharmacophore groups). F2 and F6 were the most similar to morphine. The rms were 0.0504 nm and 0.0726 nm. The results of simulations also show that Tyr amino N corresponds to N on piperidine ring in morphine, Tyr phenol corresponds to the phenol in morphine, the aromatic ring of Phe corresponds to the cyclohexene ring in morphine. The distances between the three pharmacophores, d1 (Tyr N to Tyr OH), d2 (Tyr N to Tyr du1), d3(Tyr N to Phe du2) and d4(Tyr N to Phe du2) were found to be about 0.8, 0.5, 0.7-0.9 and 0.5 nm, respectively, the corresponding, distances of morphine were found to be 0.7697(N18 to O6),0.5143(N18 to du25), 0.3962(N18 to du24)和0.5566(N18 to O15)nm. Therefore, they may be acted on the same receptor. This model should aid in pharmaceutical design of peptide and nonpeptide ligands with opioid.     

银盐法合成6-(4-卤代苯基)-3(2H)-哒嗪酮葡萄糖苷

Four pyridazinone gluosodes 4 were synthesized by Koenig' s-Knorr reaction of 6-(4-halophenyl)-3 (2H)-pyridazinone silver salt 2 with bromoaeetylglueose 3. Treatment of 4 with dry ammonia at 0 ～ - 5 ℃ effeeted a removal of the acetyl protecting groups to yield compounds 5. When the substituent on the benaene ring was F-or Cl-,O-glueoside was synthesized prineipaUy. However, when the substituent was Br-or I-, N-glueoside was mainly obtained. Their struetures were confirmed by ^1H NMR, IR and elemental analysis.     

锂离子电池硅-锰复合材料的电化学性能

The Si-Mn composites were synthesized by ball-milling mixtures of four different atomic ratios of Si/Mn. The phases of composites were analyzed with X-ray diffraction. Their charge-discharge performance as negative electrodes in Li-ion batteries were tested and the formation of SEI film was studied by differential capacity plots. The results show that materials prepared by ball-milling technology are composites consisting of Si and Mn. The insertion of lithium ions leads to the formation of amorphous Li-Si alloy. The initial reversible capacity and efficiency of Si-Mn composites are increased and the cycle life is enhanced obviously，especially after their heat treatment. The composite of Si∶Mn=4∶6 exhibits a reversible capacity of 546.0 mAh·g^-1 and a charge-discharge efficiency of 70%. The reversible capacity maintains at 374.2 mAh·g^-1 after 40 cycles.     

含能笼型碳硼烷衍生物的合成及其热性能

以DMSO或DMF为溶剂,1-溴甲基碳硼烷(1)分别与亚硝酸钠和叠氮钠发生亲核取代反应,合成了两种新型的含能笼型碳硼烷——1-硝基甲基碳硼烷(2)和1-叠氮基甲基碳硼烷(3),其结构经1H NMR和FT-IR表征。用DSC分析了1~3的热性能,结果表明:1和2分别在162.2℃和168.7℃分解,分解热分别为130.4 J.g-1和245.6 J.g-1。     

新型含1,2,4-三唑基的1,5-苯并硫氮杂的合成和表征

以α-溴代苯乙酮为原料,在三乙胺作用下制备α-(1,2,4-三唑-1-基)-芳基乙酮(1a～1c),再与芳香醛发生羟醛缩合反应制备相应的含三唑基的查尔酮2a～2l,将中间体2a～2l同邻氨基硫酚合成新型的2,4-二芳基-3-(1,2,4-三唑-1-基)-2,3-二氢-1,5-苯并硫氮杂(3a～3l).所得化合物的结构经元素分析,IR,MS和1HNMR确认,同时用X射线衍射法测定了化合物2a和3a的晶体结构.     

Characterization of Chitosan/Alginate Self-Assembled Nanoparticles as a Protein Carrier

The aim of this study was to evaluate the effect of the polymeric ratios on the characteristics of chitosan/alginate (ch/alg) self-assembled nanoparticles and their potential as protein delivery vehicle. The nanoparticles were prepared using proper mixing of polymers in presence or absence of bovine serum albumin (BSA) as a protein model. Three formulations of nanoparticles comprising ch/alg ratios of 2:1, 1:1, and 1:2 were prepared. Size, shape and zeta potential of the formulations were studied by scanning electron microscopy (SEM) and nanosizer instruments. FTIR, and differential scanning calorimetery (DSC) studies were performed to investigate polymer-polymer or polymer-protein interactions. Release profiles and entrapment efficiencies of the nanoparticles were determined by calorimetric technique using appropriate techniques. Entrapment efficiency was 70% for ch/alg ratio of 1:1, 65% for 1:2, and 60% for 2:1. The z-average size of the nanoparticles were 403, 205, and 318 nm for ch/alg ratios of 2:1, 1:1, and 1:2, respectively. Average zeta potentials were ?47, +15, ?25 mV for 2:1, 1:1, and 1:2 as well. Considering the favorable features required for protein delivery systems, ch/alg (1:1) due to its smallest size, highest loading, and most homogenous shape was regarded as the best ratio.     

Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects

Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 6(0)(1), 1(0)(1)6(0)(1), and 1(0)(2)6(0)(1) bands of the S1(1)B2u<--S(0)(1)A1g transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 1(0) (1)6(0) (1) band and 928 lines of the 1(0)(2)6(0)(1) band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S1(1)B2u(v1=1,v6=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S1(1)B2u(v1=2,v6=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S1(1)B2u and S2(1)B1u states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra.     

咪喹莫特的波谱学数据与结构表征

对咪喹莫特的红外(IR)、紫外(UV)、质谱(MS)、氢-氢相关谱(^1H--^1H COSY)、碳氢相关谱(HMQC)、碳氢远程相关谱(HMBC)予以解析并进行了报道。对所有的^1H NMR、^13C NMR谱的信号进行了归属；讨论了质谱的主要碎片离子的可能的裂解方式和红外特征吸收峰所对应的官能团的振动形式。     

PMMA-b-QPDMAEMA的合成及其抗菌活性

以α-溴代丙酸乙酯为引发剂,CuCl/二乙烯三胺为催化剂,采用ATRP法制得5个不同分子量的聚甲基丙烯酸甲酯-聚甲基丙烯酸二甲氨乙酯嵌段共聚物(PMMA-b-PDMAEMA, P¹~P⁵); P¹~P⁵经溴代辛烷季铵化合成了5个聚季铵盐(Q¹~Q⁵),其结构和性能经¹H NMR, FT-IR, GPC和DSC表征。结果表明：P⁴和Q⁴的玻璃化转变温度分别为109.67 ℃和117.95 ℃。采用平板活菌计数法研究了Q¹~Q⁵对金黄色葡萄球菌(S. aureus)和大肠杆菌(E. coli)的抗菌活性。结果表明：Q¹~Q⁵对S. aureus的抗菌活性优于E. coli,其MIC值分别为300 mg·L^-1, 250 mg·L^-1, 275 mg·L^-1, 225 mg·L^-1和150 mg·L^-1。     

新型水溶性超支化聚酰胺-酯的合成

均苯四甲酸酐与二乙醇胺经酰化反应制得中心核(4);4与AB2单体2,2-二羟甲基丙酸经熔融缩聚合成了一种新型水溶性的二代超支化聚酰胺-酯(1),其结构与性能经FT-IR,GPC,粘度法,化学滴定等表征。4的Mn=1 683,Mw=1 911,Mw/Mn=1.14,[ηinh]=0.067 6 dL·g-1;1的Mn=3 750,Mw=4 904,Mw/Mn=1.31,[ηinh]=0.086 1 dL·g-1。     

1,1'-不同酰基二茂铁衍生物的合成和波谱研究

以乙酰基二茂铁和相应的乙酰氯在三氯化铝存在下在 流室温条件下合成了不对称二乙酰基二茂铁衍生物; 1-乙酰基-1'-卤素取代苯甲酰基二茂铁, 除了获得预期产品以外, 当反应在 流温度下进行时, 还得到1,3-二(二茂铁基)-丁烯-2-酮-1, 用同样方法还合成了1-乙酰基-1'-棕榈酰二茂铁和1-苯甲酰-1'-棕榈酰基二茂铁.     

Synthesis of new analogues of diphenylpyraline

1-Unsubstituted 4-dimethylamino-5,6-dihydropyridine-2(1H)-thiones were converted to isomeric piperidin-4-ols which were separated and N-methylated to 2-substituted 1-methylpiperidin-4-ols. Their 1-phenyl analogues were prepared from 4-dimethylamino-5,6-dihydro-1-phenylpyridine-2(1H)-thiones. After their conversion to dihydro-1-phenylpyridin-4(1H)-ones the hydrogenation gave isomeric 1-phenylpiperidin-4-ols which were separated. O-Alkylation of the 1-substituted piperidin-4-ols by various methods yielded 2-substituted analogues of diphenylpyraline. Their antimycobacterial activity was examined. The configurations and conformations of the piperidine derivatives were investigated by NMR spectroscopy.     

无溶剂自催化合成吡咯或吲哚Michael加成产物

在吡咯或吲哚自身N－H的催化下,在无溶剂条件下合成了3个吡咯和5个吲哚Michael加成产物(2a～2c和3a～3e,其中2b和3a～3e为新化合物),收率80%～92%, 3a~3c的d/r值分别为3.8 : 1, 1.3 : 1和1.1 :1,其结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。