含葡萄糖基团缩氨基硫脲Schiff Base的合成

本论文以 2 ,3 ,4,6-四 -O-乙酰基 -β-D-吡喃葡萄糖基异硫氰酸酯为原料 ,制得了 8个未见报道的含葡萄糖基硫脲基 Schiff base(希夫碱类化合物 ) :芳香醛缩 N-氨基 -N′-2′,3′,4′,6′-四 -O-乙酰基 -β-D-吡喃葡萄糖基硫脲 ,所有目标化合物均经 IR,1 HNMR进行了表征。

L-苯丙氨酸Schiff Base金属铜配合物的合成、表征及理论研究

氨基酸Schiff Base金属配合物由于在磁学、非线性光学材料、荧光探针、生物活性等诸多领域有着潜在的应用价值,受到了极大的关注。本文采用L-苯丙氨酸与2-乙酰吡啶反应,合成了一种新型Schiff Base。随后用溶剂热合成法制得蓝色的L-苯丙氨酸Schiff Base金属铜的配合物单晶,并通过X射线单晶衍射、红外光谱、热重分析等对实验产物进行了结构解析和性质表征。为进一步了解其内在结构和性质,采用密度泛函理论,在分子水平进行了理论计算,对配合物进行了全优化,并在优化构型的基础上探讨了其平衡结构、NBO电荷分布和转移以及红外光谱等。结果表明,2个金属Cu(Ⅱ)离子分别与配体中的2个N、1个O原子配位,形成中心对称的六配位的弱氯桥双核化合物。该晶体属单斜晶系,晶胞参数a=1.246nm,b=0.886nm,c=1.451nm,α=90°,β=101.982(2)°,γ=90°。通过对单晶结构、NBO电荷、红外光谱的探讨,进一步说明了配位键的形成和配体在配位前后结构的变化,可为氨基酸金属配合物的合成、性质及应用研究提供理论参考。

In vivo anticancer activity of vanillin semicarbazone

Objective:To evaluate the anticancer activity of vanillin semicarbazone(VSC) against Ehrlich ascites carcinoma(EAC) cells in Swiss albino mice.Methods:The compound VSC at three doses(5, 7.5 and 10 mg/kg i.p.) was administered into the intraperitoneal cavity of the EAC inoculated mice to observe its efficiency by studying the cell growth inhibition, reduction of tumour weight,enhancement of survival time as well as the changes in depleted hematological parameters. Allsuch parameters were also studied with a known standard drug bleomycin at the dose of 0.3 mg/kg(i.p.).Results:Among the doses studied, 10 mg/kg(i.p.) was found to be quite comparable in potency to that of bleomycin at the dose of 0.3 mg/kg(i.p.). The host toxic effects of VSC was found to be negligible.Conclusions:It can be concluded that VSC can therefore be considered as potent anticancer agent.

Dioxygen Affinities and Biomimetic Catalytic Performance of Transition-metal Complexes with Benzoin Schiff Bases

The oxygenation constants of transition-metal complexes with benzoin Schiff bases were measured and these complexes were first employed as models for mimicking monooxygenase in catalytic epoxidation of styrene. The highest conversion and selectivity were up to 39.6% and 100% respectively at ambient temperature and pressure. The effects of structures of the bridge group R in the ligands on the dioxygen affinities and catalytic activities to epoxidize styrene were also investigated.

Syntheses,Crystal Structures and Complexing Properties of 1,3-Distal Calix[4]arene Schiff Bases

Novel 1,3-distal p-tert-butylcalix[4]arene Schiff bases were efficiently synthesized in three steps. At first p-tert-hutylcalix[4]arene was reacted with N-2-hydroxyethylphthalimide catalyzed by TPP/DEAD or alkylated with ω-hatoalkylphthalimide in the system of K2CO3/KI/CH3COCH3 to give 1,3-distal diphthalimidoalkyl calixarenes, which were in turn hydrazinolyzed to give diaminoalkyl calixarenes. Then with the aid of the condensation of active calixarene amines with salicylaldehyde, 2-hydroxy-l-naphthaldehyde or pyridine-2-carboxaldehyde, a series of 1,3-distal calixarene Schiff bases was prepared in satisfied yields. The single crystal structures and complexing properties of these Schiff bases for transition metal ions were studied.

Crystal Structures of Two Potential Tumor Imaging Agents and Therapeutic Agents-Copper(Ⅱ) Ternary Complexes with Salicylidene-tyrosinato Schiff Base and Nitrogen-donor Chelating Lewis Base

The crystal structures of two potential tumor imaging agents and therapeutic agents -copper(Ⅱ) complexes with salicylidene-tyrosinato Schiff base and nitrogen-donor chelating Lewis base, [Cu(sal-tyr)(bipy)] 1 and [Cu(sal-tyr)(phen)]2CH3OH 2 are presented. Our work is helpful to get deep understanding of novel 64Cu tumor imaging agents and therapeutic agents.

Synthesis, Characterization and Thermodecomposition Kinetics of Dy-Complex with Furfural and DL-α-Alanine

A new schiff base complex derived from furfural-DL-α-alanine and Dy(NO_3)·6H_2O was synthesized. It was characterized by elemental analysis, infrared spectra, ultraviolet spectra, molar conductivity measurements and thermogravimetric analysis. The stoichiometry was deduced to be [Dy(C_8H_8NO_3)(H_2O)(NO_3)](H_2O)(NO_3). Its thermal decomposition reaction kinetics was studied by thermogravimetry.

Synthesis of Calix[4]resorcinarene Core Dendrimers with Peripheral Salicylideneimine Functional Groups

First to third-generation calix[4] resorcinarene core dendrimers, compounds 4a, 4b, 7a, 7b, 10a and 10b, were prepared via the divergent method in seven steps with the corresponding tetraphenyl- and tetra （hydroxyphenyl） calix[4] resorcinarenes （compounds 1a, 1b） as the starting material. The repeat units of the polyamidoamines of these dendrimers were obtained by the ammonolysis of ethyl calixarylacetates 2a and 2b with 1,3-diaminopropane, that is, amide derivatives with terminal amino groups, which in turn reacted with ethyl acrylate to give a higher generation of ester derivatives. The structures of these dendrimers were characterized by IR, ^1H and ^13C NMR spoctrometries. The crystal structure of compound 2b with 12 ethoxycarbonylmethoxy groups was determined by X-ray analysis.

Synthesis and Color-tunable Fluorescence Properties of Schiff Base Zinc (II) Complexes Used as Electroluminescent Materials

Four kinds of bis(N-alkylsalicylaldiminato) zinc(II) complexes were synthesized, and their molecular structures were determined by FT-IR and elemental analysis. Their photoluminescence properties were determined, which indicated that they could emit strong fluorescence varying from blue to yellow to reddish orange depending on their different molecular structures. They had good thermostability, solubility and film forming capability, and can be used as organic lectroluminescent materials. These new complexes may afford the feasibility to realize full-color display with materials based on similar molecular structures.

Syntheses, Crystal Structures and Antibacterial Activities of Copper(Ⅱ) and Zinc(Ⅱ) Complexes Based on (E)-4-fluoro-2-((3-morpholinopropylimino)methyl)phenol

Two Schiff base complexes [Cu（L）2] （1） and [Zn（L）2]·3H2O（2） of （E）-4-fluoro-2-（（3-morpholino propylimino）methyl）phenol （HL） have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group Pī with a=4.8000（10）, b=11.109（2）, c=13.921（3）,α=66.55（3）,β=80.35（3）,γ=81.09（3）°, V=668.2（2）3 , Z=1, Dc=1.477g/cm 3 , F（000）=311, and the final R=0.0744 and wR=0.1601 for 2301 observed reflections with I 〉 2σ（I）. And those for 2： monoclinic, space group P21 /c with a=14.789（3）, b=11.713（2）, c=18.846（4）,β=107.85（3）°, V=3107.4（11）3 , Z=4, D c=1.389 g/cm 3 , F（000）=1368, and the final R=0.0749 and wR=0.1348 for 5423 observed reflections with I 〉 2σ（I）. Both 1 and 2 are four-coordinated complexes, with a square-planar geometry of copper（Ⅱ） in 1 and a slightly distorted tetrahedral geometry of zinc（Ⅱ） in 2. An asymmetric unit consists of only one half of a Cu ion and one L ligand in 1, while an asymmetric unit is composed of one Zn ion, two L ligands and three water molecules in 2. Non-classical C-H···O and C-H F hydrogen bonds play important roles in the formation of a 1D chain of 1, but O-H O and O-H N hydrogen bonds play dominant roles in the self-assembly of a 3D network of 2. The antibacterial activities of 1 and 2 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli and E. cloacae have been evaluated by MTT method.

Lanthanide amino acid Schiff base complexes:synthesis,spectroscopic characterization,physical properties and in vitro antimicrobial studies

Complexes of La （III）, Nd（III）, Gd（III）, Sm（III）, and Ce（IV） were synthesized with Schiff base [（3,5-di-tert-butyl-2-hy- droxybenzyl） amino] acetic acid （H3L）. The ligand and its complexes were synthesized and characterized based on the following analysis： elemental analyses, FAB-mass, molar conductance measurements, magnetic measurement, UV-visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to metal ion through ONO donor sequence. Thermal degradation studies of the ligand and its complexes showed that the previous lanthanide complexes were more thermally stable than the ligand itself. The Schiff base and its complexes were screened for their antibacterial （Escherichia coli, Staphylococcus aureus） and antifungal （Aspergillus flavus and Candida Albicans）.

An Effective Asphalt UV Blocking Material Based on Host-Guest Schiff Base/Layered Double Hydroxides

The development of asphalt-based UV blocking materials is important to extend the alphalt lifespan in road construction. In this work, we put forward that the fabrication of host-guest system can be an effective way to obtain UV blocking materials. Firstly, a new anionic Schiff base, N,N＇bis（salicylidine）-4,4＇-diaminostilbene-2,2＇-disulfonic acid （SDSD）, has been synthesized, which was intercalated into Zn-Al-LDH by anion-exchange method. FT-IR and XRD illustrate the layered organic-inorganic composite, Zn-Al-SDSD-LDH, has been successfully synthesized with high crystallinity. Laser particle size analyzer, SEM and TEM show that particle size distributions of Zn-Al-SDSD-LDH is in the range 100--500 nm. UV-vis absorption spectra show that Zn-Al-SDSD-LDH has better UV absorption than the pristine Zn-Al-LDH and SDSD. Furthermore, the mixture of asphalt and 3 wt% Zn-Al-SDSD-LDH presents enhanced UV blocking property relative to the pristine asphalt after irradiating by UV spray accelerated weathering test. Therefore, this work not only develops a new type of host-guest Zn-Al-SDSD- LDH, but also confirms it can be an effective asphalt UV blocking material for practical application.

Design and Synthesis of a Selective Chemosensor for Zn^2＋

A hydroxyl substituted phenolic Schiff base 1, used as sensor for detection of Zn^2＋, was synthesized and investigated. It was found that a strong fluorescence emission was observed when 1 bound to Zn^2＋ in acetonitrile, whereas no fluorescence emission was detected when 1 bound to other metal ions （Fe^2＋, Co^2＋, Ni^2＋, Cu^2＋, Cd^2＋, Hg^2＋, Mg^2＋, Pb^2＋, Ca^2＋, Ba^2＋, Sr^2＋） except for Mg^2＋, for which a weak fluorescence emission was detected in the same condition. Competition experiment showed that no obvious interference was observed in its fluorescence while 1 performed the titration with Zn^2＋ in the different mixtures of metal ions. To understand the site where Zn^2＋ coordinated to the ligand and the mechanism of binding, three other hydroxyl substituted phenolic Schiff bases 2-4 were synthesized and their binding reactions with Zn^2＋were also investigated.

Synthesis and Properties of Functionalized Schiff Bases of 5α,10α-Di（4-hydroxylphenyl）calix[4]pyrrole and 5α,15β-Di（4-hydroxylphenyl）calix｜4] pyrrole

A series of calix[4]pyrrole meso-substituted Schiff bases was synthesized with 5α,10α-di（4- hydroxylphenyl）calix[4]pyrrole or 5α,15β-di（4-hydroxylphenyl）calix[4]pyrrole as starting materials. The synthetic routes included alkylation with methyl a-chlroroaceate, ammonolysis with alkylene diamine, and condensation with salieylladehyde or 2-hydroxynaphthaldehyde. The crystal structures of the new calix[4]pyrroles and their Schiff bases were determined by X-ray diffraction. The coordination properties of the representative ealix[4]pyrrole Sehiff bases to transition metal ions were also investigated by UV-Vis spectra.

Synthesis and Crystal Structure ofp-tert-Butylcalix[4]arene 1,3-Distal and Monosubstituted Semicarbazones and Thiosemicarbazones

A series of p-tert-butylcalix[4]arene 1,3-distal and monosubstituted semicarbazones and thiosemicarbazones was preparedd by acid catalyzed condensation reaction of active calixarene aldehydes with semi- carbazide and thiocarbazide in methanol. One representative single crystal was determined by X-ray dirraction method, which shows that calixarene exists in cone configuration and intramolecular hydrogen-bands exist in the crystal.

Highly Sensitive and Selective Chemosensor for Cu2＋ Based on a Schiff Base

A new chemosensor based on a Schiff base has been designed and synthesized. Its sensing behavior toward various metal ions was investigated by fluorescence and UV-Vis spectroscopic methods. The fluorescence of the sensor was quenched and the color rapidly changed from canary yellow to brown after the addition of Cu2＋, while no changes occurred after the addition of other metal ions, which contributes to the detection of Cu2＋ with naked eyes. The fluorescence quantum yield of the ligand was calculated to be 0.52. The corresponding detection limit of Cu2＋ was 5.721 × 10-7 mol/L, and the 1：1 binding mode of the sensor with Cu2＋ was revealed by Job＇s plot.

Synthesis and Characterization of Novel Azo-containing or Azoxy-containing Schiff Bases and Their Antiproliferative and Cytotoxic Activities

A series of novel Schiff base derivatives was designed and synthesized from 3,3＇-azobenzaldehyde and 3,3＇-azoxybenzaldehyde. The newly synthesized compounds were characterized by FTIR, ^1H NMR, MS and elemental analysis and tested for their in vitro antiproliferative activities against HeLa cell lines. At the same time, the impact on the antitumor activity of the sulfanilamido, benzamido, phenolic hydroxyl or thiourea groups was investigated and discussed. Compounds 4, 6 and 10 were found to exhibit strong cytotoxic activity.

Spectral Characterization and Antimicrobial Activity of Some Schiff Bases Derived from 4-Chloro-2-aminophenol and Various Salicylaldehyde Derivatives

A series of N-（5-chloro-2-hydroxyphenyl）-（3/4/5-substituted）-salicylaldimines （I--XI） were synthesized using appropriate synthetic route. Their structures were characterized by FT-IR, UV-Visible, ESI-MS, 1H and 13C NMR spectroscopic techniques and analytical methods. The crystal structure of N-（5-chloro-2-hydroxyphenyl）-5-bromo- salicylaldimine （V） was determined by X-ray diffraction at room temperature. Relationship between the melting points and the structures of the compounds was examined. Antimicrobial activity of the compounds was evaluated against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Proteus mirabilis. Antifungal activities were reported for Candida albicans. Schiff bases showed considerable antimicrobial activity against S. aureus, S, epidermidis and C. albicans. N-（5-Chloro-2-hydroxyphenyl）-3-hydroxy-salieylaldimine （II） has the broadest and highest antimicrobial activity according to the others.

Synthesis and Fungicidal Activity of Some Novel Thiazole Schiff Bases Derived from Benzo[d][1,3]dioxole

A series of novel thiazole Schiff base derivatives containing benzo[d][1,3]dioxole moiety was designed, synthesized and screened for their fungicidal activities. The preliminary results demonstrated that compounds 6p, 6q and 6r possessed potent activities against Phytophthora infestans, Pyricularia oryzae and Septoria tritici in vitro. Compounds 6d and 6r exhibited remarkable activities against Botrytis cinerea（whole plant） and Phytophthora in- festans（leaf disk） respectively in vivo, which were identified as the most promising candidates for further study and could be used as possible lead compounds for developing new fungicides.

Synthesis of 4-aminoantipyrine Schiff bases and their antimicrobial activities

Various compounds of 4-aminoantipyrine Schiff bases(M1–M12) were synthesized via a condensation reaction of 4-aminoantipyrine with different benzaldehydes through a conventional method of refluxing the mixture for 3–4 h. The synthesized Schiff bases were characterized by using elemental analyses, FT-IR, UV-Vis, Mass, 1 H and 13 C NMR spectroscopy. The antimicrobial activity of the synthesized Schiff bases was investigated against 12 bacterial strains(Mycobacterium smegmatis, Bacillus cereus, Bacillus subtilis, Enterococcus faecalis, Staphylococcus epidermidis, Klebsiella pneumonia, Escherichia coli, Enterobacter cloacae, Klebsiella oxytoca, Proteus vulgaris, Enterobacter aerogenes, and Pseudomonas aeruginosa), and antifungal activities were tested against seven fungal strains(Aspergillus flavus, Aspergillus carbonarious, Aspergillus parasiticus, Aspergillus fumigatus, Aspergillus niger, Fusarium verticillioides and Fusarium proliferatum). The antimicrobial activities of the synthesized compounds were compared with standard streptomycin and nalidixic acid. The results obtained from antibacterial assay indicated that M1–M12 inhibited potential growth of Proteus vulgaris with minimum inhibitory concentrations(MICs) ranging from 15.6–250 μg/mL compared with the standard nalidixic acid with an MIC of 500 μg/mL. Moreover, we could conclude that most of the tested compounds experienced mild to low activities at 15.6 μg/mL. Their activities could be attributed to their low concentration s. The antifungal analysis showed that the tested fungi were not sensitive to the prepared Schiff bases at the prepared concentration of 500 μg/mL. Therefore, we recommended further analysis on both cytotoxicity and minimum bactericidal concentration(MBC) to ascertain their potential effects against human cells.