Synthesized of Sporopollenin-Immobilized Schiff Bases and Their Vanadium(IV) Sorption Studies

This study investigated the potential use of a biologic polymer Lycopodium clavatum spores (Sporopollenin) for removal of vanadium ions (V(IV)) from aqueous solution. Three Schiff base derivative compounds immobilized sporopollenin were prepared and characterized. Immobilized sporopollenin was characterized via a scanning electron microscope, elemental analysis, infrared spectroscopy and thermal analysis techniques. The sorption capacities of the immobilized surfaces toward V(IV) ions were investigated by batch sorption experiments. V(IV) concentration, initial pH and the temperature effects were studied. The isotherm data of V(IV) ions were correlated reasonably well both Langmuir, Freundlich sorption isotherm. The thermodynamic studies showed that the V(IV) sorption onto immobilized sporopollenin derivatives is a spontaneous, endothermic and a chemical reaction.     

两种新型席夫碱的合成与表征

以对羟基苯乙醇为原料,首先经过三步反应得到中间体5-碘乙基水杨醛,然后分别与邻苯二胺、4'-乙烯基-3,4-联苯二胺反应,得到两种不同的新型席夫碱,分别对各步反应中间体以及两种目标席夫碱进行红外、核磁表征,确定结构。     

含靛红基新型席夫碱的合成与表征

以无水乙醇作为溶剂,回流条件下,通过靛红、N-甲基靛红、N-苄基靛红和5-甲基靛红与4-氨基安替比林的缩合反应合成了系列Schiff碱类化合物,对加样方式、物料比、反应温度和反应时间等反应条件进行了研究,产物通过IR1、H NMR、MS和元素分析进行了结构鉴定。其中靛红与4-氨基安替比林在乙醇中,物料比(靛红∶4-氨基安替比林)为1∶0.9,78℃反应1 h,产物收率可达到94.4%。     

N-1,3,4-噻二唑基取代水杨醛Schiff碱的合成与表征

以氨基硫脲和羧酸为原料,在浓硫酸或三氯氧磷作用下合成了2-氨基-5-烃基(芳基)-1,3,4-噻二唑类化合物1,并通过化合物1与水杨醛的缩合反应合成了相应的含1,3,4-噻二唑基席夫碱类化合物3。研究结果表明在合成芳基取代的1,3,4-噻二唑时,浓硫酸作脱水剂的反应收率较低,三氯氧磷作脱水剂时得到较高的收率。同时研究了不同反应条件对化合物3的收率的影响,发现当反应以对甲苯磺酸为催化剂,在乙醇溶液中加热回流时的收率较高。合成的目标化合物的结构用IR、1H NMR、13C NMR等进行了分析与表征。     

Ruthenium(III) Complexes of Heterocyclic Tridentate (ONN) Schiff Base: Synthesis,Characterization and its Biological Properties as an Antiradical and Antiproliferative Agent

The current work reports the synthesis, spectroscopic studies, antiradical and antiproliferative properties of four ruthenium(III) complexes of heterocyclic tridentate Schiff base bearing a simple 2′,4′-dihydroxyacetophenone functionality and ethylenediamine as the bridging ligand with RCHO moiety. The reaction of the tridentate ligands with RuCl₃·3H₂O lead to the formation of neutral complexes of the type [Ru(L)Cl₂(H₂O)] (where L = tridentate NNO ligands). The compounds were characterized by elemental analysis, UV-vis, conductivity measurements, FTIR spectroscopy and confirmed the proposed octahedral geometry around the Ru ion. The Ru(III) compounds showed antiradical potentials against 2,2-Diphenyl-1-Picrylhydrazyl (DPPH) and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals, with DPPH scavenging capability in the order: [(PAEBOD)RuCl₂] > [(BZEBOD)RuCl₂] > [(MOABOD)RuCl₂] > [Vit. C] > [rutin] > [(METBOD)RuCl₂], and ABTS radical in the order: [(PAEBOD)RuCl₂] < [(MOABOD)RuCl₂] < [(BZEBOD)RuCl₂] < [(METBOD)RuCl₂]. Furthermore, in vitro anti-proliferative activity was investigated against three human cancer cell lines: renal cancer cell (TK-10), melanoma cancer cell (UACC-62) and breast cancer cell (MCF-7) by SRB assay.     

生理活性氨基酸Schiff碱的合成与表征

用天冬酰胺分别与水杨醛、邻香草醛、2 ,4 二羟基苯甲醛在甲醇中反应 ,然后加入异丙醇析出产物的方法合成了三种氨基酸Schiff碱 ,产物收率分别为 84 3 %、81 2 %、76 7%。用元素分析、红外光谱、紫外光谱等手段对所合成的Schiff碱进行了表征。采用EPR技术对所合成的Schiff碱清除超氧阴离子自由基 (O2 ·)的性能进行了研究 ,结果表明 ,所合成的氨基酸Schiff碱质量浓度为 5kg/m3 时 ,对O2 ·的清除率分别达到 6 3 4%、6 2 .0 %、84 2 % ,具有明显的生理活性。     

1,4-双(邻苯甲醛基)-1,4-二氧丁烷氨基酸类Schiff碱的制备及表征

在弱碱性条件下,以水杨醛、氨基酸和1,4-二溴丁烷为原料,以DMF为溶剂,制备1,4-双（邻苯甲醛基）-1,4-二氧丁烷氨基酸类Schiff碱,并用红外光谱和核磁共振对其结构进行了表征。考察了pH值和溶剂对合成反应的影响。     

4,5-二甲基-3-腈基呋喃Schiff碱的合成与表征

以自制的4,5-二甲基-3-腈基-2-氨基呋喃与取代芳醛为主要原料,以乙醇为溶剂、醋酸为催化剂,通过回流反应合成了新型4,5-二甲基-3-腈基呋喃Schiff碱化合物。目标化合物通过IR、1HNMR、MS进行了表征。     

4-氨基-1,2,4-三氮唑并芳香醛类希夫碱的合成与表征

三氮唑环为抗真菌药物的基本药效基团,为探索芳香醛缩氨基三氮唑的合成条件,以4-氨基-1,2,4-三氮唑与芳香醛为原料,在冰醋酸催化下合成了9种芳香醛类希夫碱,收率71.6%~92.3%,并通过元素分析、IR和1H NMR确定了目标化合物的结构。其中几种鲜见文献报道。同时讨论了影响反应收率的因素。     

Electrochemical Nanogravimetric Studies of Ruthenium(III) Trichloride Microcrystals

Ruthenium (III) trichlorid solid crystals have been mechanically attached to gold and paraffin-impregnated graphite surfaces and studied in the presence of aqueous solutions of M⁺Cl⁻ electrolytes, where M⁺ = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and K₂SO₄ by cyclic voltammetry and electrochemical nanogravimetry at a quartz crystal microbalance (EQCM). The electrochemical reduction of the layered α-RuCl₃ microcrystals causes drastic changes in the composition and the structure of crystals. The comparison of the current—potential and surface mass change—potential functions belonging to the first reduction-reoxidation cycle with the subsequent ones reveals that the simple intercalation scheme described in the literature cannot be entirely valid. During the first reduction step at ca. 0.2 V vs. SCE the charge consumption is substantially higher than in the course of the further potential cycling, and the simultaneous rapid and intense mass decrease indicates that considerable chemical and structural transformations occurs. Although a loss of the surface mass cannot be entirely excluded, the frequency increase most likely is not related to the dissolution of the microcrystals, however, large amounts of water molecules and—to a much smaller extent—chloride ions leave the crystal phase, and in fact a new material, which remains strongly attached to the gold or graphite surface, is formed. The extremely high frequency change at the first reduction process during the first cycle is most likely related to the stress effect originating in the phase transition of the surface layer and/or the removal of the water rigidly coupled to the surface into voids of the immobilized microcrystals. Depending on the amount of microcrystals on the electrode surface and the experimental conditions (the nature and concentration of the contacting electrolyte, scan rate, and potential range) used, after the “break-in” cycle stable electrochemical and nanogravimetric responses develop. The several reduction and reoxidation pairs of waves in the cyclic voltammograms and the simultaneous mass changes are in connection with the wide variety of intercalation reactions and complex formation during the electrochemical transformations. The mass change was reversible, in general, during reduction mass increase, while during oxidation mass decrease occurred at medium electrolyte concentrations in three or more steps. The mass excursions are rather complicated, involving different mass increase/decrease regions as a function of potential and the composition of the contacting solution. Taking into account the layered structure of RuCl₃, the electrochemical reduction can be explained as an intercalation reaction in that mixed valence intercalation phases with a general formula K Ru [Ru Cl_3z-y (H₂O)_y] • dH₂O are formed from z (RuCl₃ · H₂O). The reduction/reoxidation waves are related to the redox transformations of Ru(III) to Ru(II) sites and the insertion/deinsertion of cations and water molecules, while the composition of the polynuclear complexes and the structure of microcrystals change.     

绿色合成香草醛缩芳胺类席夫碱及其结构表征

以香草醛和取代苯胺为原料,采用绿色合成法合成香草醛缩芳胺类席夫碱3a~3c。通过对溶剂法、无溶剂加热法和无溶剂研磨法三种不同合成方法进行了条件探讨,发现合成该类席夫碱衍生物的较优方法。所合成化合物的结构通过IR、1H NMR、13C NMR和HRMS进行了鉴定和表征。     

含噻吩环新型席夫碱的合成研究

报道了2-乙酰噻吩(中间体)和两种新席夫碱的合成。以噻吩为原料与乙酸酐反应生成中间体。并用中间体分别和邻苯二胺及邻氨基对甲苯酚在无水乙醇中反应,得到了两种新型结构的席夫碱,并对中间体和产物的合成条件分别进行了探索性试验,确定了合成它们的各自优化条件;并对它们进行了UV、IR、1H NMR和13C NMR分析。     

研磨固相法合成Schiff碱钍(IV)金属配合物

以水杨醛、邻香草醛、2,6-二氨基吡啶和硝酸钍为原料,采用研磨固相法合成了2,6-二氨基吡啶双Schiff碱钍(IV)配合物[ThL1(NO3)2] (NO3)2,[ThL2(NO3)2] (NO3)2。通过元素分析、EDTA滴定法、红外光谱分析、紫外光谱分析、热分析等方法对配合物的组成和结构进行了表征。实验结果表明,金属钍与席夫碱配体中的亚氨基氮、酚羟基氧以及硝酸根离子形成了配位数为8的配合物。     

含噻唑环席夫碱及其配合物的合成与性能研究进展

噻唑环具有良好的热稳定性和耐酸、碱及氧化等化学稳定性,而席夫碱拥有优良的配位能力,因而含噻唑环的席夫碱及其配合物已成为有机功能材料的研究热点之一.阐述了含噻唑环席夫碱的合成工艺及其在化学荧光、生物抑菌、模拟酶催化和电磁性能等方面的研究进展,最后对噻唑环席夫碱今后的研究方向作了简要的展望.     

含水杨基新型席夫碱的合成与表征

研究水杨醛分别与间苯二胺、邻氨基对甲苯酚、邻氨基苯甲醇、邻氨基苯甲醚进行反应合成了新型的席夫碱。以无水乙醇作为溶剂,在pH 7~8的条件下顺利合成了对应的Schiff碱,并对各个Schiff碱的合成条件分别进行了探索性试验,确定了合成它们的各自优化条件;产品通过元素、UVI、R1、H NMR和13C NMR分析。     

Spectroscopic Characterization and Biological Activity of Hesperetin Schiff Bases and Their Cu(II) Complexes

The three Schiff base ligands, derivatives of hesperetin, HHSB (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]isonicotinohydrazide), HIN (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]benzhydrazide) and HTSC (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]thiosemicarbazide) and their copper complexes, CuHHSB, CuHIN, and CuHTSC were designed, synthesized and analyzed in terms of their spectral characterization and the genotoxic activity. Their structures were established using several methods: elemental analysis, FT-IR, UV-Vis, EPR, and ESI-MS. Spectral data showed that in the acetate complexes the tested Schiff bases act as neutral tridentate ligand coordinating to the copper ion through two oxygen (or oxygen and sulphur) donor atoms and a nitrogen donor atom. EPR measurements indicate that in solution the complexes keep their structures with the ligands remaining bound to copper(II) in a tridentate fashion with (O^–, N, O_ket) or (O^–, N, S) donor set. The genotoxic activity of the compounds was tested against model tumour (HeLa and Caco-2) and normal (LLC-PK1) cell lines. In HeLa cells the genotoxicity for all tested compounds was noticed, for HHSB and CuHHSB was the highest, for HTSC and CuHTSC–the lowest. Generally, Cu complexes displayed lower genotoxicity to HeLa cells than ligands. In the case of Caco-2 cell line HHSB and HTSC induced the strongest breaks to DNA. On the other side, CuHHSB and CuHTSC induced the highest DNA damage against LLC-PK1.     

Development of Isatin-Based Schiff Bases Targeting VEGFR-2 Inhibition: Synthesis,Characterization, Antiproliferative Properties,and QSAR Studies

Three sets of isatin-based Schiff bases were synthesized utilizing the molecular hybridization approach. Some of the synthesized Schiff bases show significant to moderate antiproliferative properties against MCF7 (breast), HCT116 (colon), and PaCa2 (pancreatic) cancer cell lines with potency compared to reference drugs 5-fluorouracil (5-FU) and Sunitinib. Among all, compound 17 f (3-((1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino)-1-((1-(2-methoxyphenyl)-1H-1,2,3-triazol-4-yl)methyl)-5-methylindolin-2-one) exhibits promising antiproliferative properties against the MCF7 cancer cell line with 2.1-fold more potency than Sunitinib. However, among all the synthesized compounds, three (5-methylisatin derivatives) were the most effective against HCT116 in comparison to 5-FU. Compound 17 f exhibited the highest anti-angiogenic effect on the vasculature as it significantly reduced BV from 43 mm to 2 mm in comparison to 5.7 mm for Sunitinib and flow cytometry supports the arrest of the cell cycle at G1/S phases. In addition, compound 17 f also showed high VEGFR-2 inhibition properties against breast cancer cell lines. Robust 2D-QSAR studies supported the biological data.     

5-甲基-4-乙氧羰基-3-腈基-2-呋喃胺Schiff碱的合成与表征

以自制的5-甲基-4-乙氧羰基-3-腈基-2-呋喃胺与取代芳醛为主要原料,以乙醇为溶剂、醋酸为催化剂,通过回流反应合成了新型5-甲基-4-乙氧羰基-3-腈基-2-呋喃胺Schiff碱化合物。目标化合物通过IR、1HNMR、MS进行了表征。