吖啶-4-甲酰胺衍生物的合成与表征

吖啶类衍生物作为生物大分子探针具有广阔应用前景。本文以4-羧基吖啶酮为母体,在4位上引入N-（2-二甲氨基）乙基,并进一步在9位引入α-丙氨酸或N-（2-二甲氨基）乙基,合成了3种吖啶-4-甲酰胺衍生物：N-（2-二甲氨基）乙基-9-氯吖啶-4-甲酰胺（NCAF）、9-[（N-2-二甲氨乙基）吖啶-4-甲酰胺]-α-丙...     

羧基苯偶氮基杯[4]芳烃衍生物的合成、表征及光谱特性

以邻、间、对氨基苯甲酸和杯 [4]芳烃为原料 ,经重氮化 -偶联反应合成了发色邻、间、对羧基苯偶氮基杯 [4]芳烃 ,产物的结构经 IR,1H NMR和元素分析表征 ;研究了它们的生色原理和光谱性能。结果表明它们是一类新型指示剂和具有新型配位空腔的主体分子。     

Synthesis,Structural, and Theoretical Studies of Quinazoline-2,4-dione Derivatives

New quinazolin-2,4-dione derivatives have been synthesized and fully characterized. The new derivatives were synthesized using 3-(2-imino-4-oxo-3H,4H,5H-thiazolidin-3-yl)-1H-quinazolin-2,4-dione by nucleophilic addition mechanism. DFT calculations using B3LYP/6–311++G(d,p) level of the theory were used to investigate the molecular structures and the relative stabilities of the anticipated isomers (E and Z). Both experimental and theoretical calculations confirmed the higher stability of the Z-isomers compared to the E-isomers. The former is stabilized by two intramolecular hydrogen bonds compared to only one in the latter isomer. The frontier orbital calculations (HOMO and LUMO), and the energy gap confirmed the stability of the molecules.     

三种小檗碱衍生物的结构性质及与DNA作用的理论研究

运用Materials Studio程序的DMol3模块对小檗碱衍生物(即9-氧-二胺乙基小檗碱)分别与乙醛、苯甲醛和l-萘醛发生缩合反应所得产物的几何结构和性质(振动频率、反应活性及热力学性质)进行了理论研究,得到了分子的稳定几何构型、Fukui指数、前线分子轨道和热力学性质.通过计算得到的吉布斯自由能的改变量,预测...     

一种ALS型胆固醇衍生物的合成及凝胶性研究

以胆固醇、丁二酸酐、对羟基苯甲醛、对硝基苯乙腈等为原料,经过三步反应,以较高产率合成了一种基于α-苯基肉桂腈单元的ALS型胆固醇衍生物。考察了其在十二种代表性有机溶剂中的凝胶性能,发现它可在DMF中形成稳定的分子凝胶,这是一种新的有机小分子凝胶因子。     

咪唑类离子液体的合成和光谱表征

以N-甲基咪唑为原料合成了离子液体氯化1-丁基-3-甲基咪唑盐([BMIm]Cl)、1-丁基-3-甲基咪唑氟硼酸盐([BMIm]BF4)、1-丁基-3-甲基咪唑六氟磷酸盐([BMIm]PF6),并对合成的产物作了紫外光谱、红外光谱、核磁共振的结构表征。     

Theoretical and Experimental Spectroscopic Analysis of Cyano-Substituted Styrylpyridine Compounds

A combined theoretical and experimental study on the structure, infrared, UV-Vis and ¹H NMR data of trans-2-(m-cyanostyryl)pyridine, trans-2-[3-methyl-(m-cyanostyryl)] pyridine and trans-4-(m-cyanostyryl)pyridine is presented. The synthesis was carried out with an efficient Knoevenagel condensation using green chemistry conditions. Theoretical geometry optimizations and their IR spectra were carried out using the Density Functional Theory (DFT) in both gas and solution phases. For theoretical UV-Vis and ¹H NMR spectra, the Time-Dependent DFT (TD-DFT) and the Gauge-Including Atomic Orbital (GIAO) methods were used, respectively. The theoretical characterization matched the experimental measurements, showing a good correlation. The effect of cyano- and methyl-substituents, as well as of the N-atom position in the pyridine ring on the UV-Vis, IR and NMR spectra, was evaluated. The UV-Vis results showed no significant effect due to electron-withdrawing cyano- and electron-donating methyl-substituents. The N-atom position, however, caused a slight change in the maximum absorption wavelengths. The IR normal modes were assigned for the cyano- and methyl-groups. ¹H NMR spectra showed the typical doublet signals due to protons in the trans position of a double bond. The theoretical characterization was visibly useful to assign accurately the signals in IR and ¹H NMR spectra, as well as to identify the most probable conformation that could be present in the formation of the styrylpyridine-like compounds.     

苯菌酮的谱学分析与结构特征

以3,4,5-三甲氧基甲苯和5-溴-2-甲氧基-6-甲基苯甲酰氯为原料,在氯苯溶液中,无水三氯化铁的催化下,合成并分离出苯菌酮(3′-溴-2,3,4,6′-四甲氧基-2′,6-二甲基二苯酮).通过红外光谱(FT-IR)、氢谱核磁共振谱(1H NMR)、紫外-可见光谱(UV-Vis)、高效液相色谱(HPLC)以及单晶X-...     

Optimized Synthesis of New Thiosemicarbazide Derivatives with Tuberculostatic Activity

Original results are presented in the field of research that addresses the extension of the reaction of residue of acyl-thiosemicarbazide fixation on the structure of 5-nitrobenzimidazole by a sulphonic group. The aim of the study is the increase of new thiosemicarbazide derivatives’ applicative potential in the field of biochemistry, with a wide range of medical applications. The newly obtained compounds were characterized by using elemental analysis and spectral analysis (FT-IR and ¹H NMR). A study regarding the optimization of the chemical reactions was made. The performed in vitro biological tests confirmed the tuberculostatic activity of three newly obtained compounds against Mycobacterium tuberculosis.     

Synthesis,X-ray Structure,Spectroscopic Properties and DFT Studies of a Novel Schiff Base

A series of Schiff bases, salicylideneaniline derivatives 1–4, was synthesized under mild conditions and characterized by ¹H NMR, HRMS, UV-Vis and fluorescence spectra, and single-crystal X-ray diffraction. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess an intramolecular six-membered-ring hydrogen bond. A weak intramolecular C–H···F hydrogen bond is also observed in fluoro-functionalized Schiff base 4, which generates another S(6) ring motif. The C–H···F hydrogen bond further stabilizes its structure and leads it to form a planar configuration. Compounds 1–3 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 4 shows remarkable dual emission originated from the excited-state intramolecular charge transfer (ESICT) and excited-state intramolecular proton transfer (ESIPT) states. Furthermore, the geometric structures, frontier molecular orbitals (MOs) and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT) and time-dependent DFT calculations.     

Synthesis, Spectroscopic and Structural Properties of Heteropolynuclear Cyano-Bridged Complexes

Two novel cyano-bridged heteropolynuclear complexes, [Zn(mprd)₂Ni(μ-CN)₄]_n (1) and {[Cd(mprd)₂Ni(μ-CN)₄]·2H₂O}_n (2), (mprd = 4-methylpyrimidine), have been synthesized and characterized by FT-IR spectroscopy, Raman spectroscopy, thermal analyses (TG, DTG and DTA) and elemental analyses. The crystal structure of the 1 was determined by X-ray single crystal diffraction. The complex crystallizes in the monoclinic, space group C2/c. The crystal structure of 1 consists of a corrugated 2D network in which the Zn(II) and Ni(II) atoms are linked by cyanide groups. The Ni(II) atom is four coordinate with four carbon atoms in a square-planar geometry; and, the Zn(II) atom is six coordinate with four cyanide-nitrogen and two mprd-nitrogen atoms with a distorted octahedral geometry. The shifts of the cyano stretching vibration are evidence for the formation of cyano bridges. Vibration assignments are given for all the observed bands and the spectral features support the structure of the polymeric complexes.     

新型含噻吩类衍生物的合成与光谱特性

在四(三苯基膦)钯(Pd(PPh3)4催化作用下,通过催化偶合法可合成5,8-二噻基-萘基喹喔啉(DThQx(ace))和3,6-二噻基-哒嗪(DThPD)两种新型噻吩衍生物,同时也可合成了4,7-二噻基-2,1,3-苯并噻二唑(DThB)和1,4-二噻基-苯(DThPh),上述化合物产率分别为75%,78%,82%和67%。用红外光谱、核磁共振谱、元素分析等方法进行了表征,并对噻吩与不同芳香环构成的衍生物的紫外-可见吸收光谱和荧光光谱进行了对比研究。这四种化合物的紫外-可见吸收光谱中分别在435,336,446,325 nm处有最大吸收波长。其中DThQx(ace)、DThB和DThPh的荧光光谱中分别在564,568 nm和384 nm处观察到荧光,而DThPD无荧光。     

Synthesis,Crystallographic, Quantum Chemical,Antitumor, and Molecular Docking/Dynamic Studies of 4-Hydroxycoumarin-Neurotransmitter Derivatives

In this contribution, four new compounds synthesized from 4-hydroxycoumarin and tyramine/octopamine/norepinephrine/3-methoxytyramine are characterized spectroscopically (IR and NMR), chromatographically (UHPLC-DAD), and structurally at the B3LYP/6-311++G*(d,p) level of theory. The crystal structure of the 4-hydroxycoumarin-octopamine derivative was solved and used as a starting geometry for structural optimization. Along with the previously obtained 4-hydroxycoumarin-dopamine derivative, the intramolecular interactions governing the stability of these compounds were quantified by NBO and QTAIM analyses. Condensed Fukui functions and the HOMO-LUMO gap were calculated and correlated with the number and position of OH groups in the structures. In vitro cytotoxicity experiments were performed to elucidate the possible antitumor activity of the tested substances. For this purpose, four cell lines were selected, namely human colon cancer (HCT-116), human adenocarcinoma (HeLa), human breast cancer (MDA-MB-231), and healthy human lung fibroblast (MRC-5) lines. A significant selectivity towards colorectal carcinoma cells was observed. Molecular docking and molecular dynamics studies with carbonic anhydrase, a prognostic factor in several cancers, complemented the experimental results. The calculated MD binding energies coincided well with the experimental activity, and indicated 4-hydroxycoumarin-dopamine and 4-hydroxycoumarin-3-methoxytyramine as the most active compounds. The ecotoxicology assessment proved that the obtained compounds have a low impact on the daphnia, fish, and green algae population.     

含三嗪结构吗啉衍生物的合成与表征

文章以三聚氯氰、脂肪胺、二乙醇胺、氯磺酸为原料,分三步合成了含有三嗪结构的吗啉衍生物,所得产物纯度好,收率高。并用FT-IR(傅立叶红外光谱仪)、ESI-MS(质谱)对产物结构进行了表征,证实所合成的产物结构正确。     

Synthesis,DNA Binding,and Antiproliferative Activity of Novel Acridine-Thiosemicarbazone Derivatives

In this work, the acridine nucleus was used as a lead-compound for structural modification by adding different substituted thiosemicarbazide moieties. Eight new (Z)-2-(acridin-9-ylmethylene)-N-phenylhydrazinecarbothioamide derivatives (3a–h) were synthesized, their antiproliferative activities were evaluated, and DNA binding properties were performed with calf thymus DNA (ctDNA) by electronic absorption and fluorescence spectroscopies. Both hyperchromic and hypochromic effects, as well as red or blue shifts were demonstrated by addition of ctDNA to the derivatives. The calculated binding constants ranged from 1.74 × 10⁴ to 1.0 × 10⁶ M⁻¹ and quenching constants from −0.2 × 10⁴ to 2.18 × 10⁴ M⁻¹ indicating high affinity to ctDNA base pairs. The most efficient compound in binding to ctDNA in vitro was (Z)-2-(acridin-9-ylmethylene)-N-(4-chlorophenyl) hydrazinecarbothioamide (3f), while the most active compound in antiproliferative assay was (Z)-2-(acridin-9-ylmethylene)-N-phenylhydrazinecarbothioamide (3a). There was no correlation between DNA-binding and in vitro antiproliferative activity, but the results suggest that DNA binding can be involved in the biological activity mechanism. This study may guide the choice of the size and shape of the intercalating part of the ligand and the strategic selection of substituents that increase DNA-binding or antiproliferative properties.     

两个新的苯并噻唑衍生物的合成与光物理性质

以苯并噻唑、苯乙酰基和吡啶阳离子为电子受体，二乙烯基苯为共轭桥，合成了两个新的A-π-A’型苯并噻唑衍生物：4-（2-苯并噻唑）-乙烯基查尔酮（1）和4-{4-[2-（苯并噻唑）乙烯基]苯乙烯基}-N-甲基吡啶碘盐（2）．研究了它们在溶液和固体基质中的光物理性质．研究发现：染料2由于具有较强的极性和较好的平面性，从而具有较长的吸收、发射峰和较强的荧光发射．有机染料在聚甲基丙烯酸甲酯／溶胶-凝胶复合玻璃中的发光行为与聚甲基丙烯酸甲酯和溶胶-凝胶玻璃二者的基质性质有关，同时由于固体基质中分子发生聚集的可能性降低，荧光强度相对于同浓度溶液增强，稳定性提高．     

Synthesis, Characterization, and Photovoltaic Properties of Soluble TiOPc Derivatives

We have synthesized soluble TiOPc derivatives containing alkoxy groups for use as additives in dye-sensitized solar cells (DSSCs). The DSSC devices containing these TiOPc derivatives exhibited short-circuit current densities of 8.49~10.04 mA/cm² and power conversion efficiencies of 2.73~3.62 % under AM 1.5 illumination and 100 mW/cm² irradiation.     

硼氟二吡咯亚甲基衍生物的合成、表征及光物理性质的研究

成功合成了中位为2-喹啉噻吩基硼氟二吡咯亚甲基和对葡萄糖四乙酸酯苯基的化合物4,4-二氟-8-[5'-(2-喹啉基)-2-噻吩基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省和4,4-二氟-8-[4'-(2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖-1-氧基)苯基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省,通过核磁进行表征。研究了这两个化合物在二氯甲烷中的紫外可见吸收光谱和荧光光谱,研究了化合物在薄膜和固体状态下的吸收光谱和荧光光谱,同时通过研究电化学性质得到化合物的HOMO和LUMO轨道。