Structure, solution chemistry, antiproliferative actions and protein binding properties of non-conventional platinum(II) compounds with sulfur and phosphorus donors

Twelve Pt(II) complexes with cis-PtP(2)S(2) pharmacophores (where P(2) refers to two monodentate or one bidentate phosphane ligand and S(2) is a dithiolato ligand) were prepared, characterized and evaluated as potential antiproliferative agents. The various compounds were first studied from the structural point of view; afterward, their solubility properties as well as their solution behaviour were analyzed in detail. Antiproliferative properties were specifically evaluated against A2780 human ovarian carcinoma cells, either resistant or sensitive to cisplatin. For comparison purposes similar studies were carried out on four parent cis-dichloro bisphosphane Pt(II)complexes. On the whole, the cis-PtP(2)S(2) compounds displayed significant antiproliferative properties while the cis-PtP(2)Cl(2) (cis-dichloro bisphosphane Pt(II)) compounds revealed quite poor biological performances. To gain further insight into the molecular mechanisms of these bisphosphane Pt(II) compounds, the reactions of selected complexes against the model protein cytochrome c were investigated by ESI-MS and their adduct formation explored. A relevant reactivity with cyt c was obtained only for cis-PtP(2)Cl(2) compounds, whereas cis-PtP(2)S(2) compounds turned out to be nearly unreactive. The obtained results are interpreted and discussed in the frame of the current knowledge of anticancer platinum compounds and their structure-activity-relationships. The observation of appreciable antiproliferative effects for the relatively inert cis-PtP(2)S(2) compounds strongly suggests that these compounds will undergo specific activation within the cellular environment.     

Determination of the volatile composition in brown millet, milled millet and millet bran by gas chromatography/mass spectrometry

The volatile compounds from brown millet (BM), milled millet (MM) and millet bran (MB) were extracted using simultaneous distillation/extraction with a Likens-Nickerson apparatus. The extracts were analysed using gas chromatography coupled with mass spectrometry (GC-MS). A total of 65 volatile compounds were identified in all of the samples. Among these compounds, 51, 51 and 49 belonged to BM, MM and MB, respectively. Aldehydes and benzene derivatives were the most numerous among all of the compounds. Three compounds (hexanal, hexadecanoic acid and 2-methylnaphthalene) were dominant in the BM and MM materials. Eight compounds (hexanal, nonanal, (E)-2-nonenal, naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, hexadecanoic acid and 2-pentylfuran) were dominant in the MB materials. Apart from the aromatic molecules, which were present in all fractions, compounds present only in BM, MM or MB were also identified.     

三(2-甲基-2-苯基丙基)锡芳氧乙酸酯的合成

三（２－甲基－２－苯基丙基）锡芳氧乙酸酯的合成刘宝殿,宁志刚,朱东升,包明（东北师范大学化学系,长春,１３００２４）关键词三（２－甲基－２－苯基丙基）锡芳氧乙酸酯,三（２－甲基－２－苯基丙基）氢氧化锡,芳氧乙酸,杀螨活性１９６６年Ｒｅｉｃｈｌｅ［１］...     

Self-assembly of diorganotin(IV) moieties and 2-pyrazinecarboxylic acid: syntheses, characterizations and crystal structures of monomeric, polymeric or trinuclear macrocyclic compounds

A series of diorganotin(IV) compounds of the type [R(2)Sn(pca)Cl](3)(R = CH(3); (n)Bu; C(6)H(5); C(6)H(5)CH(2); Hpca = 2-pyrazinecarboxylic acid), R(2)Sn(pca)(2)(mH(2)O)xnH(2)O (m= 1: R = CH(3), n= 2, R =(n)Bu, n= 0; m= 0, n= 0: R =(n)Bu, C(6)H(5), C(6)H(5)CH(2)) and (Et(3)NH)(+)[R(2)Sn(pca)(2)Cl](-)xmH(2)O (m= 0: R = CH(3), (n)Bu, C(6)H(5)CH(2); m= 1: R = C(6)H(5)) have been obtained by reactions of 2-pyrazinecarboxylic acid with diorganotin(iv) dichloride in the presence of sodium ethoxide or triethylamine. All compounds were characterized by elemental, IR and NMR spectra analyses. Except for compounds, and, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that compounds and were trinuclear macrocyclic structures with six-coordinate tin(IV) atoms, compounds and were monomeric structures with seven-coordinate tin(IV) atoms, compounds and were polymeric chain structures with seven-coordinate tin(IV) atoms and compounds and were stannate with seven-coordinate tin(IV) atoms.     

Isolation of toxic compounds from wild Phaeocystis globosa

Two new compounds, namely taenialactam C and globorin A (1 and 2), as well as six known compounds, cornoside (3), 2-phenylethyl-b-D-glucoside (4), 3-isopropyl-5-acetoxycyclohexene-2-one-1 (5), 4-methyl-phenol (6), 5-[(2S)-2-aminobutyl]-2-methyl-phenol (7), and 1-(4-methylphenyl)-1-propanone (8) were isolated from wild Phaeocystis globosa. The structures of the new compounds were established by detailed spectroscopic analysis and by comparison with spectral data of related known compounds. The structures of the known compounds were identified by comparing their spectroscopic data with those reported in the literature. This paper also reports toxicity properties of the eight compounds against the brine shrimp Artemia salina and juvenile Epinephelus akaara fish. Some of these compounds showed significant lethality on the brine shrimp A. salina and the juvenile E. akaara fish.     

Synthesis and anti-bacterial activities of some novel Schiff bases derived from aminophenazone

A series of 1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one-containing Schiff bases were synthesized, characterized and screened for their antibacterial activities. The structures of the synthesized compounds were established by spectroscopic (FT-IR, 1H-NMR, 13C-NMR, MS) and elemental analyses. The anti-bacterial activities (with MIC values) of compounds were evaluated. The anti-bacterial screening results reveal that among the six compounds screened, four compounds showed moderate to good anti-bacterial activity. Among the tested compounds, the most effective compounds against four bacterial strains, viz. Escherichia coli, Staphylococcus aureus, Salmonella typhimurium and Streptococcus pyogenes, are [(2-chlorobenzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one (4) and [(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino)methyl]benzonitrile (5) with MIC values of 6.25 μg/mL.     

Characteristic aroma compounds from different pineapple parts

Characteristic aroma volatile compounds from different parts of cayenne pineapple were analyzed by headspace-solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC/MS). The main volatile compounds were esters, terpenes, ketones and aldehydes. The number and content of aroma compounds detected in pulp were higher than those found in core. In pulp, the characteristic aroma compounds were ethyl 2-methylbutanoate, ethyl hexanoate, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF), decanal, ethyl 3-(methylthio)propionate, ethyl butanoate, and ethyl (E)-3-hexenoate; while in core the main compounds were ethyl 2-methylbutanoate, ethyl hexanoate and DMHF. The highest odor units were found to correspond to ethyl 2-methylbutanoate, followed by ethyl hexanoate and DMHF. The odor units found for pulp were higher than those for core.     

Dendronized diruthenium compounds via the copper(I)-catalyzed click reaction

Novel Ru2-containing dendritic compounds were prepared from the CuI-catalyzed 1,3-dipolar cycloaddition between Ru2 compounds containing one or two ethynes, Ru2(D(3,5-Cl2Ph)F)4-n(DMBA-4-C2H)n with n=1 and 2, and azidopoly(benzyl ether) dendrons. These new compounds were also characterized with X-ray diffraction and voltammetric techniques.     

六核钴原子簇化学 3: 一些含Co~6八面体簇骼的原子簇化合物的合成、结构和电化学性质

(R~8P)~4-nCoX~n(R=Ph,Et 等;X=C,B=1,2)与Na~E~x(E=S,Se;X=1,2)在DMF或DMF/乙醇介质中反应得到了一系列六核钴的原子簇化合物Co~6(μ~3-E)~8(PR~3)~6.这些化合物含有正规的或畸变的Co~6八面簇骼.化合物可以用I~2氧化生成正一价的簇合物而不改变簇骼的几何构型,反达来,正一价的簇合物也可以被苊烯钠还生成中性的簇合物.本文还研究了这些化合物的电化学性质并提出了氧化还原反应的电子传递过程.     

A new tricyclic-alpha,beta-unsaturate ketone and a new delta-hexano lactone glycoside from Adenocaulon himalaicum

Two new compounds, a tricyclic-alpha,beta-unsaturate ketone (adenocaulone) (1) and a delta-hexanolactone glycoside (adenocaulolide) (2), along with 10 known compounds 3-12 were isolated from Adenocaulon himalaicum Edgew. Their structures were elucidated by spectroscopic methods (IR, MS, 1H, 13C and 2D NMR). In addition, the antibacterial activity of compounds 2, 3 and 4 were tested.     

Anti-Inflammatory Effects of Auranamide and Patriscabratine—Mechanisms and In Silico Studies

Auranamide and patriscabratine are amides from Melastoma malabathricum (L.) Smith. Their anti-inflammatory activity and nuclear factor erythroid 2-related factor 2 (NRF2) activation ability were evaluated using Escherichia coli lipopolysaccharide (LPSEc)-stimulated murine macrophages (RAW264.7) and murine hepatoma (Hepa-1c1c7) cells, respectively. The cytotoxicity of the compounds was assessed using a 3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide (MTT) assay. The anti-inflammatory activity was determined by measuring the nitric oxide (NO) production and pro-inflammatory cytokines (Interleukin (IL)-1β, Interferon (IFN)-γ, tumour necrosis factor (TNF)-α, and IL-6) and mediators (NF-κB and COX-2). NRF2 activation was determined by measuring the nicotinamide adenine dinucleotide phosphate hydrogen (NADPH) quinone oxidoreductase 1 (NQO1), nuclear NRF2 and hemeoxygenase (HO)-1. In vitro metabolic stability was assessed using the mouse, rat, and human liver microsomes. The compounds were non-toxic to the cells at 10 μM. Both compounds showed dose-dependent effects in downregulating NO production and pro-inflammatory cytokines and mediators. The compounds also showed upregulation of NQO1 activity and nuclear NRF2 and HO-1 levels. The compounds were metabolically stable in mouse, rat and human liver microsomes. The possible molecular targets of NRF2 activation by these two compounds were predicted using molecular docking studies and it was found that the compounds might inhibit the Kelch domain of KEAP1 and GSK-3β activity. The physicochemical and drug-like properties of the test compounds were predicted using Schrodinger small molecule drug discovery suite (v.2022-2).     

FUNCTIONAL POLYMERS 65. SYNTHESIS AND BRIEF CHARACTERIZATION OF SURFACE ACTIVE 2(2-HYDROXYPHENYL)2H-BENZO-TRIAZOLE ULTRAVIOLET STABILIZERS

A number of 2(2-hydroxyphenyl)2H-benzotriazoles substituted in the 5-position with reactive hydroxyl and carboxyl groups have been synthesized. They include compounds with a tert butyl substitution in the 3-position or without substitution. The latter compounds were subjected to a reaction with N-hydroxy-methyl-(meth)acrylamide to form acrylic polymerizable 3(meth)acrylamidomethyl-2(2-hydroxyphenyl)2H-benzotriaz-oles. Hydroxyl reactive compounds were allowed to react with long chain acids, compounds with carboxyl groups with long chain hydrocarbon, fluorocarbon or silicon oligomer alcohols. The polymerizable 2(2-hydroxyphenyl)2H-benzotriazoles were then copolymerized with methyl methacrylate. Films made from such polymers showed by contact angle measurements, substantial migration of the fluorocarbon or silicon component to the surface of the film.     

Preparation and Properties of Inclusion Compounds of Cyclodextrins with Organotransition Metal Complexes

Inclusion compounds of transition metal complexes of cycloocta-1,5-diene (cod) and norbornadiene (nbd) with cyclodextrins were prepared. Two-to-one (cyclodextrin:guest) inclusion compounds were obtained in high yields by the treatment of β-cyclodextrin (β-CD) with [(L)RhCl]₂ (L = nbd or cod) and 1:1 inclusion compounds were obtained by the reaction of β-CD with (cod)PtX₂ (X = Cl, Br, or I) in high yields, while γ-CD formed 1:1 inclusion compounds with (cod)PtX₂ (X = Br or I). The formation of inclusion compounds is selective. α-CD did not form inclusion compounds with any transition-metal complexes with cycloocta-1,5-diene. Thermogravimetric measurements show that the complexes are stabilized by inclusion in cyclodextrin cavities. The inclusion compounds were characterized by ¹ H-NMR, IR, UV, and circular dichroism spectra.     

Chemical constituents of the Gorgonian Dichotella fragilis (Ridleg) from the South China Sea

Two new steroidal glycosides, fragilioside A (1) and fragilioside B (2), along with five known compounds (3-7) were isolated from the gorgonian Dichotella fragilis (Ridleg) collected from the South China Sea. The structures of the new compounds (1 and 2) were elucidated by comprehensive analysis of spectral data, especially 2D NMR. The brine shrimp lethality and antifouling activity of the isolated compounds were also evaluated.     

New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

Nd、Er—氟哌酸配合物的合成、结构及其抗菌活性

引言 氟哌酸(norfloxacin),属于含氟喹诺酮类化合物,是一种八十年代发展起来的广谱抗菌药。在临床上,它已被广泛用于尿道感染、肠道感染等领域,疗效显著。此外,在烧伤领域及对性病的治疗中也得到了应用。为了考察金属离子对氟哌酸抗菌作用的影响,探测氟哌酸抗菌作用的本质,我们合成了氟哌酸与Nd~(3+)、Er~(3+)形成的固体配合物(它们在水和甲醇中的溶解度都明显优于氟哌酸),并对其结构进行了初步探讨,又将它们分别对革兰氏阴性菌(大肠杆菌、痢疾杆菌)和革兰氏阳性菌(金黄色葡萄球菌)采用纸片扩散法进行了抗菌活性实验。     

3-取代-6-吡唑基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类衍生物的合成及生物活性

将5-取代吡唑-3-甲酸乙酯1位甲基化,经水解反应得到3种中间体1-甲基-5-取代1H-吡唑-3-甲酸（2a~2c）;以不同取代的羧酸为原料经一系列反应合成6种中间体3-取代4-氨基-5-巯基-1,2,4-均三唑（3a~3f）;将中间体（2a~2c）和（3a~3f）在三氯氧磷条件下反应,合成出18种1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类化合物(4a~4r),均未见文献报道。 通过IR、1H NMR、13C NMR和元素分析表征了化合物结构。 初步的生物活性测试结果显示,所合成的化合物均表现出不同程度的生长素活性和抑菌活性。 并选取抑菌活性较好的两个化合物进行抗菌药物最低抑菌浓度(MIC)的测定。     

GC-MS法测定大蒜中的挥发性物质

大蒜(AlliumsatiuvmL.)是多年生草本百合科植物大蒜的鳞茎,按皮的颜色不同可分为紫皮蒜和白皮蒜两种。大蒜原产于意大利的西西里岛,约在两千多年前传入我国。大蒜不仅是极佳的调味食品,而且还有很好的药用功能。近年来,科学家研究证明,大蒜是一种健康食品,有助人体防病保健、延年益寿,是药食兼优的佳品,对人体具有多种药用价值。大蒜具有一种强烈的蒜臭气味,这种特殊的气味由许多复杂的硫化物组成。这类有机硫化物可促进消化,健胃整肠,强化抗菌作用,消肿止痛,改善机体机能的功能,大蒜中还含有乙烷硫代磺酸乙酯和二烯丙基三硫化物等,能阻断强烈致癌物质亚硝胺类在胃部的形成和积累,可预防胃癌、食道癌、肝癌、鼻咽癌的发生。本试验采用"同时蒸馏-萃取方法"(simultaneousdistillationandextraction,SDE)提取白皮和紫皮大蒜的挥发性成分,经GC-MS分析,确定了化合物的化学组成和相对百分含量。     

Enhanced light harvesting efficiencies of bis(ferrocenylmethyl)-based sulfur rich sensitizers used in dye sensitized TiO2 solar cells

In this work, the photosensitizing properties of ferrocene (Fc)-based compounds FcCH(2)CS(3)CH(2)Fc (1) and FcCH(2)SSCH(2)Fc (2) were investigated and significant enhancement in the light harvesting efficiency was observed compared to those achieved with previously reported compounds from our lab. The compounds were fully characterized by spectroscopy and X-ray crystallography, and their electrochemical properties studied. DSSCs based on these dyes display efficiencies comparable to those of a standard cell based on N719 under similar experimental conditions. These studies demonstrate that ferrocenyl-based sulfur rich compounds with proper orientation of the Fc groups assisted via suitable linkers, together with desired redox properties and visible region electronic absorption features could constitute a new class of photosensitizers targeting light driven reactions.     

Novel Substituted Imidazo[2,1‐b][1,3,4]Thiadiazole Derivatives: Synthesis,Characterization, Molecular Docking Study,and Investigation of Their In Vitro Antifungal Activities

In this study, a new series of substituted imidazo[2,1‐b][1,3,4]thiadiazole derivatives were synthesized. To this end, first 2‐amino‐1,3,4‐thiadiazole derivatives (compounds 2a and 2b ), the starting materials, were synthesized with high yields (82% and 79%, respectively). Then imidazo[2,1‐b][1,3,4]thiadiazole derivatives ( 4 – 16 ), the target compounds, were synthesized from reactions of 2‐amino‐1,3,4‐thiadiazole derivatives ( 2a and 2b ) with 2‐bromoacetophenone derivatives ( 3a – 3i ) (in yields of 52% to 71%). All of the synthesized compounds were characterized by ¹H NMR, ¹³C NMR, Fourier transform infrared, elemental analysis, mass spectroscopy, and X‐ray diffraction analysis (compounds 4 – 12 , 14 , and 15 ) techniques. In vitro antifungal activity tests were performed for all of the synthesized compounds. Inhibition zones, percentage of inhibition, minimum fungicidal activity, minimum inhibitory concentration, and lethal dose values of the target compounds were determined against some plant pathogens. According to the results of the biological activity tests, all of the synthesized compounds showed moderate to high levels of antifungal activity. Theoretical calculations were performed to support the experimental results. The geometric parameters of selected compounds ( 5 , 6 , and 8 ) were optimized using the density functional theory B3LYP/6‐31G(d) method in the Gaussian 09W package program, and the frontier molecular orbitals (highest occupied molecular orbital–lowest unoccupied molecular orbital) were calculated theoretically. Finally, molecular docking studies were performed for antifungal activity studies of the selected compounds and to determine whether or not these compounds could be inhibitor agents for the 2RKV protein structure.