Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Extraction Behavior of Rare Earths with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 Using Solid-liquid Extraction Technique

The extraction behavior of rare earths was studied by using paraffin with ceresin as a diluent containing 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5.In solid phase,the composition of complexes is REP_3.The equilib- rium extraction constants and pH_(1/2) values of solid-liquid extraction are higher than those of normal liquid-liquid extraction.The extraction efficiency tends to maximum when the ratio of phases is 1:1.When the extraction temperature is higher than the melting point of paraffin and the extraction time is over 10 min,the extraction efficiency keeps constant.Moreover,the relationship among separation factor,equilibrium extrac- tion constant,pH_(1/2) value and atomic number was obtained.The mechanism of solid-liquid extraction is analogous to that of liquid-liquid extraction.

Dissolution Properties of 2-(Dinitromethylene)-5-methyl-1,3-diazacyclopentane in Dimethyl Sulfoxide and N-Methyl Pyrrolidone

The molar enthalpies of dissolution for 2-（dinitromethylene）-5-methyl-1,3-diazacyclopentane（DNMDZ） in dimethyl sulfoxide（DMSO） and N-methyl pyrrolidone（NMP） were measured using an RD496-2000 Calvet microcalorimeter at 298.15 K under atmospheric pressure.Empirical formulae for the calculation of the molar enthalpies of dissolution（Δ diss H） were obtained from the experimental data of the dissolution processes of DNMDZ in DMSO or NMP.The relationships between the rate constant（k） and the molality（b） and between the reaction order（n） and the molality（b） were determined.The corresponding kinetic equations describing the two dissolution processes were dα/dt=10^-2.16（1-α） ^1.01 for the dissolution of DNMDZ in DMSO,and dα/dt=10^-2.02（1-α）^ 0.85 for the dissolution of DNMDZ in NMP,respectively.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

Two New Schiff Bases Based on 5-Chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde: Syntheses, Crystal Structures and Properties

Two new Schiff bases based on 5-chloro-3-methyl-1-phenyl-1 H-pyrazole-4-carbaldehyde, namely, N-((5-chloro-3-methyl-1-phenyl-1 H-pyrazol-4-yl)methylene)-4-morpholinoaniline(Ⅲa) and N-((5-chloro-3-methyl-1-phenyl-1 H-pyrazol-4-yl)methylene)-3-fluoro-4-morpholinoaniline(Ⅲb), were synthesized and characterized by IR, LC-MS, 1 H NMR and 13 C NMR spectroscopy. Meanwhile, the three-dimensional configurations of the two title compounds were further characterized by single-crystal X-ray diffraction analyses. Both the compounds are thermodynamically stable trans-isomers. Moreover, the fluorescence properties and antioxidant activities against DPPH of the two target compounds have been investigated, and the results showed that the title compounds both have fluorescence performance and certain antioxidant activities against DPPH radical.

Dual-parameter Correlation Analysis of the Fluorescence Data of 1-Methyl-2-formyl-5-substituted Pyrrole(4-nitrophenyl)hydrazones

By using 1-methyl-2-formyl-5 -Y-substituted pyrrole (4-nitrophenyl)hydrazones as a model for nitrogen-containing heterocyclic aromatic compounds, the emission wavelength [lambda(max(em))] values df their fluorescence spectra have been measured. Correlation results show that the Delta E-em values are mainly affected by polar effects, but spin-delocalizatin effects also exist.

Thermodynamic Study and Spectroscopic Analysis of a Charge-Transfer Complex between 3,5-Diamino-1,2,4-Triazole and 6-Methyl-1,3,5-Triazine-2,4-Diamine with Chloranilic Acid

Studying of charge-transfer (CT) and proton transfer interactions is essential due to their important role in many biological field and industrial applications. The current work will add more information’s about the nature of interaction between 3,5-diamino-1,2,4-triazole (DAT) and 6-methyl-1,3,5-triazine-2,4-diamine (MTDA) with 3,6-dichloro-2,5-dihydroxy-p-benzoquinone (chloranilic acid CLA) which was studied spectrophotometrically in Ethanol (EtOH) and Methanol (MeOH) solvents at different temperatures. The molecular composition of the formed complexes was studied by applying continuous variation and spectrophotometric titration methods and found to be 1:1 charge transfer complex for both Complex (DAT:CLA) and (MTDA:CLA) which are produced. Minimum-Maximum absorbance’s method has been applied to calculate the formation constant KCT and molecular extinction coefficient (ε);they recorded high values confirming high stability of the produced complexes. Oscillator strength (f), transition dipole moment (μ), ionization potential (IP) and dissociation energy (W) of the formed CT-complexes were also determined and evaluated;they showed solvent dependency. It is concluded that the formation constant (KCT) of the complexes is found to depend on the nature of both electron acceptor and donors and on the polarity of solvents.

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- (naphthalen-1-yl)-1-tosyl-1H-pyrrol-2(5H)-one

The title compound 4-bromo-5-ethoxy-3-methyl-5-（naphthalen-l-yl）-l-tosyl-lH- pyrrol-2（5H）-one 1 （C24H22BrNO4S, Mr = 500.40） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562（15）, b = 18.118（3）, c = 14.055（2）A, β = 99.855（3）^o, V= 2221.9（6）A3, Z = 4, Dc = 1.496 g/cm^3,μ= 1.975 mm^-1, 2 = 0.71073A, F（000） = 1024, R = 0.0607 and wR = 0.1371.

Synthesis, Reactions and Characterization of 1,1’-(1,4-Phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(ethan-1-one)

Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

5-甲基苯并三氮唑作为电腐蚀抑制剂在铜电化学机械平坦化中的应用(英文)

根据电化学分析,5-甲基苯并三氮唑(m-BTA)的腐蚀抑制能力要高于苯并三唑(BTA)的。当羟基乙叉二膦酸(HEDP)电解液中同时含有m-BTA及氯离子时,其抑制解离能力比只含有m-BTA的更好,即使施加更高的阳极氧化电位依然能保持良好的抑制能力。由电化学阻抗谱法、纳米划痕实验以及能谱分析结果得知,m-BTA抑制能力的提升是因为整体钝化膜厚度的增加而引起的。由X射线光电子能谱分析得知,氯离子与m-BTA钝化层形成[Cu(I)Cl(m-BTA)]n高分子化合物,使得整体钝化层厚度增加。因此,在含有m-BTA的HEDP电解液中添加氯离子有助于m-BTA钝化层抑制能力的增强,进而更有效的电位操作区间得到扩展。

The First Two-dimensional Supramolecular Network Constructed by Na(Ⅰ) with 2-Methylimidazole-4,5-dicarboxylate Building Blocks

The title complex [Na（H2MIA-）（H2O）]（1,H3MIA = 2-methyl-1H-imidazole-4,5-dicarboxylic acid） has been synthesized by hydrothermal synthesis and structurally characterized by X-ray crystallography.Compound 1 crystallizes in orthorhombic,space group ibam with a = 14.4737（19）,b = 17.553（2）,c = 6.5285（9）,V = 1658.6（4） 3,C6H7N2NaO5,Mr = 210.12,Z = 8,Dc = 1.675 g/cm3,F（000） = 864,μ = 0.188 mm-1,λ（MoKα） = 0.071073 ,R = 0.0383 and wR = 0.0987 for 1046 observed reflections（I 2σ（I））.In the structure of 1,each coordination water coordinates with two Na（I） ions at the same time and links the neighboring Na（I） ions to form a one-dimensional Na（I）-water chain.Each H2MIA-ligand links the neighboring Na（I） of Na（I）-water chain to form a novel two-dimensional supramolecular network.The 2-D network is stabilized by O-H…N hydrogen bonds and π-π interaction.The 2D network is further linked via O-H…O hydrogen bonds to yield a three-dimensional framework.

Solid State Synthesis and Crystal Structure of 3—Methly—1—phenyl—4—phe

The solid state thermal reaction of benzil with 3-methyl-1-phenyl-5-pyrazolone gave the title compound 1 (C_24H_18N_2O_2) and its isomer 2. The crystal structure of the title compound has been determined by X-ray analysis. The crystal belongs to monoclinic system, space group P2_1/n, with cell parameters a = 7. 479 ( 1 ), b =16. 992(1), c=15. 165(1) A , β= 100. 99(1)°, V= 1891. 9 A￣3, M_r=366. 42, Z=4, D_c= 1. 286 g/cm￣3, μ= 6. 236 cm￣-1, F(000) = 768. In the molecule of 1, benzoyl group and CO group of five-member ring are in cis-positions, the interaction of oxygen atoms leads to the noncoplanarity.

Protective effect of Fructus Mume total flavone against SH-SY5Y cells damage induced by MPP+and its mechanism

Objective:To investigate the neuroprotective effects of Fructus Mume total flavone(FMF)against cell apoptosis and mitochondrial injury induced by 1-methyl-4-phenylpyridinium(MPP^(+))in human neuroblastoma(SH-SY5Y)cells and explore its molecular mechanisms.Methods:MPP^(+) induced SH-SY5Y cells injury model were established in vitro cell culture,the cells were divided into 5 groups:normal control group,model group(250μmol·L^(-1) MPP^(+)),FMF low-and middle-and high-dose experimental group(10,50,100μmol·L^(-1) FMF).After 72 h administration,4’,6-diamidino-2-phenylindole(DAPI)staining was used to observe the effects of different concentrations of FMF on the morphologic changes of apoptotic cells,the ratio of cell apoptosis was measured by Annexin-FITC/PI double staining.The mitochondrial membrane electro-bit were detected by flow cytometry(FCM).The expression of Bcl-2,Bax and Caspase-3 were detected by Western blot.Results:The results of DAPI staining showed that the injury SH-SY5Y cells induced by MPP+were densely condensed,the nucleus showed nuclear shrinkage,showing an apoptotic characteristic morphology;after 72h of FMF action,the apoptotic morphology of the cells showed different degrees of improvement,and the apoptotic number of SH-SY5Y cells also decreased.Compared with that in the normal control group,the apoptotic rate and of mitochondrial membrane electrobit of SH-SY5Y cells in the model group increased significantly(P<0.01),the expression of Bax and Caspase-3 proteins increased significantly(P<0.01),Bcl-2 protein and the ratio of Bcl-2/Bax decreased significantly(P<0.01).Compared with that in the model group,the apoptotic rate and mitochondrial membrane electro-bit of SH-SY5Y cells in FMF groups(10,50,100μmol·L^(-1))were significantly lower,while Bax and Caspase-3 proteins were significantly lower(P<0.01),and Bcl-2 protein and the ratio of Bcl-2/Bax were significantly higher,with statistically significant difference in FMF middle-and high-dose experimental groups(P<0.01).The results indicated that FMF can decrease the experession level of Bax and Caspase-3 and increase the ratio of Bcl-2/Bax,inhibit MPP+induced apoptosis.Conclusion:FMF improves the damage of SH-SY5Y cells induced by MPP+,and plays a neuroprotective effect by regulating the expressions of related proteins in mitochondrial apoptosis pathway.

Extraction and Separation of Rare Earths from Nitrate Medium by Mixtures of p-Phosphorylated Calixarene and 1-Phenyl-3-methyl-4-benzoyl-pyrazalone-5

The gadolinium extraction by the mixtures of p-phosphorylated calixarene and 1-phenyl-3-methyl-4-benzoylpyrazalone-5 from nitrate medium was studied,which indicated an obvious synergistic effect between these two extractants.The extractants exhibit no interaction with each other before the metal extraction.Gadolinium(Ⅲ)was extracted by the species of Ln(PMBP)_(2)L_(2)(NO_(3))instead of Ln(PMBP)_(3)•(HPMBP)or Ln(NO_(3))_(3)•2L which are extracted by HPMBP or L alone.Thermodynamic functions(ΔG,ΔH,ΔS)were calculated.The extraction of other rare earths was also investigated and compared.Possible single rare earth separation was discussed.