Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.

Electrochemical Sensors Based on Modification of Carbon Fiber Microelectrode by Nickel Phthalocyanine Polymer for 3-Methyl-4-Nitrophenol Analysis in Water

3-methyl-4-nitrophenol (MNP) is the main by-product of the organophosphate insecticide fenitrothion (FT), used in locust control. MNP is highly toxic because it is an endocrine disruptor and then may cause adverse in the biological systems. Then, it is necessary to develop analytical methods for determination of this pollutant in the environment. In this sense, we reported herein the development of an electrochemical sensor for the detection of 3-methyl-4-nitrophenol (MNP), one of the metabolites of fenitrothion (FT), by using naked and modified carbon fiber microelectrode (CFME) by nickel tetrasulfonated phthalocyanine polymer (CFME/p-NiTSPc). The voltammogram showed that MNP presents one irreversible anodic peak corresponding to the oxidation of the phenol group at 0.9 V vs Ag/AgCl. The effect of pH of the buffer on the peak current and SWV parameters such as frequency, scan increment and pulse amplitude were investigated in order to optimize the electrochemical response of the sensor. The obtained results lead to the following optimum value: pH = 6;frequency = 25 Hz, pulse amplitude = 50 mV, scan increment = 10 mV. With these optimum values, the calibration curves show that the peak current varied linearly upon MNP concentration leading to a limit of detection (LoD) for naked CFME close to 3 μg/L whereas for CFME modified by p-NiTSPc, it reaches 0.75 μg/L. This results prove that the presence of p-NiTSPc increasing the sensitivity of the sensor could be used to monitor 3-methyl-4-nitrophenol residue in real matrix.

Alleviative effect of quercetin on germ cells intoxicated by 3-methyl-4-nitrophenol from diesel exhaust particles

As a component of diesel exhaust particles, 3-methyl-4-nitrophenol （4-nitro-m-cresol, PNMC） is also a metabolite of the insecticide fenitrothion and imposes hazardous effects on human health. In the present study, the alleviative effect of a common antioxidant flavonoid quercetin on mouse germ cells intoxicated by PNMC was inves- tigated. Results showed that a single intraperitoneal injection of PNMC at 100 mg/kg induced severe testicular damage after one week. PNMC-treated mice showed a significant loss of germ cells （approximate 40% loss of round germ cells）. PNMC caused an increase of hydroxyl radical and hydrogen peroxide production and lipid peroxidation, as well as a decrease in glutathione level, superoxide dismutase and glutathione peroxidase activities. Furthermore, treatment of PNMC increased expression of the pro-apoptotic protein Bax and decreased expression of the anti-apoptotic protein BcI-XL in germ cells. In addition, testicular caspase-3 activity was significantly up-regulated and germ cell apoptosis was significantly increased in the PNMC-treated mice. In contrast, combined administration of quercetin at 75 mg/kg significantly attenuated PNMC-induced testicular toxicity. These results indicate that the antioxidant quercetin displays a remarkable protective effect on PNMC-induced oxidative damage in mouse testes and may represent an efficient supplement to attenuate reproductive toxicity by environmental toxicants to ensure healthy sperm production.

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).

环境污染物三甲基四硝基苯酚上调中性粒细胞CD64引发重症哮喘的作用研究

目的利用卵白蛋白(OVA)和环境污染物三甲基四硝基苯酚(MNP)建立小鼠哮喘模型,探讨MNP引发小鼠重症哮喘的作用。方法将24只小鼠随机分为Control组、MNP组、OVA+Alum组、OVA+MNP组四组,每组各6只。通过3次皮下致敏(Control组100μl PBS、MNP组100μg MNP、OVA+Alum组100μg OVA+2 mg Alum,OVA+MNP组100μg OVA+100μg MNP)和连续7 d的滴鼻激发(20μg OVA),以HE染色、PAS染色、Elisa等作为小鼠重症哮喘的评价指标。流式细胞术,Western Blot、RT-qPCR作为中性粒细胞CD64表达上调的评价指标。结果与Control组比较,MNP+OVA组小鼠血清OVA特异性IgE和IgG1水平升高,肺泡灌洗液中IL-4、IL-5、IL-13含量升高,中性粒细胞表达上调,CD64蛋白表达水平和mRNA表达水平也明显上调,差异均具有统计学意义(P<0.05)。结论MNP可以上调中性粒细胞CD64的表达引发小鼠重症哮喘。

Synthesis, Crystal Structure and Antitumor Activity of 2-(3-Methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione

The title compound 2-（3-methyl-5-（methylthio）-4H-1,2,4-triazol-4-yl）isoindoline- 1,3-dione （C12H10NaO2S, Mr= 274.30） has been synthesized by a three-step procedure including the cyclization, hydrazinolysis and substitution reactions, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P2/c with a = 12.264（3）, b = 14.646（3）, c = 14.349（4） A,β = 91.69（3）°,μ = 0.255 mm1, Mr = 274.30, V = 2576.2（10） A3, Z =8, Dc = 1.414 g/cm3, F（000） = 1136, R = 0.0487 and wR = 0.1329 for 4048 observed reflections with I 〉 2σ（I）. In addition, the preliminary bioassay suggested that the title compound 6 exhibits relatively good antitumor activity against HT-29 and MCF-7.

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.

Differential protein expression in substantia nigra induced by 1-methyl-4-phenyl-1, 2, 3, 6-tetrahydropyridine in a mouse model of chronic Parkinson’s disease

BACKGROUND： To date, a complete protein expression profile of the midbrain substantia nigra in a mouse model of chronic Parkinson＇s disease, induced by 1-methyl-4-phenyl-1, 2, 3, 6-tetrahydropyridine （MPTP）, does not exist. In addition, there are no reports of analysis of differential protein expression. OBJECTIVE： To separate and evaluate MPTP-induced differential protein expression through the use of proteomics in the substantia nigra of a mouse model of chronic Parkinson＇s disease. DESIGN： Randomized controlled animal study. SETTING： Department of Neurology, the First Affiliated Hospital, Chongqing Medical University. MATERIALS： Sixteen 8-10-week old, healthy, male, C57BL mice, weighing 20-25 g, and of clean grade, were provided by the Experimental Animal Center of Chongqing Medical University. The experimental animals were disposed according to ethical criteria. MPTP was provided by Sigma Company, USA; Pdquest 2D image analysis software and gelatum/irradiance image analysis system （ChemiDoc XRS） by Bio-Rad, USA; and Voyager DE-PROMALD1-TOF-MS mass spectroscopy analyzer by AB1 Company, USA. METHODS： This study was performed in Chongqing Neurological Laboratory between November 2006 and July 2007. Mice were randomly divided into model and control groups, with 8 mice in each group. Mice in the model group were received a subcutaneous injection of MPTP （25 mg＆g）, twice a week, for five successive weeks, to establish a chronic Parkinson＇s disease model. Mice in the control group received the same volume of a subcutaneous saline injection at the same time points. Mice were sacrificed by anesthesia to rapidly obtain the midbrain for protein separation of the substantia nigra. MAIN OUTCOME MEASURES： （1） 2-ED handbook （Bio-Rad Company） was referenced for two-dimensional electrophoresis, （2） PDQUEST8,0 analytical electrophoresis pattern was adopted to evaluate differential protein expression. （3） Peptide mass finger print map and data were retrieved on http：//www.prospector.ucsf.edu to compare differential substantia nigral protein expression in the two groups. RESULTS： Two-dimensional gel electrophoresis of substantia nigra tissue indicated that there were 33 differential protein expressions between the two groups. Three new proteins were evaluated, including α -enolase, which exhibited regulated expression, tumor necrosis factor ligand superfamily member 4, and cyclin-dependent kinase inhibitor 1B. CONCLUSION： There are three proteins that exhibit differential expression in the substantia nigra- α -enolase, tumor necrosis factor ligand superfamily member 4, and cyclin-dependent kinase inhibitor 1B.

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 of fused pyran and arylbis(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)methane in ionic liquid

Promoted and mediated by an ionic liquid-[bmim][BF4], fused pyrans or arylbis（4-hydroxy-6-methyl-2-oxo-2H-pyran-3- yl）methanes were efficiently and selectively prepared from the reaction of aldehyde and 4-hydroxy-6-methyl-2-oxo-pyran with or without acetic anhydride. By using these novel procedures, pyrimidine nucleoside-fused pyran and arylbis（pyranon-3-yl）methane hybrids with potential biological activities were constructed.

Alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor antagonist inhibits apoptosis of retinal ganglion cells in a rabbit model of optic nerve injury

A rabbit model of traumatic optic nerve injury, established by occlusion of the optic nerve using a vascular clamp, was used to investigate the effects of alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor antagonist GYKI 52466 on apoptosis of retinal ganglion cells following nerve injury. Hematoxylin-eosin staining and a terminal deoxynucleotidyl transferase dUTP nick end labeling assay showed that retinal ganglion cells gradually decreased with increasing time of optic nerve injury, while GYKI 52466 could inhibit this process. The results demonstrate that following acute optic nerve injury, apoptosis of retinal ganglion cells is a programmed process, which can be inhibited by the alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor antagonist.

1-methyl-4-phenylpyridinium ion induces endoplasmic reticulum stress through glycogen synthase kinase-3 beta activation in PC12 cells

1-methyl-4-phenylpyridinium ion （MPP^＋） induces endoplasmic reticulum stress and activates caspase-12 in PC12 cells, leading to neuronal apoptosis. However, the underlying molecular mechanism remains unknown. The present study investigated the regulatory effects of nerve growth factor （Akt activator） and lithium chloride （glycogen synthase kinase-3β inhibitor） on the endoplasmic reticulum stress signaling pathway. The results revealed that MPP＋ induced expression of Bip and C/EBP homologous protein. The upregulation of Bip and C/EBP homologous protein, as well as the decreased pro-caspase-12 level induced by MPP^＋ were inhibited by pretreatment of the nerve growth factor or lithium chloride. These results suggest that the phosphatidylinositol 3 kinase-Aktglycogen synthase kinase-3β pathway is involved in MPP-induced endoplasmic reticulum stress.

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.

Synthesis and Crystal Structure of (Z)-Methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)methyl]phenyl}acrylate

The title compound,(Z)-methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the triclinic system,space group P1 with a=8.0157(8),b=12.5748(13),c=13.3768(14)Å,α=64.770(2),β=75.720(2),γ=89.784(2)°,μ=0.085 mm^(-1),Mr=442.49,V=1174.1(2)Å3,Z=2,Dc=1.252 g/cm^(3),F(000)=468,T=294(2)K,R=0.0603 and wR=0.1498 for 2644 observed reflections with I〉2σ(I).X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds.The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.

Synthesis and Characterization of Novel-4-Methyl-3-isoxazolidinone Derivatives

A novel type of aeetohydrexyacid synthase inhibitors, 4-methyl-3-isoxazolidinone derivatives of sulfonylurea, was designed and synthesized. The structures of these compounds were confirmed by using MS, NMR, and elemental analysis. The results of preliminary active tests indicate that the compounds show a herbicidal activity.

Synthesis and Crystal Structure of 3-Nitrophthalic Acid·3-methyl-4-nitropyridine N-Oxide Adducts

The title compound, a 1：1 molecular adduct of 3-nitrophthalic acid and 3-methyl- 4-nitropyridine N-oxide （PPOM）, has been synthesized and characterized by X-ray single-crystal structure analysis. It crystallizes in triclinic, space group PI with α = 7.6076（15）, b = 7.8180（16）, c = 14.546（3）A, α= 93.90（3）, β = 97.21（3）, γ= 114.43（3）°, C14H1N3O9, Mr = 365.26, Z = 2, V = 774.6（3） A^3, Dc = 1.566 g/m^3,μ（MoKa） = 0.134 mm^-1, F（000） = 376, R = 0.0538 and wR = 0. 1460 for 885 observed reflections （1 〉 2σ（I））. The protons of the carbonylic acids in the molecule are not transferred and the O-H…O and C-H…O hydrogen bonds form zigzag chains in the molecule.

Synthesis,Crystal Structure and Magnetic Property of a New One-dimensional Complex [Mn(μ_(1,5)-dca)_2(POM)_2] (POM = 3-Methyl-4-nitropyridine-N-oxide,dca = Dicyanamide)

The title complex [Mn（μ1,5-dca）2（POM）2] （C16H12MnN10O6,Mr = 495.30） has been prepared and structurally characterized. It crystallizes in triclinic,space group P1 with a = 7.4685（9）,b = 7.5406（9）,c = 9.8646（12）A,α = 83.202（2）,β = 69.1200（10）,γ = 79.4130（10）o,V = 509.38（11） A^3,Z = 1,Dc = 1.602 g/cm^3,F（000） = 249,μ（MoKa） = 0.704 mm^-1,the final R = 0.0701 and wR = 0.2071 for 1615 observed reflections with I 〉 2σ（I）. Each Mn（Ⅱ） exhibits a slightly distorted octahedral environment and connects with each other to form a one-dimensional complex by double bridging μ1,5-N≡C-N-C≡N ligands. The magnetic susceptibility of the title complex has been measured,and it displays weak antiferromagnetic interactions.

Theoretical Study on the Structure and Vibrational Spectra for 4-methyl-3-penten-2-one

Density functional theory BLYP (using Becke's and Lee-Yang-Parr's correlation functionals), nb initio Hartree-Fock (HF) and hybrid DFT/HF B3LYP calculations were carried out to study the structure and vibrational spectra of 4-methyl-3-penten-2-one. The BLYP/6-31G* and scaled HF/6-31G* frequencies correspond well with each other and with available experimental assignment of the functional vibrational modes.

First Synthesis of (±)-3-(5-Hyd roxy-4-Methyl-7-Isopropyl-3E,7-Octadienyl)- △~2-Butenolide

An efficIent total synthesis of (±)-3-(5-hydroxy-4-methyl-7 △-butenolide, a new fi1n1esane-b;.Fed homosesquiterPeIle lactone. starting from geraniol through eightsteps are described.