Synthesis, Crystal Structure and DNA-Binding Property of a Mn(Ⅱ) Complex Based on 5-(Tri-fluoromethyl)pyridine-2-carboxylic Acid

A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?3, Z = 1, Dc = 1.793 g·cm-3, μ = 0.855 mm-1, Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I > 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.

Synthesis and fluorescence properties of Tb(Ⅲ) complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.

Influence of surfactant concentration on counter-ion induced solubility of poly(pyridine-2,5-diyl)

Protonating the pyridine rings of poly(pyridine-2,5-diyl) with dodecybenzenesulfonic acid and camphorsulphonic acid produces polymer materials which can be dissolved in chloroform (in contrast to the unprotonated polymer, which can only be dissolved in strong acids such as formic acid) and allows mixing the protonated polymers with other chloroform soluble conju- gated polymers for use in electronic devices. The protonating behavior of poly(pyridine-2,5-diyl) with two kinds of surfactants is different in some levels. Dodecybenzenesulfonic acid has higher protonating ability than camphorsulphonic acid.

Excess Molar Volume and Apparent Molar Volume of Binary Mixtures of 2-Methyl-3-buten-2-ol with 1-Alcohol at 298.15K

Excess molar volumes (V^E_m) of binary mixtures of2-methyl-3-buten-3-ol [CH_3C(OH)(CH_3)CHCG_2] with four 1-alcohols:methanol, ethanol, 1-propanol and l-butanol at 298.15 K andatmospheric pressure are derived from density measurements with avibrating-tube densimeter. All the excess volumes are negative in thesystems over the entire composition range. The results are correlatedwith the Redlich-Kister equation. The effects of chain length ofl-alcohols on V^E_m are discussed. The apparent molar volumes of2-methyl-3-ol and l-alcohols are calculated respectively.

Photoionization and Dissociation Study of 2-Methyl-2-propen-1-ol:Experimental and Theoretical Insights

The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.

Crystal Structures of Schiff Base from 4-Aminoantipyrine and Pyridine-2-carboxaldehyde and Its Perchlorate

The Schiff base pyridine-2-carboxaldehyde-4-aminoantipyrine （CI7H16N4O 1） and its perchlorate （C17H17N4O·ClO4 2） have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray crystallography analysis. Both 1 and 2 crystallize in the monoclinic system, space group P21/c. For 1, a = 8.6820（12）, b = 24.934（3）, c = 7.0064（10） A,, β= 97.942（3）°, V = 1502.2（4） A^3, Z = 4, Dc = 1.293 g/cm^3, F（000） = 616,μ = 0.084 mm^-1, the final R = 0.0592 and wR = 0.1244. For 2, a = 5.9302（2）, b = 20.347（7）, c = 14.663（6） A, β= 90.200（9）°, V= 1769.201） A^3, Z = 4, Dc = 1.475 g/cm^3, F（000） = 816, μ = 0.254 mm^-1, the final R = 0.0533 and wR = 0.0819. As expected, both molecular structures of 1 and 2 adopt a trans configuration about the central C=N double bond. 2 is an ionic compound with the protonation at N（1） of pyridine-2-carboxaldehyde-4- aminoantipyrine.

Neuropathy and chloracne induced by 3,5,6-trichloropyridin-2-ol sodium:Report of three cases

BACKGROUND Chloracne is a rare skin condition that is caused by systemic exposure to halogenated aromatic compounds.The main characteristic of chloracne is blackhead,and in severe cases,it can be accompanied by systemic symptoms.Sodium 3,5,6-trichloropyridin-2-ol(STCP)is a necessary precursor compound for the production of chlorpyrifos and triclopyr,which are extensively used as a pesticide and herbicide,respectively.STCP is also a chlorophenol that has been associated with chloracne.STCP poisoning could induce mild myelin sheath damage.We herein report three cases with chloracne due to exposure to STCP.CASE SUMMARY Three young men,aged 29,33,and 26 years,respectively,in the same workplace had polymorphic skin lesions,characterized mainly by comedones and cysts,and one of them also had acne like lesions in the genital area.These clinical manifestations appeared when they were exposed to STCP for 3 d,1 wk,and 2 wk,respectively.Among them,polyneuropathy and liver damage occurred.We performed dermoscopy and clinical and laboratory tests on these patients.Additionally,histopathology was used for further diagnosis in the serious patient.These patients were diagnosed with chloracne and separated from STCP.The patients were prescribed oral viaminate capsules,topical adapalene gel,and regular hematologic follow-up for aspartate transaminase and lipids.They are still under follow-up.There was no new lesions and the laboratory tests returned to normal in two patients.Pigmentation and shallow scars remained in the original areas of papules.However,in the most serious patient,new papules still appeared intermittently.All these remind us that the treatment of chloracne caused by STCP is difficult,and we should attach great importance to this new compound related with the neuropathy and chloracne.CONCLUSION STCP is becoming a new chemical product to induce chloracne,which should attract the attention of all medical professionals,especially dermatologists.Due to the lack of knowledge on the new chemical,the diagnosis of chloracne cannot be made in time.Chloracne still deserves our attention.

Theoretical Study on the Reaction Mechanism of 2-Methoxybenzaldehyde,4-Bromo-indanone,Malononitrile and Ammonium Acetate One-pot to Form 6-(2-Methoxyphenyl)-2-amino-6-bromo-5H-indeno[1,2-b]pyridine-3-carbonitrile

The reaction mechanism of 2-methoxybenzaldehyde, 4-bromo-indanone, malononitrile and ammonium acetate one-pot to form 6-（2-methoxyphenyl）-2-amino-6-bromo-5 Hindeno[1,2-b]pyridine-3-carbonitrile was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Reaction pathways were investigated in this study. The result indicates that the reaction Re→ TSB1→IMB1→ TSB2→ IMB2→TSB3→IMB3→TSB4→IMB4→TSB5→IMB5→TSB6→IMB6→TSB7→IMB7→ TSB8→IMB8→TSB9→IMB9→P2 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.

Green Chemistry Approach to Fast and Highly Efficient One-Pot Synthesis of Bis-Isoxazolyl-1,2,5,6-Tetrahydro Pyridine-3-Carboxylates

The synthesis of the bis-isoxazolyl-1,2,5,6-tetrahydro pyridine-3-carboxylates is achieved in high yield without the production of toxic waste products by using room temperature ionic liquid (RTILs) triethyl ammonium acetate (TEAA). The RTIL TEAA played the dual role of efficient green solvent as well as recyclable catalyst.

THE FIRST BINUCLEAR MOLYBDENUM AND TUNGSTEN COMPLEXES WITH DOUBLY-BRIDGING PYRIDINE-2-THIOLATO LIGANDS.X-RAY CRYSTAL STRUCTURE OF THE COMPLEX[Mo_2(CO)_4(μ-pyS)_2(PPh_3)_2].2C_7H_8

The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.

Synthesis of Some New Pyridine-2-yl-Benzylidene-Imines

A series of new Schiff bases derived from 2-aminopyridenes and various aromatic aldehydes have been synthesized and thoroughly investigated by 1H and 13C NMR spectroscopy. The imines were found to exist as only a single E-isomer at ambient temperature. Interestingly, 1H- and 13C-NMR chemical shifts of the (CH=N) amino group are affected by the type of substituent group (X) on the aryl ring. Furthermore UV and IR Spectra of some of the title compounds are also reported.

Crystal Structure of Trans-2-Amino-3-Cyano-4-(3',4'-Methylenedioxyphenyl)-1-Phenyl-2-Cyclopentene-r-1-ol

The crystals of the title compound C19H16N2O3 were synthesized by thereaction of 4, 4-dicyano-1-phenyl-3-(3', 4'-methylenedioxyphenyl)-l-butan withlow-valent titanium reagent. It belongs to the orthorhombic system, space group Pea21with a=11. 547(2), b=13. 168(4), c=10. 645(3) A, V=1618. 4(8) A3, Dc=1.315 g/cm3, Z=4, Mr=320.35. A=0. 71069 A, u(MoKa) =0. 90 cm-1, F(000)=672. The structure was refined to R=0. 036, Rw=0. 044 for 962 observed reflections(I＞3(I) ). X-ray analysis reveals that in the five membered ring the C(11) -C(12)bond is longer than normal double C=C bond while the C(11) -N (1) bond is shorterthan normal C(sp)2-N bond.

Crystal Structure of (1R,4R;1S,4S)2-Amino-3-Cyano-1,4-Diphenyl-2-Cyclopentene-1-ol

The crystal of title compound C18H16N2O was obtained by recrystal-lizing from ethanol solution. It belongs to orthorhombic system, space group Pbca witha=23. 229(2), b=11. 880(3), c=10. 733(3) A, V=2961 (0) A3, Mr=276. 34, Dc=1. 239 g/cm3, Z=8, A(MoKa)=0. 78 cm-1, F(000) =1168. 00. The structurewas refined to R=0. 049 and Rw=0. 046 for 1102 observed reflections (I＞2d(I) ).The bond lengths of C(3) -C(4) and C(3) -N(1) are 1. 349(5) A and 1. 340(6) A,respectively. The bond angles of N (1) -C(3) -C(2), AN (1) -C(3) -C(4), AC(2) -C(3) -C(4) and C(3) -C(4) -C(5) are 121. 1 (4), 128. 4(4), 110. 5(4)and 113. 1 (4), respectively. The dihedral angle between two phenyl rings is 29. 29.

Synthesis, Structure and Property of a Novel Coordination Polymer [Tb(C_7H_3NO_4)(C_6H_4NO_2)(H_2O)]

A novel terbium(III) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a = 9.2252(11), b = 14.1477(16), c = 10.5134(12) A, β = 95.770(2)°, V = 1365.2(3) A3, Z = 4, Dc = 2.248 g·cm-3, F(000) = 880, the final R = 0.0176 and w R = 0.0411 for 2149 observed reflections with I 】 2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4 → 7F5 transition of the Tb(III) ion.

Effect of （＋）-limonene and 1-methoxy-2-propanol on Ips typographus response to pheromone blends

We compared two different strategies to increase the catches oflps typographus （L.）, particularly males, in pheromone-baited traps. The first of these strategies, the barrier approach, used alternating pheromone blends, targeting males and females respectively, in closely-spaced traps forming a barrier around forest stands. The second strategy, the single trap approach, used widely-spaced traps that were all baited with the same lure and intended to trap the highest possible numbers of males without compromising trapping of females. In the blend used for the barrier traps targeting primarily males, with a lower percentage of （4S）-cis-verbenol （cV）, the （-）-α-pinene was replaced step wise with （＋）-limonene at rates of 0%, 1%, 10%, 35%, 60% and 90%. This replacement had no significant effect on the numbers of responding 1. typographus males, but there was a slight effect on the percentage of males caught. In the attractant blend for the barrier traps targeting females, with a higher percentage of cV, the 2-methyl-3-buten-2-ol （MB） was replaced with 1-methoxy-2-propanol （MP） in a similar fashion as for the male-specific blends. The replacement did not significantly affect the catch of females. Thus, it is pos- sible to use the MP in the blend with cV and ipsdienol without significant change in catch efficacy. In the blends for single traps, the （-）-α- pinene was replaced with （＋）-limonene and MB with MP. The replacement of （-）-α-pinene had only a slight effect on the percentage of males, but the results suggest that replacing MB with MP in the blend will not significantly reduce trapping efficacy.

Synthesis and Crystal Structure of (Z)-1- (3-Fluorobenzyl)-5-((3-fluorobenzylimino)(2-hydroxy-4-methoxyphenyl)methyl)pyridin-2(1H)-one

The title compound （Z）-1-（3-fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4- methoxyphenyl）methyl）pyridin-2（1H）-one （C27H22F2N2O3,Mr = 460.47） was synthesized and crystallized. The crystal belongs to the triclinic system,space group P1 with a = 9.951（6）,b = 10.059（6）,c = 12.927（7）A,α = 109.828（7）,β = 102.304（7）,γ = 104.898（7）°,Z = 2,V = 1110.2（11）A^3,Dc =1.377 Mg/m^3,μ（MoKα） = 0.102 mm^-1,F（000） = 480,the final R = 0.0449 and Rw = 0.1250 for 4595 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that both m-fluorobenzyl groups are diorientationally disordered because of the rotation of C–C single bond which was represented as F（1）,F（2） and F（1＇）,F（2＇）. The diorientational disorder was refined and gave the occupancies of 0.665（4） and 0.335（4） for F（1） and F（1＇）,0.631（3） and 0.369（3） for F（2） and F（2＇）. Hydrogen bonds existing in the cell link different components to stabilize the crystal structure. The active data proved that the title compound has good anti-HBV activity.

新型白念珠菌生物被膜抑制剂IMB-H12的活性和作用机制研究

白念珠菌是真菌感染疾病中的主要病原菌,生物被膜的形成是白念珠菌毒力特征,同时也是重要的耐药机制,开发具有生物被膜抑制活性的抗真菌药物具有重要的意义。本研究对前期获得的新型的具有生物被膜抑制活性的化合物1-(cyclopentylamino)-3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propan-2-ol(简称IMB-H12)进行了深入的研究。IMB-H12对生物被膜的形成具有良好的抑制活性,并且对成熟的生物被膜具有一定的清除作用;初步作用机制研究发现IMB-H12能够抑制酵母-菌丝相的转换、抑制菌丝体的形成,降低白念珠菌的黏附活性和疏水性;IMB-H12能够诱导生物被膜菌细胞壁成分含量的改变,下调多个与黏附和菌丝形成相关的基因的表达。因此,对该化合物的进一步研究,有望发现新型的具有抗真菌活性的先导化合物。

川黄柏中原小檗碱型生物碱及其细胞毒性研究

采用甲醇溶剂对芸香科黄柏属川黄柏的茎进行回流提取,利用硅胶、胺基硅胶和葡聚糖凝胶等多种柱色谱法对提取物化学成分进行研究,通过核磁共振和电喷雾质谱等波谱技术以及与文献报道数据比对,从中分离鉴定了4个原小檗碱型生物碱,分别鉴定为二氢小檗碱(1),hediamine(2),2-methoxy-berbin-10-ol(3),3-methoxy-berbin-10-ol(4).并对化合物1的波谱进行详细归属,对化合物2进行单晶衍射实验,确定其绝对构型.所有化合物均对人肝癌细胞(HepG2)有较强的细胞毒性.

Polymerization of 1,3-Butadiene Catalyzed by Cobalt(Ⅱ) and Nickel(Ⅱ) Complexes Bearing Pyridine-2-imidate Ligands

Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.