Synthesis, Crystal Structure, Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

固定化β-葡萄糖醛酸酶反应器的制备及其在4-甲基亚硝胺基-1-(3-吡啶)-1-丁醇的O-糖苷化合物分析中的应用

采用溶胶-凝胶法,以丙烯酰胺作为单体,制备了基于有机-硅胶杂化整体柱的β-葡萄糖醛酸酶反应器。优化了硅酸甲酯和γ-(甲基丙烯酰氧)丙基三甲氧基硅的物质的量的比、丙烯酰胺和聚乙二醇的用量,以及水浴温度等制备条件,获得了孔隙均匀、通透性良好、机械强度高的有机-硅胶杂化整体柱。采用光学显微镜和扫描电镜表征杂化整体柱。进一步将β-葡萄糖醛酸酶共价键合在整体柱上,以4-甲基亚硝胺基-1-(3-吡啶)-1-丁醇(NNAL)的O-糖苷化合物(NNAL-O-Gluc)为底物研究酶反应器的水解效果,实验结果证明酶反应器在室温条件下的水解效率大大提高,实现了NNAL-O-Gluc高效水解与分析,解决了目前NNAL-O-Gluc分析中前处理水解效率低的问题。

Hydrothermal Synthesis and Crystal Structure of One Novel 1-D Copper(Ⅱ)-organic Framework:{[Cu_2(PP)_2(CBPC)]_2·7H_2O}_n

One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.

Synthesis and Solid Phase Extraction Performance Study of NNAL-specific Molecularly Imprinted Polymers Using Dummy Templates

Dummy molecularly imprinted polymers （DMIPs） for 4-（methylnitrosamino）-1-（3-pyridyl）-1-butanol （NNAL） were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-（acetymethylamino）-1-（3-pyridyl）-butanol, 4- （methylamino）-1-（3-pyridyl）-1-butanol, and 1-（3-pyridyl）-1,4,-butanediol. The molecular recognition characteristics of the produced polymers were evaluated by X-ray photoelec- tron spectroscopy （XPS） and Fourier transform infrared spectroscopy （FT-IR）. Interactions between NNAL and methacrylic acid should be cooperative hydrogen bonds while the ni- trogen atom of the pyridine ring and the oxygen atom of the nitroso group in NNAL are two of the hydrogen-bond acceptors. It was further demonstrated that DMIP synthesized by 4-（acetymethylamino）-1-（3-pyridyl）-butanol had the best binding performance by XPS and FT-IR. Then dummy molecularly imprinted solid phase extraction （DMISPE） was developed for the determination of the analyte using the hit polymer as the sorbing material. Under optimal conditions, the recovery of NNAL dissolved in standard solution reached 93%. And the investigated polymer exhibited much higher binding of NNAL when nicotine was acted as the competitive molecule. Also the proposed method was applied to the measurement of NNAL spiked in blank urine samples with recoveries ranging from 87.2% to 101.2%.

Synthesis,Structure,and Magnetic Property of One Snake-shaped Copper(Ⅱ)-organic Compound:Cu[Cu_2(PP)_2](CBPC)_2]·2(H_2O)

One novel copper（II）-organic compound,namely Cu[Cu2（PP）2]（CBPC）2]·2（H2O）（1,H2CBPC = 1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-（2-pyridyl）pyrazole）,was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu（II）ions in the quasi-planar dimmer of [Cu2（PP）2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1：C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900（7）,b = 15.029（7）,c = 12.308（6）,β = 102.519（9）o,V = 2691（2）3,Z = 2,Dc = 1.530 g/cm3,F（000）= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780（I 2σ（I））and S = 0.999.

Lipopolysaccharide enhances the inhibition of NF-κB expression in NNK-mediated peritoneal macrophages

Objective： The aim of the study was to investigate the effect of lipopolysaccharide （LPS） on the expression of nuclear factor kappa B （NF-κB） in 4-（methylitrosamino）-1-（3-pyridyl）-1-butanone （NNK）-mediated primary mouse peritoneal macrophages in vitro. Methods： The activity of peritoneal rnacrophages treated with different concentrations of LPS was detected by MTT assay in rider to find the optimal concentration. Peritoneal macrophages were also treated with NNK （100-500 μM）, with or without LPS for 9 h. The expression of NF-κB was demonstrated via immunocytochemistry （ICC） and Western- blot, respectively. Results： The concentration of LPS at 25 μg/mL was found to be the optimal concentration to improve the activity of peritoneal macrophages （P 〈 0.01）. Simultaneously, LPS （25 μg/mL） increased the expression of NF-κB in both the nucleus and cytoplasm and facilitated transfer of NF-κB to the nucleus. NNK treatment significantly inhibited the expression of NF-κB in a concentration-dependent manner, among the LPS-stimulated or unstimulated peritoneal macrophages, especially when cotreated with LPS （25 μg/mL, P 〈 0.01 ）. Furthermore, NNK treatment （500 μM） with LPS yielded a significant decrease in NF-κB translocation to nucleus and inhibited the expression of NF-κB （P 〈 0.005）. Conclusion： LPS enhances the suppression of NF-κB expression in NNK-mediated mouse peritoneal macrophages, which may provide a theoretical basis for the inhibition of cancer.

4-(甲基亚硝胺基)-1-(3-吡啶基)-1-丁酮接触生物标志物的研究进展

4-(甲基亚硝胺基)-1-(3-吡啶基)-1-丁酮(NNK)是烟草特有亚硝胺(TSNA)中具有强烈致癌性的物质之一,NNK在人体和动物体内产生的主要代谢物是4-(甲基亚硝胺基)-1-(3-吡啶基)-1-丁醇(NNAL)和它的糖苷化合物(NNAL-N-Glucuronidec和NNAL-O-Glucuronide)。NNAL是一种研究NNK在人体内代谢过程中致毒与解毒机制有价值的接触生物标志物。该文对NNK的流行病学、毒理学、代谢途径及其接触生物标志物的研究进展进行综述。

烟草与尿样中的代谢标记物

卷烟烟气进入人体后会对人体的代谢物产生影响,目前研究较多的是稠环芳烃类、烟草特有亚硝胺类和尼古丁的代谢物。文章分别介绍了稠环芳烃类代谢物1-羟基芘,烟草特有亚硝胺类代谢物NNAL和NNAL-Gluc,尼古丁的代谢物可天宁,对这些代谢物的检测方法、体内的含量水平、各种条件的影响进行了综述。

A New Co(Ⅱ)Coordination Compound Constructed by Tripyridyltriazole and Pyromellitic Acid:Synthesis,Crystal Structure and Antifungal Activity

A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.