2-萘甲酸/1,10-菲啰啉共同构筑Mn(II)配合物的合成及固态发光

在溶剂热条件下,以2-萘甲酸(HL)与1,10-菲啰啉(phen)为配体、碳酸锰为金属源合成了一例双核锰配合物[Mn_(2)(L)_(4)(phen)_(2)(H_(2)O)_(2)](1)。通过单晶X射线衍射、元素分析、傅里叶变换红外光谱、粉末X射线衍射和热重分析等对配合物1进行结构表征。单晶衍射分析表明配合物1属于三斜晶系,P1空间群,晶胞参数为a=0.76989(5)nm,b=1.17586(5)nm,c=1.66830(9)nm,α=107.074(5)°,β=96.167(5)°,γ=106.901(5)°。不对称单元由一个锰离子、两个2-萘甲酸根、一个1,10-菲啰啉和一个水分子组成,Mn(II)呈扭曲的八面体构型。两个不对称单元之间通过羧基氧原子桥接形成双核分子,双核结构之间通过π…π堆积作用形成2D超分子结构。荧光光谱分析结果表明:配合物1具有良好的荧光性能,最大发射波长为416 nm(λ_(ex)=302 nm)。热重分析表明配合物1能够稳定到117℃,之后开始失水(失水量为3.18%),脱水之后的结构能稳定到223℃,之后有机骨架开始坍塌。Hirshfeld表面分析研究了分子间的相互作用。

含四氮杂大环的双(O,O'-二(2-苯乙基)二硫代磷酸根)合镍(II)或铜(II)配合物的合成和晶体结构

合成了含四氮杂大环hmta(hmta = meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷 )和O,O-二(2-苯乙基)二硫代磷酸根的配合物 [Ni(hmta){SSP(OCH2CH2Ph)2}2] 1和 [Cu(hmta){SSP(OCH2CH2Ph)2}2] 2 , 并测定了它们的晶体结构。配合物1属单斜晶系,空间群为P21/c,晶胞参数为: C48H72N4O4P2S4Ni, a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) 3, Z = 2, Dc = 1.285 g/cm3, = 0.635 mm-1, F(000) = 1076, 最终的偏离因子为R = 0.0434, wR = 0.1078, 相应的可观测反射数为2306; 配合物2属单斜晶系, 空间群为P21/c, 晶胞参数为: C48H72N4O4P2S4CuO25, a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624 (1) 3, Z = 2, Dc = 1.295 g/cm3, = 0.681 mm-1, F(000) = 1086, 最终的偏离因子为R = 0.0465, wR = 0.1222, 相应的可观测反射数为2492。结构测定表明:两配合物中的配体 (PhCH2CH2O)2PS2-均为单齿配体,金属离子与硫和氮形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性; 同时晶胞中配合物的两配体之间形成了2种N-H贩稴氢键。

NoV GⅡ.2亚型RT-RPA-CRISPR/Cas12a检测方法的建立

近年来,一种新的诺如病毒GⅡ.2亚型(norovirus GⅡ.2,NoV GⅡ.2)通过牡蛎等生食海鲜感染人群,引发急性胃肠炎,并在全球广泛传播。为实现NoV感染的现场诊断和快速疫情响应,亟需建立快速便捷的NoV GⅡ.2亚型核酸检测方法。本研究通过设计引物、crRNA,经优化反应条件后,建立了NoV GⅡ.2亚型RTRPA-CRISPR/Cas12a检测方法。结果显示:利用引物NoV-GⅡ.2-F1B和NoV-GⅡ.2-R1对NoV GⅡ.2标准RNA进行RT-RPA扩增,结合crRNA1介导的CRISPR/Cas12a报告体系,能在40 min内完成NoV GⅡ.2核酸检测;该方法检测灵敏度为10 copies/μL,且与轮状病毒、腺病毒、星形病毒、人副肠孤病毒、博卡病毒和札如病毒无交叉反应;应用该方法和qRT-PCR法,分别对30份临床模拟样本进行检测,发现总符合率达96.67%。结果表明,本研究建立的NoV GⅡ.2亚型RT-RPA-CRISPR/Cas12a检测方法无需依赖昂贵设备,具有灵敏度高、特异性强、操作便捷快速等特点,为NoV GⅡ.2感染的现场检测和防控提供了新方法。

Synthesis, Crystal Structure and DNA Binding Studies of a Nickel(II) Complex with 2-Aminomethylbenzimidazole and Demethylcantharate

A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.

MoS_(2)/Fh复合材料的制备及高盐条件下EDTA-Pb(Ⅱ)的去除研究

水铁矿(Fh)因其比表面积大、吸附能力强等优点,对络合态重金属表现出良好的吸附能力,但是盐离子的存在会阻碍Fh对络合态重金属的去除。本研究引入了二硫化钼(MoS_(2)),利用其优异的阻盐能力弥补Fh去除性能被抑制的情况。考察了溶液pH、盐度等不同因素对MoS_(2)/Fh复合材料吸附性能的影响,在15 g/L NaCl的背景盐度、pH=4条件下,1 g/L MoS_(2)/Fh复合材料对20 mg/L EDTA-Pb(Ⅱ)的去除率仍能达到96.72%,较相同条件下Fh的去除率显著提高。通过对吸附机理的探究发现EDTA-Pb(Ⅱ)主要以静电吸附方式被去除。

Ca2+/calmodulin-dependent protein kinase II regulates colon cancer proliferation and migration via ERK1/2 and p38 pathways

AIM To investigate the role of calmodulin-dependent protein kinase Ⅱ(Ca MKⅡ) in colon cancer growth,migration and invasion.METHODS Ca MKⅡ expression in colon cancer and paracancerous tissues was evaluated via immunochemistry. Transcriptional and posttranscriptional levels of Ca MKⅡin tissue samples and MMP2,MMP9 and TIMP-1 expression in the human colon cancer cell line HCT116 were assessed by q RTPCR and western blot. Cell proliferation was detected with the MTT assay. Cancer cell migration and invasion were investigated with the Transwell culture system and woundhealing assay.RESULTS We first demonstrated that CaMK Ⅱ was ove rexpressed in human colon cancers and was associated with cancer differentiation. In the human colon cancer cell line HCT116,the Ca MKII-specific inhibitor KN93,but not its inactive analogue KN92,decreased cancer cell proliferation. Furthermore,KN93 also significantly prohibited HCT116 cell migration and invasion. The specific inhibition of ERK1/2 or p38 decreased the proliferation and migration of colon cancer cells.CONCLUSION Our findings highlight Ca MKⅡ as a potential critical mediator in human colon tumor development and metastasis.

Spectroscopic and molecular structure characterization of the bis(2-aminophenol)(5, 10, 15, 20-tetraphenylporphyrinato) cobalt(II) complex

The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.

Synthesis and Electrochemical, Fluorescent and Magnetic Properties of a New Cadmium(II) Complex with 2-Benzoylbenzoic Acid

A new cadmium(II) complex Cd(OBBA)2(2,2A-bipy)2 with 2-benzoylbenzoic acid(HOBBA) and 2,2-bipyridine(2,2A-bipy) as ligands has been synthesized. Crystal data for the complex are as follows: monoclinic, space group P21/c with a = 16.402(3), b = 10.4191(18), c = 23.395(4) A, β = 91.765(2)o, V = 3996.2(12) A3, Dc = 1.455 gAcm-3, Z = 4, μ(Mo Kα) = 0.603 mm-1, F(000) = 1784, the final R = 0.0218 and w R = 0.0558. In the electrode reaction, its electron transfer is quasi reversible and the electrode reaction corresponds to Cd(II)/Cd(0). Under 618 nm radiation, the title complex shows a strong fluorescent band at around 326 nm. In addition, in the range of 2~300 K, this complex displays diamagnetic property.

Crystal Structure and Inhibitory Activity against Xanthine Oxidase of Bis(μ_2-chloro)-chloro-(μ-N,N'-(2-pyridylmethylene) Furanmethanoamine Copper(II) Complex

A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Clinical Observation of rhIL-2 Combined with Zhenqi Fuzheng and BaofuKang Suppository in the Treatment of Cervical Intraepithelial Neoplasia II with HPV Infection

Objective: To investigate the clinical effects of recombinant human interleukin-2 (rhIL-2) combined with Zhenqi Fuzheng and Baofukang on cervical intraepithelial neoplasia II (CINII) combined with human papilloma virus infection. Methods: There were 593 patients diagnosed with CINII with HPV infection, including 296 in the control group and 297 in the experimental group. The control group was given only Zhenqi Fuzheng oral and Baofukang suppository vaginal medicine. The experimental group was treated with rhIL-2 injection in addition to Zhenqi Fuzheng oral and Baofukang suppository vaginal medicine which is treated for 3 months. After 3 months, Thinprep cytologic test (TCT), human papilloma virus (HPV) quantitative examination and colposcopy biopsy were reviewed. Results: After 3 months of treatment, the negative conversion rate and total effective rate of HPV in the control group were 58.11% and 70.95% respectively, and the negative conversion rate and total effective rate of the experimental group were 79.46% and 90.57% respectively. There was significant difference between the two groups (p = 0.000). The curative rate of cervical lesions was significantly higher in the test group than in the control group, 89.56%, 68.91%, respectively. The statistical difference between the two groups is significant (p = 0.000). Conclusion: It has an essential clinical value that HPV infection patients and cervical intraepithelial neoplasia II associated with HPV infection patients are treated by rhIL-2 combined with Zhenqifuzheng and Baofukang, which is safe, effective, non-invasive, reusable advantages. However, the long-term efficacy and side effects need to be further studied.

Synthesis, Characterization and DFT Studies of Two Zinc(II) Complexes Based on 2-Isopropylimidazole

Two novel coordination compounds, [Zn(L)2(OOCH)2] (1) and [Zn(L)3(OCHO)](OCHO)]·H2O (2) (where L = 2-isopropylimidazole, C6H10N2) have been prepared by reaction of 2-isopropylimidazole with zinc(II) formate at room temperature using toluene as solvent. These compounds were characterized by elemental and thermal analyses, IR, 1HNMR and 13CNMR spectroscopies, single crystal X-ray diffraction and DFT studies. The Zn centers in 1 and 2 adopt pseudo-tetrahedral coordination geometries. Compound 1 crystallizes in the monoclinic system P2/c space group whereas compound 2 crystallizes in the P-1 space group of the triclinic crystal system. Several types of hydrogen intra-/intermolecular interactions are observed in these materials and extend into a two-dimensional leaf like network in 1 and a two-dimensional lattice of rectilinear pillars in 2. Compounds 1 and 2 were also optimized and their frontier molecular orbitals, global reactivity descriptors, molecular electrostatic potential, natural bond orbitals were investigated using density functional theory (DFT). In fact the induced structural differences from complex 1 to complex 2 led to the reduction of the frontier molecular orbital energy gap by 1.338 eV and a decrease of the chemical hardness by 0.669 eV.

Synthesis and Crystal Structure of Dichlorobis-(1-methylimidazoline-2(3H)-thione-S) Cobalt(II)

The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) ?, β = 91.181(3)o, V = 1457.70(17) ?3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm–1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2σ(I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N–H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face dis- tance of 3.604 ? are found in the packing diagram.

Development of a Highly Sensitive Extractive Spectrophotometric Method for the Determination of Nickel(II) from Environmental Matrices Using 2-Acetylpyridine-4-methyl-3-thiosemicarbazone

Nickel(II) reacts with 2-acetylpyridine-4-methyl-3-thiosemicarbazone (APMT) and forms a yellow colored complex, which was extracted into n-hexanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-APMT complex was measured at different intervals of time at 375 nm to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72 hrs. The system obeyed Beer’s law in the concentration range of 0.235 - 2.43 μg·ml–1 of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell’s sensitivity of the extracted species were found to be 2.16 × 104 L mol–1 ·cm–1 and 0.003 μg·cm–2 at 375 nm, respectively. Hence a detailed study of the extraction of nickel(II) with APMT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.

血管紧张素Ⅱ-2型受体A1675G基因多态性与家族性高血压的相关性研究

目的:探讨血管紧张素Ⅱ-2型受体(AT2R)A1675G基因多态性与家族性高血压的相关性。方法:选取高血压家系(高血压家系组)30个(120例受试者)和正常血压家系(正常血压家系组)29个(115例受试者)进行对照研究。采用聚合酶链式反应(PCR)技术分析AT2R A1675G基因多态性;采用酶联免疫吸附试验(ELISA)技术测定AT2R的表达。结果:高血压家系组AA型、AG型频率分布(53.3%、16.7%)比正常血压家系组(38.2%、12.2%)均升高,GG型频率分布(30.0%vs 49.6%)降低,高血压家系组比正常血压家系组等位基因A的频率分布(61.7%vs 44.3%)升高、G的频率分布(38.3%vs 55.7%)降低,差异均有统计学意义(P<0.05)。高血压家系组与正常血压家系组比较,AG型患者和GG型患者的AT2R表达浓度[(43.4±12.4)ng/ml vs(52.4±11.6)ng/ml,(53.2±15.3)ng/ml vs(65.9±16.9)ng/ml]均降低,差异有统计学意义(P<0.05)。结论:AT2R基因A1675G多态性与家族性高血压有明显相关性;G基因和AT2R在家族性高血压的发病中起着重要的保护作用。

胃大部分切除术后ROUX-en-Y吻合及毕Ⅱ式吻合对2型糖尿病血糖的影响

目的:研究胃大部分切除手术后进行ROUX-en-Y吻合与毕II式吻合重建对2型糖尿病患者血糖的影响。方法前瞻、非随机对我科2006年1月至2009年12月收治的40例不合并肥胖的胃癌及胃溃疡患者接受ROUX-en-Y吻合重建26例与毕II式吻合重建24例。检测手术前后血糖及糖化血红蛋白(HbA1c)的变化。结果 ROUX-en-Y吻合重建组:空腹血糖在术后1月下降(P<0.05),餐后2h血糖在术后第1周下降(P<0.05),糖化血红蛋白在术后1月下降(P<0.05);毕II式吻合重建组:空腹血糖在术后6月下降(P<0.05),餐后2 h血糖在术后第1月下降(P<0.05),糖化血红蛋白在术后3月下降(P<0.05)。两组相比:术后1月空腹血糖及6月餐后2 h血糖差异有统计学意义(P<0.05),术后3月糖化血红蛋白差异有统计学意义(P<0.05)。结论胃大部分切除手术后进行ROUX-en-Y吻合重建与毕II式吻合重建均能够降低2型糖尿病患者的血糖,但以ROUX-en-Y吻合重建手术效果较为显著。ROUX-en-Y吻合重建术后血糖的下降可能与血中胰高血糖素样肽-1水平升高有关。

2-苯甲酰苯甲酸铜配合物的合成、电化学、荧光及磁性研究(英文)

以2-苯甲酰苯甲酸(HL)和1,10-邻菲啰啉(Phen)为配体合成了一个新的铜(Ⅱ)配合物{[Cu2(Phen)4(NO3)][Cu(Phen)2(L)]2(L)2(NO3)3}·2H2O(1)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.138 57(5)nm,b=1.193 49(7)nm,c=2.615 31(13)nm,α=89.428 0(10)°,β=82.753(2)°,γ=74.537 0(10)°,V=3.3968(3)nm3,Dc=1.408 g·cm-3,Z=1,μ(Mo Kα)=0.700 mm-1,F(000)=1 480,最终偏离因子R1=0.057 1,wR2=0.133 4。在标题配合物分子中,有2个单核阳离子[Cu(Phen)2(L)]+和1个双核阳离子[Cu2(Phen)4(NO3)]3+,中心铜(Ⅱ)离子的配位数都是五。测定了标题配合物的电化学、荧光和磁性。结果表明:在循环伏安过程中,配合物的电子转移是准可逆的,对应的电极反应是Cu(Ⅱ)/Cu(Ⅰ);当激发波长为488 nm时,配合物在494 nm附近有较强的荧光发射峰;在300～52 K,配合物具有抗磁性。

超级稻新组合II优航2号产量结构及增产途径分析

利用DPS数据统计软件,对II优航2号的6个产量构成因素进行多元逐步回归分析、相关分析、通径分析以及Eberhard and Russell模式分析。结果表明,穗数对II优航2号产量的作用最大,结实率和穗实粒数对产量也有较大影响。高产栽培策略是在确保足够有效穗的前提下,适度促大穗,提高结实率。笔者还对该组合的丰产稳产性进行分析,结果表明,II优航2号丰产性、稳产性及适应性都优于对照,是一个较为理想的迟熟杂交稻新组合。

基于2-(4-甲基苯甲酰基)苯甲酸及2,2′-联吡啶的双核铜(Ⅱ)配合物的晶体结构、荧光和磁性(英文)

以2-（4-甲基苯甲酰基）苯甲酸（HL）及2，2＇-联吡啶（2，2＇-bipy）为配体合成了一个双核铜（Ⅱ）配合物[Cu2（L）4（2，2＇-bipy）2]·H2O（1），并对其进行了晶体结构测定。测定结果表明，该配合物晶体属于三斜晶系，空间群为P1，晶胞参数：a=1.01257（15）nm，b=1.3125（2）nm，c=1.3170（2）nm，α=82.985（2）°，β=76.437（2）°，γ=88.290（2）°，V=1.6887（4）nm3，Dc=1.391g·cm-3，Z=2，F（000）=732，GooF=1.027，最终偏离因子R1=0.0375，wR2=0.0914。在配合物分子中相邻的2个铜（Ⅱ）离子通过2个2-（4-甲基苯甲酰基）苯甲酸根桥联配位连接起来，其端位各与1个2-（4-甲基苯甲酰基）苯甲酸根和1个2，2＇-联吡啶分子配位，整个分子形成了双核结构。测定了标题配合物的荧光和磁性，结果表明：当激发波长为608nm时，配合物在472和476nm处有2个较强的荧光发射峰；在2~100K，配合物具有顺磁性。