Cyclocondensation Reactions of Hydrazonoyl Chlorides with Some Azines: Synthesis of New Fused Heterocycles of Expected Microbiological Activity

New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]-tetrazin-6-ones (16) were synthesized via reaction of the hydrazonoyl chlorides (1) with 1,3,6-triphenyl-9-thioxo-9,10-dihydro-pyrimido [4,5-b]pyrido[4,5-d][1,2,4]triazolo[4,3-a]pyrimidin-5,7(1H,8H)-di-one (5) and 4-amino-6-[(2-thiophen-2-yl)ethenyl]-3-thioxo-3,4-dihydro-[1,2,4]triazin-5(2H)-one (11), respectively. The mechanism and the regioselectivity of the studied reactions have been discussed. The biological activity of the products has been evaluated against some fungi and bacteria species. The tested compounds exhibited moderate activity against the bacteria species.

An Improved Synthesis of Azines under Solvent-Free Conditions

A new convenient and environmentally benign procedure for synthesis of azines from hydrazme sulfate with several aromatic aldehydes coupled with grinding is studied. This reaction is carried out under solvent-free conditions and in absence of catalyst to afford high yields of relevant azines.

A bench-stable reagent for C-4 selective deuteriodifluoromethylation of azines

Deuteriodifluoromethyl(CF_(2)D)is a challenging and important functional group due to difficult deuterium incorporation and lack of effective precursor reagents.Herein,we report a bench-stable reagent,deuteriodifluoromethyl phosphine(DDFP)from cheap deuterium source for selectivity deuteriodifluoromethylation of azines with a high deuterium incorporation yield.The late-stage modification of complex molecules further confirmed the potential of this reagent for practical applications.We expect that our reagent to find applications in synthesis of isotope-labelled molecules of interests for drug-discovery and related ilucidation of mechanism of action.

Cp^*Co(Ⅲ)-catalyzed C—H amidation of azines with dioxazolones

Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.

Cycl[3，2，2]azine类化合物的合成及光谱性能研究

合成了4个不同取代基的cycl[3,2,2]azine类化合物,首次研究了它们各自的紫外光谱和荧光光谱,计算了它们的荧光量子效率和stoke’s位移,对比讨论了取代基效应对其紫外光谱和荧光光谱的影响,发现了其分子结构与光谱性质之间的某些规律性的关系。部分化合物在蓝光区发射强烈的荧光,有望作为难得的蓝光区荧光材料。

溶剂效应对Cycl[3，2，2]azine类化合物光谱性能的影响

合成了4个不同取代基的Cycl[3,2,2]az-ine类化合物,首次研究了溶剂效应对其紫外光谱和荧光光谱的影响,发现这4种化合物在极性较大的乙醇和DMF溶剂中的紫外吸收峰值都比较大,而在乙醇和DMF溶剂中的荧光也都比较强。溶剂效应对这些化合物的紫外吸收波长和荧光发射波长无明显的影响,表明这些化合物对环境有这良好的适应性。这些化合物在蓝光区均能发射强烈的荧光,有望作为难得的蓝光区荧光材料。

3,4-Diphenylcycl[3,2,2]azine类化合物的合成及其光学性质研究

合成了3个不同取代基的3,4-Diphenylcycl[3,2,2]azine类化合物,首次测试了它们各自的紫外光谱和荧光光谱,计算了它们的荧光量子效率和Stoke’s位移,对比讨论了取代基效应对其紫外光谱和荧光光谱的影响,发现了其分子结构与光谱性质之间的某些规律性的关系.

腐胺对小鼠成纤维细胞中Atp8a1基因表达的影响

目的:研究腐胺对小鼠成纤维细胞中Atp8a1基因表达的影响,初步探讨其作用机制。方法:用基因芯片和Real-timePCR检测正常小鼠和Azin1(Antizyme inhibitor 1)基因敲除小鼠肝脏组织中Atp8a1基因的在mRNA水平上的表达;构建Atp8a1基因启动子的虫荧光素酶报告质粒pGL3-Atp8a1-P;将重组质粒转染NTH3T3成纤维细胞中,分别在含有4μg/ml腐胺和不含腐胺的条件下,用双荧光素酶检测系统检测虫荧光素酶活性。结果:在含有腐胺的培养条件下,转染Atp8a1基因启动子虫荧光素酶报告质粒的细胞虫荧光素酶的活性明显改变。结论:腐胺能够抑制Atp8a1基因启动子活性而降低其在NIH3T3成纤维细胞中的表达。

N-Cycl[3,2,2]azine甲酰脲衍生物对金属离子的选择性研究

比较了Ca2+、Ni2+、Cu2+、Zn2+、Sn2+、Pb2+、Mn2+、Al3+等8种金属离子对所合成的N-Cycl[3,2,2]azine甲酰脲衍生物荧光性能的影响,旨在探明该化合物衍生物对金属离子的选择识别性.结果发现在所选金属离子中只有Zn2+对其荧光淬灭较为显著,而对其他金属离子几乎无选择性.因此,该化合物衍生物有望能作为识别锌离子的有机荧光探针.

Cycl[3，3，2]azine类化合物光谱行为研究Ⅰ取代基种类和位置的影响

合成了具有不同取代基的12个cycl[3,3,2]azine类化合物.首次研究其紫外和荧光性能,分析了取代基效应对其光谱行为的影响,发现其分子结构与光谱性质之间存在着某些联系;其中A型化合物具有更强的蓝光荧光发射能力,使其有望成为难得的蓝光区荧光有机功能材料。

AZIN1慢病毒的制备及EC109稳定感染细胞株的建立

目的:制备野生型和编辑型AZIN1的慢病毒并建立稳定感染的食管癌EC109细胞株。方法:用RT-PCR法从人食管鳞状细胞癌组织中扩增出AZIN1基因的c DNA序列,选取测序结果中目标位点的A峰与G峰均高且与NCBI公布的基因编码序列一致的PCR产物,克隆至慢病毒表达载体p Lenti6/V5-D-TOPO,构建野生型和编辑型AZIN1的重组慢病毒表达载体,经酶切和测序鉴定后,经293FT细胞包装,制备相应的慢病毒,然后感染EC109细胞株,行RT-PCR、测序和Western blot鉴定稳定感染的EC109细胞株。结果:双酶切重组慢病毒表达载体后产生了1 347 bp和6 915 bp的片段,经测序证实1 347 bp片段为正确的AZIN1基因编码序列;RT-PCR、测序和Western blot结果证实成功建立了稳定感染的EC109细胞株。结论:成功制备了野生型和编辑型AZIN1的慢病毒并建立了稳定感染的EC109细胞株。

ORGANOMETALLIC FERROELECTRIC LIQUID CRYSTALS Ⅰ. LIQUID CRYSTAL PROPERTIES OF ORTHO—PALLADATED BINUCLEAR COMPLEXES OF AZINE, IMINE AND AZO DERIVATIVES

The mesomorphie properties of title complexes are investigated by means of DSC and polarizing microscopy. The mesophase temperature ranges of complexes are wider than that of corresponding organic ligands. The bridging groups of the complexes have profoand effects on the mesomorphic behavior, When the bridging groups are opticallhy active. the compleve show chiral smectic

Synthesis and mesomorphic properties of new azine-type liquid crystals

A series of symmetrical azine-type liquid crystals were synthesized. The characteristic of these liquid crystals is that they had high clearing point （～320℃） and broad thermal range of nematic phase （～154℃）. It was also found that the end groups of the liquid crystals had effect on the mesomorphic properties.

Synthesis and Crystal Structure of 4,5-Diazafluorene-9-one Azine Hydrochloride Hydrate

Crystals of the title compound C22H12N62HCl?H2O (DAA稨Cl) were obtained from a HCl aqueous solution of 4, 5-diazafluorene-9-one azine. The crystal belongs to monoclinic, space group P21/c with a = 5.203(3), b = 8.991(3), c = 22.17(1) , b = 92.13(4), V = 1036.2(9) 3, Z = 2, C22H18N6O2Cl2, Mr = 468.1, Dc = 1.503 g/cm3, F(000) = 484, m(MoKa) = 0.344 mm-1, R = 0.052 and wR = 0.056 for 755 observed reflections. The Cl…N(2) distance of 2.999(6) ?and Cl…HN(2) angle of 160.8(8)o imply the existence of a stronger H-bond between Cl and DAA. And both the rather longer ClH distance of 1.814(2) ?and the unexpected shorter N(2)H distance of 1.236(6) ?suggest the protonation of DAA molecule and explain the weak coordination ability of DAA to a metal center in the acidic solution.

ADAR1和AZIN1在胃癌患者癌组织与癌旁组织中的表达及临床意义

目的探究ADAR1和AZIN1在胃癌患者癌组织与癌旁组织中的表达及其临床意义研究。方法选取2020年1月至2021年1月在济宁医学院附属医院消化内科和肿瘤科治疗的116例I~III期胃癌患者为研究对象。所有患者均经手术切除治疗,并经组织病理学分析确诊。分析患者胃癌组织中ADAR1、AZIN1表达与临床病理特征的关系。通过qPCR分析胃癌及癌旁组织中ADAR1和AZIN1 mRNA表达。通过免疫组化分析胃癌及癌旁组织中ADAR1和AZIN1表达。分析ADAR1和AZIN1与患者术后3年生存率的关系。通过多变量Logistic回归分析影响胃癌患者预后不良的影响因素。使用ROC曲线分析ADAR1和AZIN1表达水平在胃癌患者预后中的诊断效能。结果ADAR1和AZIN1在未分化胃癌组织、有淋巴结转移和较高TNM分期的患者中表达水平较高,表明这两个基因的高表达与胃癌的恶性程度密切相关。qPCR分析显示,胃癌组织和癌旁组织中ADAR1 mRNA表达分别为1.96±0.18、1.12±0.03,胃癌组织和癌旁组织中AZIN1 mRNA表达分别为1.85±0.16、1.04±0.02,胃癌组织较癌旁组织升高(P<0.05)。ADAR1和AZIN1阳性患者与更低的3年生存率相关(P<0.05)。预后不良多因素Logistic回归分析中发现,胃癌低分化程度、浸润程度加深、淋巴结转移、较高的TNM分期、ADAR1阳性表达及AZIN1阳性表达均显著增加了胃癌不良预后的风险(P<0.05)。联合检测的敏感性和AUC值都高于ADAR1、AZIN1单独检测(P<0.05)。结论ADAR1和AZIN1在胃癌组织中的表达显著高于癌旁组织,特别是在未分化的肿瘤、有淋巴结转移和高TNM分期的患者中。这两个基因的高表达与胃癌患者的不良预后密切相关,联合检测显示出更高的诊断效能。ADAR1和AZIN1作为胃癌发展和预后的关键生物标志物,为胃癌治疗提供了新的靶点。

Pillar[5]arene and Azine Derivative Assembly Improved Dual-Channel Detection of CN-

The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-guest assembly.

Converting Azine Linkage into Highly Stable(Thio)Urea-Based Bicyclic-Fused-Ring Connections in Covalent Organic Frameworks via Criss-Cross[3+2]Cycloaddition

Exploring new linkage chemistry is of fundamental significance for covalent organic frameworks(COFs)to expand their structure and functional diversity.Herein,we report a strategy for converting azine linkage into urea-and thiourea-based fused-ring connections in COFs by criss-cross[3+2]dipolar cycloaddition of azine with HNCO or KSCN.The as-prepared COFs with cyclized linkages exhibited enhanced chemical and thermal stability by locking the dynamic C=N linkages in the progenitor.Moreover,functions could be introduced into the skeleton of COFs by this postsynthetic cyclization method,which enabled significant improvements in functionality,demonstrated by the studies on CO_(2)/N_(2) selective sorption,proton conduction,and Hg^(2+)adsorption.The use of this[3+2]cycloaddition strategy not only enriched the chemistry of linkage conversion for COFs but also offered a new way to fabricate fused-ring-linked COFs,thereby representing a high level of controllability on connectivity and functionality of COFs.

Structure-property relationship on aggregation-induced emission properties of simple azine-based AIEgens and its application in metal ions detection

In recent twenty years,aggregation-induced emission(AIE),due to its excellent application prospect,has aroused widespread interests.The development of novel and easy to make AIE luminogens(AIEgens)is an attractive subject.For this purpose,it is very important to study the structure-property relationship of AIEgens.Because azine derivatives are easy to synthesis and some of them have nice AIE properties,herein,a series of azine derivatives(ADs)were employed as models to study the influence of different functional groups,electronic effects and structures on the AIE properties of azine derivatives.The AIE mechanism were studied by single crystal analysis,density functional theory(DFT)calculations and so on.The results indicated that the o-hydroxyl aryl substituted azine compounds could show good AIE properties.Meanwhile,the AIE properties of o-hydroxyl aryl substituted azine compounds were also influenced by the electronic effects of the aryl groups in the azine compounds.The o-hydroxyl groups could form intramolecular hydrogen bond with imine group,which play key role to restrict the intramolecular rotation of the aryl groups and act as base stone for the AIE process of this kind compounds.The HOMO-LUMO energy gaps of o-hydroxyl substituted azine are smaller than other homologous compounds,which is agree with the proposed AIE mechanism.Finally,thanks to the AIE properties,the o-hydroxy-substituted azines could be used as efficient Al^(3+)and Cu^(2+)fluorescent chemosensors in different conditions.In addition,test strips based on AD10 has been prepared,which can conveniently detect Cu^(2+)in industrial wastewater.This research supplied a way for the design of novel easy to make AIEgens through simple azine derivatives.