N-甲基吡咯类聚酰胺的合成及其与DNA的相互作用

本研究主要是设计并合成了3个含有4个N-甲基吡咯的聚酰胺化合物(PyPyPyPyβDp,PyPyPyPyγDp, NO₂PyPyPyPyβDp),并使用ESI-MS法研究了其与DNA的相互作用.     

一些烷氧基亚甲基二苯胂基二茂铁衍生物的质谱分析

对６个新的烷氧基亚甲基二苯胂基二茂铁衍生物进行质谱分析研究，在它们的电子轰击电离质谱中显现了强的分子离子峰和表征主体结构的一系列特征峰。通过磁场／静电场联动扫描和精确质量的测定探索了这类化合物的质谱裂解规律。     

活性炭固相萃取-气相色谱-质谱法检测人尿中N,N-二甲基乙酰胺和N-甲基乙酰胺

建立了活性炭固相萃取-气相色谱-质谱同时测定尿中N,N-二甲基乙酰胺与N-甲基乙酰胺的气相色谱-质谱测定方法。在pH 7.0条件下,以活性炭固相萃取小柱萃取、净化,以甲醇洗脱,采用Innowax毛细管柱分离,选择离子检测。结果表明,N,N-二甲基乙酰胺和N-甲基乙酰胺线性范围在0.10～40.0 mg/L,相关系数分别为0.9997和0.9995;在空白尿样中分别添加低中高3个浓度水平,N,N-二甲基乙酰胺和N-甲基乙酰胺回收率分别为94.7%～102.6%和96.6%～101.2%,相对标准偏差均小于5.5%;以3倍性噪比计算检出限,N,N-二甲基乙酰胺和N-甲基乙酰胺检出限分别为0.01和0.03 mg/L。本方法精确、稳定、灵敏度高,可用于尿中N,N-二甲基乙酰胺和N-甲基乙酰胺的测定。     

1,3-二甲基-2-二茂铁甲基苯并咪唑碘盐的合成、表征、晶体结构及量子化学计算

A novel benzimidazole derivative, 1,3-dimethyl-2-ferrocenylmethylbenzimidazolium iodide （1） was synthesized and characterized by elemental analysis, MS, IH NMR and IR spectra. Its crystal structure was determined by X-ray single crystal diffraction, and the title compound belongs to monoclinic system with space group P2（1）/c. According to the crystal structure, the quantum chemistry calculation was performed by Gaussian 03 program, and full geometry optimizations of the title compound were carried out with DFT method at B3LYP/6-31G level. Its structure, stability, frontier molecular orbital components and net charge distribution were discussed.     

9,9-二甲基-2-(N-联苯基)氨基芴的合成

以芴为原料,苄基三甲基三溴化铵为溴化试剂,室温下在甲醇和二氯甲烷中溴化得到2-溴芴,然后以四氢呋喃为溶剂,在叔丁醇钾作用下与碘甲烷反应合成9,9-二甲基-2-溴芴,最后与4-联苯胺通过Buchwald-Hartwig偶联反应合成目标化合物9,9-二甲基-2-(N-联苯基)氨基芴,总收率为56.0%～62.4%。通过1HNMR、13CNMR、MS、IR和元素分析确证了其结构。     

气固顶空-气相色谱法测定纺织品中N,N-二甲基甲酰胺与N,N-二甲基乙酰胺

采用气固顶空-气相色谱法同时测定纺织品中N,N-二甲基甲酰胺(DMF)和N,N-二甲基乙酰胺(DMAC)的残留量。样品经剪碎后,称取0.5g,在120℃顶空温度下加热30min,顶空气体采用CAM色谱柱分离,以氮磷检测器(NPD)进行检测。以基体匹配校正法消除基质效应,外标法定量。DMF、DMAC的质量在0.2~400μg范围内与峰面积呈线性关系,检出限均为0.1μg·g-1。两种物质的加标回收率在88.4%~95.3%之间,相对标准偏差(n=6)在2.4%~3.5%之间。     

1,2-二甲基咪唑啉的合成及表征

对1,2-二甲基咪唑啉的合成进行了详细研究. 以甲胺水溶液和2-溴乙胺氢溴酸盐(1)为原料进行反应, 在两种原料物质的量之比为5∶1, 缓缓回流12 h的条件下, 得到N-甲基乙二胺(2), N-甲基乙二胺经过乙酸化得到N-甲基-N,N′-二乙酰基乙二胺(3), 然后, N-甲基-N,N′-二乙酰基乙二胺和氧化钙在高温下关环得到1,2-二甲基咪唑啉(4). 并对所得到的产物1,2-二甲基咪唑啉经元素分析, 1H NMR, IR和GC-MS得到了表征.     

电喷雾电离-串联质谱法测定纺织皮革产品中4,4-二氨基二苯醚

在不需要色谱分离的前提下,应用电喷雾电离-串联质谱法(ESI-MS/MS)对纺织品中偶氮染料还原产物4,4′-二氨基二苯醚进行测定。在MS/MS中,选择电喷雾离子源,以正离子扫描,选择离子监测模式和二级选择反应监测模式对4,4′-二氨基二苯醚进行定性和定量检测。以[M+H](m/z201)为母离子,选择其二级离子中碎片离子[M+H-NH3](m/z184)和[M+H-C6H7N](m/z108)为子离子。方法的检出限(19S/N)为70 ng.L-1。以1 ng.L-14,4′-二氨基二苯醚溶液进样2μL,平行测定9次,峰面积测定值的相对标准偏差为1.7%。     

二茂铁甲基季铵盐对异烟肼的电催化氧化及其电分析方法研究

研究了铂电极上二茂铁甲基季铵盐电催化氧化异烟肼的电化学行为,并且对异烟肼药物的电分析方法进行了研究。实验结果发现,二茂铁甲基季铵盐对异烟肼的电化学氧化具有很好的催化作用。当二茂铁甲基季铵盐浓度一定时,催化氧化峰电流与异烟肼浓度在5×10-5~6×10-4mol/L的浓度范围有良好的线性关系(r=0.9984),运用方波伏安法测定了异烟肼样品含量,与紫外分光光度法所得结果进行比较,相对标准偏差在0.5%以内,标准加入的回收率在98.0%~101.0%之间。     

Synthesis of S-catecholboryl (N,N-dimethylaminomethyl)-phenyldithiophosphinate

S-Catecholboryl (N,N-dimethylaminomethyl)phenyldithiophosphinate, the first representative of S-diorganylboric derivatives of phosphonous acid was obtained by the reaction of catecholboryl (N,N-dimethylaminomethyl)phenylphosphine with sulfur.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1871–1873, August, 1990.     

Visible light active Ag,N co-doped titania in the photo-oxidation of some 9-(N,N-dimethylaminomethyl)anthracene systems

Irradiated semiconductor catalysis in the presence of molecular oxygen can be admitted as an innovative and economical process for the conversion of harmful aromatics to less harmful products. The present work reports the preparation of a co-doped system by sonication assisted sol–gel technique followed by calcination at 500 °C and checks its activity in photo-oxidation reactions. The prepared system was characterized by various physico-chemical techniques such as X-ray diffraction, Raman spectroscopy, IR spectroscopy, TG-DTG, UV-DRS, SEM, and XPS. Thermal stability and structural identity were observed from TG and XRD measurements respectively. On reaction, Tertiary amine appended anthracene and its phenyl substituted derivative in CH₃CN yielded Anthraquinone as the major product. Substituted Anthracenemethanamine reacted slowly and a relatively stable intermediate could be isolated at shorter periods of time. The products were separated and purified by column chromatography and the resultant products were characterized thoroughly by ¹H NMR, IR spectroscopy and GCMS analysis.     

A novel synthesis of α-methylene-γ-butyrolactones from 1-(N,N-dimethylaminomethyl)cyclopropanecarboxylate esters

A new method is reported for constructing α-methylene-γ-butyrolactone moiety under neutral, anhydrous conditions. Olefin-dibromocarbene adducts are transformed to methyl 1-(N,N-dimethylaminomethyl)cyclopropanecarboxylates which in turn are treated with trimethylsilyl iodide and the crude products distilled to give the title compounds with high regio- and stereoselectivity.     

二茂铁催化鲁米诺电致化学发光反应的研究

在碱性Tris缓冲体系中 ,鲁米诺与过氧化氢的电致化学发光反应要在 4 5 0mV以上的电位下才可以发生 ,加入羧基二茂铁 (FCA)可以使这一发光反应的起始电位负移 ,而且发光信号随电极电位的增大而急剧增强。详细考察了这一催化发光体系 ,研究了影响发光强度的各种因素 ,建立了Luminol H2 O2 FCA发光体系测定FCA的电致化学发光新方法。方法测定二茂铁的检出限可达 1.5nmol/L ,二茂铁浓度在 5 .0× 10 -9～ 2 .0×10 -4mol/L范围内与电致化学发光强度呈良好的线性响应关系     

Mass spectrometric structure determination of metabolites of 3-[2-(N,N-dimethylaminomethyl)phenylthio]phenol

Metabolites of 3-[2-(N,N-dimethylaminoethyl)phenylthio]phenol (I) were isolated from the urine of rats, mice, rabbit and dog and from the faeces of rats by extraction and thin-layer chromatography. From the mass spectrum of I and using characteristics mass shifts in the spectra of metabolites, the structures of four metabolites were determined, whereas for two other isomeric metabolites the structures were resolved by means of IR spectra. Conclusions regarding the structures derived from the spectra were confirmed by comparing them with synthetic standards. Generally, metabolic changes of I can be characterized by demethylation, hydroxylation combined with methylation, S-oxidation and by a combination of these metabolic reactions.     

Directly fused highly substituted naphthalenes via Pd-catalyzed dehydrogenative annulation of N,N-dimethylaminomethyl ferrocene using a redox process with a substrate

N,N-Dimethylaminomethyl ferrocenium could be generated in situ and served as a terminal oxidant for Pd-catalyzed directly dehydrogenative annulations of N,N-dimethylaminomethyl ferrocene and internal alkynes. This procedure utilized the redox activity of ferrocene and avoided adding an oxidant. A series of highly arylated naphthalenes functionalized by ferrocene were obtained in 53-81% yields.     

四氧化二氮-五氧化二氮-硝酸体系组成的分析

1引言N2O5作为新型硝化剂受到广泛的关注。N2O4电解氧化制N2O5过程中,在阳极得到N2O4、N2O5和HNO3的混合物,因此需要对N2O4-N2O5-HNO3体系进行分析。由于N2O4、N2O5和HNO3的结构相似,这给拉曼光谱等光谱分析方法定量分析此体系带来很大的困难。本实验采用简单经济的滴定法,并用     

Structural investigation of 1-(N,N-dimethylaminomethyl)-spirobi(3-oxo-2,5-dioxa-1-silacyclo-pentan)ates

1-[(N,N-Dimethyl)aminomethyl]spirobi(3-oxo-2,5-dioxa-1-silacyclopentan)ate and 1-(N,N-dimethyl)-aminomethyl]spirobi(4,4-dimethyl-3-oxo-2,5-dioxa-1-silacyclopentan)ate are representatives of amino-methylspirobi(3-oxo-2,5-dioxa-1-silacyclopentan)ates, which are electrostatically stabilized silanates (ES silanates). X-ray diffraction structural analysis and quantum-chemical calculations were used in a structural study of these compounds. The factors affecting the geometry of these molecules are discussed. Dedicated to Academician Janis Stradins on the Occasion of His 75^th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1873–1881, December, 2008. An erratum to this article can be found at