C-N化合物合成研究

用能量 50 - 1 1 0 ke V的 N离子在低于 80°C温度下注入 CVD法合成的金刚石薄膜后 ,分别用 X射线光电子谱、红外谱和拉曼谱检测注入后的薄膜中是否形成了 C- N化合物 .结果表明注入后的薄膜中存在有 3种化学键态的 C- N化合物 ,且低能离子注入更有利于 C- N化合物的形成 .由于在注入区内形成了大量的 C- N单键 ,这有利于β- C3N4 的合成 .对 C- N化合物薄膜的场发射特性也做了研究.Diamond films were implanted with 50-110 keV N ions to the dosage of 1×10 17 ions/cm 2 at the temperature below 80 °C . The possibility of the formation of C N compounds in diamond films was investigated by means of X ray photoelectron spectroscopy (XPS), X ray diffraction analysis (XRD), Fourier transform infrared absorption spectroscopy (FTIR) and Raman spectroscopy. New evidence has been presented that plenty of C-N single bonds which are necessary ...     

SPME-GC-MS分析瀑布毛峰茶叶的赋香成分

采用顶空-固相微萃取法(SPME)从瀑布毛峰茶叶中提取挥发性成分,用气相色谱-质谱法(GC-MS)分析其组成。从一级和特级茶叶中分别鉴定了相对含量大于0.50%的化合物48个和41个,其中共同组分27个。一级瀑布毛峰茶叶的主要挥发性成分有壬醛(9.22%),芳樟醇(4.75%),牛儿醇(4.07%),(Z)-3-己烯-1-醇(3.53%),十一醛(3.16%),邻苯二甲酸二异丁酯(2.94%),十六烷(2.35%),己醛(2.00%),1-辛醇(1.97%),6-甲基-5-庚烯-2-酮(1.86%)。特级瀑布毛峰茶叶的主要挥发性成分有:壬醛(8.85%),1-辛烯-3-醇(6.37%),十一醛(4.81%),2,5,5-三甲基-1-己烯(2.84%),辛醛(2.73%),1-辛醇(2.63%),6-甲基-5-庚烯-2-酮(2.60%),芳樟醇(2.20%),1-戊醇(2.20%),己醛(2.16%)。两个等级的瀑布毛峰茶的主要挥发性成分大致相同,但各成分的含量存在一定差异。     

Fluorescene Quenching of Some Organic Compounds with Nitrotoluene Vapor

Russian Physics Journal - Sensor properties of poly(9,9-di-n-octyl-2,7-fluorene) (PFO), poly[9,9-dioctylfluorenyl-2,7-diyl] end capped with dimethylphenyl (ADS), polyvinylcarbazole (PVK),...     

硒杂环-金属离子在乙醇溶液中的紫外吸收光谱

研究了不同分子结构的硒杂环化合物—金属离子在乙醇溶液中的紫外吸收光谱 ,硒杂环均为苤硒脑类化合物 (piazselenoles,简称Pis) :4 ,5 benzopiazselenole(BP) ;anthra[1,2 c][1,2 ,5 ]selenadiazol 6 ,11 dione(AS) ;piazselenole(PS) ;5 methyl piazselenole(MP) ;4 ,6 diBr piazselenole(DBP) ;4 ,4 ' dipiazselenole(DP)。结果表明 :Pis随分子共轭体系增大或共轭效应增强 ,紫外吸收波长λ呈现有规律地红移 ,摩尔吸光系数ε增大 ;Sn(Ⅳ ) ,Cd(Ⅱ ) ,Cr(Ⅲ ) ,Sb(Ⅲ ) ,Fe(Ⅲ ) ,Fe(Ⅱ )及Cu(Ⅱ ) BP≥ 1均使BP的紫外吸收增强 ,Zn(Ⅱ )的影响较小。Sn(Ⅳ ) ,Cr(Ⅲ )和Sb(Ⅲ )均可使Pis的短波位置的紫外吸收增强 ,使MP于 2 33nm处的峰形变钝。     

Pressure Induced Disordering of Vacancies in RNi 2 Compounds

As known from earlier investigations, most of the RNi 2 compounds (R…rare earth element) do not crystallize in the cubic Laves phase structure (C15), but in a superstructure of C15 with ordered vacancies at the R sites. In the present work high pressure X-ray diffraction experiments on selected RNi 2 compounds (R=Tb, Sm, Gd and Y) are presented, showing that pressures of about 8-15 GPa lead to a disordering of the vacancies in all of them. Furthermore the studies show that the pressure-induced order-disorder transition is closely related to the earlier observed disordering of the vacancies at high temperatures between 430 K (TbNi 2 ) and 740 K (YNi 2 ), and that there is a pronounced variation of the transition pressures and temperatures among the investigated compounds.     

Irradiation of Phenolic Compounds with Ultraviolet Light Causes Release of Hydrated Electrons

Phenolic compounds are widely used for a number of purposes, including medical drugs, cosmetics, food additives, and supplementary foods, and are often exposed to the ultraviolet (UV) rays of the sun. We herein examined free radicals produced from phenolic compounds by UV irradiation using an electron paramagnetic resonance (ESR)-spin trapping technique with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). The ESR signals of DMPO adducts of the hydrogen radical (DMPO–H) and hydroxyl radical were detected following the UV irradiation of polyhydric phenols, such as hydroquinone, catechol, resorcinol, pyrogallol, and methyl gallate, in an aqueous solution. Radical adducts were not detected in monohydric phenols, such as phenol and methylparaben. The signal intensity of DMPO–H became stronger as the concentration of phenolic compounds increased. The signal intensity of DMPO–H decreased when the solution in which air was replaced with N₂O, a scavenger of hydrated electrons, was irradiated. However, sodium formate, a scavenger of the hydrogen radical, did not affect the signal intensity of DMPO–H. The signal intensity of DMPO–H became stronger as the pH of the solution increased. Semiquinone-type radicals increased following the UV irradiation of solutions of polyhydric phenols in the absence of DMPO. These results indicate that hydrated electrons are generated by the UV irradiation of polyhydric phenols, and that phenoxide ions are responsible for the production of hydrated electrons.     

塑料挥发物长光程FTIR测量方法

塑料产品除了在自然环境中可降解为微塑料污染环境之外,还会产生挥发性有机物,同样对环境造成巨大的污染和危害,因此对塑料挥发物的测量就显得尤为重要。目前传统挥发物的测量方法,如环境质谱法和色谱法等,存在测量过程复杂,成本高,无法实时测量等缺点,因而需要一种快速有效的针对塑料挥发物的测量方法。采用傅里叶变换红外光谱仪（Fourier transform infrared spectrometer,FTIR Spectrometer）结合怀特池对塑料挥发物进行测量,但是由于抽取式傅里叶变换红外光谱仪本身灵敏度有限,很难实现微量的塑料挥发物的测量,所以针对这一问题,尝试通过长光程气体池提高常规傅里叶变换红外光谱仪的灵敏度从而实现不同种类塑料挥发物的测量。选取了5种塑料产品,分别是低密度聚乙烯（LDPE）,高密度聚乙烯（HDPE）,聚乙烯（PE）,聚对苯二甲酸乙二醇酯（PET）,聚丙烯（PP）,利用光程长为20 m的怀特池结合傅里叶变换红外光谱仪实现了其中一些挥发物的光谱特征观测,实验观察到所有种类的塑料在2个光谱波数段具有明显的光谱特征,分别为800~850和1 050~1 150 cm-1。除聚对苯二甲酸乙二醇酯（PET）外,其余4种塑料挥发物在2 800~3 000 cm-1还存在明显的光谱吸收波段。进一步又研究了不同温度条件下塑料产生的挥发物,通过分析不同温度条件下的塑料产生的挥发物的红外光谱,发现除低密度聚乙烯（LDPE）在两种温度条件下光谱差异较大外,其他种类的塑料挥发物红外光谱差异较小。该研究提出了一种新型的基于长光程FTIR的塑料挥发物的测量方法,证实了其在塑料挥发物测量方面的有效性,这种方法具有测量成本低,可连续观测,实时在线等优点,为实现连续在线的塑料挥发物排放通量监测奠定了基础。     

Flow Injection Analysis of Pharmaceutical Compounds. VI. Determination of Some Central Nervous System Acting Drugs by UV-Spectrophotometric Detection

Abstract

The Present work describes a direct flow injection analysis (FIA) of five commonly used central nervous system (CNS) acting drugs namely amitriptyline hydrochloride, carbamazepine, clomipramine hydrochloride, fluphenazine hydrochloride and imipramine hydrochloride. The characteristics of the system and the conditions of the speatrophotometric determination are evaluated. The proposed technique can be applied for pharmaceutical quality control of the pure material and pharmaceutical dosage forms containing the drug. Amount ranging from 16 to 80 μg. ml^?1 of amitriptyline hydrochloride.

The Present work describes a direct flow injection analysis (FIA) of five commonly used central nervous system (CNS) acting drugs namely amitriptyline hydrochloride, carbamazepine, clomipramine hydrochloride, fluphenazine hydrochloride and imipramine hydrochlorode. The characteristics of the system and the conditions of the spectrophotometric determination are evaluated. The proposed technique can be applied for pharmaceutical quality control of the pure material and pharmaceutical dosage forms containing the drug. Amount ranging from 16 to 80 μ.ml^?1 of amitriptyline hydrochloride, carbamazepine and fluphenazine hydrochloride and from 32 to 160 μ. ml^?1 of clomipramine hydrochloride and imipramine hydrochloride dissolved and/or extracted in ethanol could be accurately analyzed. Standard addition (0.5 to 3 times of the claimed amounts) of authentic samples to powdered tablets gave good mean percent recoveries with low standard deviations. Samples can be introduced at rates of about 180 per hour or even more. The results obtained by applying the proposed FIA method are statistically analyzed and compared with those obtained from applying pharmacopoeial procedures.     

硒杂环-金属离子在乙醇溶液中的发光

研究了不同分子结构的硒杂环化合物 金属离子在乙醇溶液中的发光 ,硒杂环均为苤硒脑类化合物(Piazselenoles,简称Pis) :Piazselenole(PS) ;4 ,5 benzopiazselenole(BP) ;5 methyl piazselenole(MP) ;4 ,4 ' dipi azselenole(DP)。结果表明 :Pis的Em随分子共轭体系增大或共轭效应增强而出现有规律地红移 ;Sn(Ⅳ )对Pis的发光有明显的增敏作用 :使DP的Em蓝移 ;对MP荧光减弱 ,对BP和DP均有明显的荧光增强作用 ,对常温下不发光的PS ,在Sn(Ⅳ ) PS乙醇溶液有较强的特征荧光 (Ex =35 5nm ,Em =4 2 6nm) ;此外 ,Cr(Ⅲ ) ,Cd(Ⅱ ) ,Cu(Ⅱ ) ,Sb(Ⅲ )和Sn(Ⅳ )均使BP荧光增强 ,Fe(Ⅲ )和Fe(Ⅱ )浓度较大时使BP荧光减弱 ,Zn(Ⅱ )却几乎没有影响     

三种具有Keggin结构的硅钨氧簇化合物的光谱研究

合成了三种具有Keggin结构的硅钨氧簇化合物：K₃H[SiWⅥ₁₂O₄₀]·3H₂O(Ⅰ),(H₃O)₄[H₃SiWⅥ₉WⅤ₃O₄₀]·2H₂O(Ⅱ)和[(CH₃)₄N]₄[SiWⅥ₁₂O₄₀]·4.5 H₂O(Ⅲ),用FTIR,NIR FT-Raman,UV-Vis和荧光光谱等研究手段进行了光谱研究,探讨其结构与性能的关系。在这些化合物中, 阴离子相同或类似,具有孤立的[SiW₁₂O₄₀]簇骼基元,通过静电作用和弱的氢键与阳离子及水相连。它们的FTIR和NIR FT-Raman光谱研究表明：硅钨酸盐的特征振动频率与其结构相关,由于化合物Ⅱ中的部分W6+已被还原成W5+,使ν_as(WO_d)振动频率降低,且簇阴离子电荷大小也明显地对ν_as(W—O_c—W),ν_as(Si—O_a),δ(O_a—Si—O_a)等产生影响;化合物Ⅰ和Ⅱ的UV-Vis光谱显示,在200和250 nm左右有紫外吸收谱带;化合物Ⅰ的稳态荧光光谱观察到分别以220,350和440 nm激发时,相应在350,440和520及675 nm左右产生一个或两个发射峰。     

两种新型二氯代苯基卟啉-5-氟尿嘧啶衍生物的合成与表征

用5-[4-(5-溴戊氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉或5-[4-(6-溴己氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉与5-氟尿嘧啶反应,合成了1-[5-(4-戊氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(A)和1-[5-(4-己氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(B),产率分别为29.92%和30.01%。并通过红外光谱、紫外可见光谱、核磁共振谱和质谱表征了其结构。对目标化合物的合成条件进行了研究,结果表明:以DMF为溶剂,反应温度为115℃,反应时间2h,产率较高;采用硅胶G(200—300目)装柱,以氯仿和氯仿∶乙醚(V∶V=50∶1)为洗脱液,柱层析,再用氯仿:丙酮(V∶V=7∶1)洗脱产品色带,分离效果较好。     

基于TCNQ电荷转移化合物的合成与光谱性质

π电子受体TCNQ的电荷转移化合物有奇特的电学和磁学性质,在该类电荷转移化合物中,TCNQ的形态对化合物的性质有较大的影响。文章合成了两种电荷转移化合物[RBz(4-CH₃)Py][TCNQ](R=Br(1),I(2)),通过元素分析、红外光谱和拉曼光谱对其进行了表征。这两种化合物的元素分析结果显示与理论值一致。通常在2 200 cm-1附近的C≡N的伸缩频率经常被用来确定TCNQ分子的电荷,TCNQ中性分子的ν(CN)在2 222 cm-1以上,而这两种化合物的ν(CN)都向低波数移动,在2 185～2 156 cm-1之间。通过对两种化合物红外和拉曼光谱的测定,显示了其中的TCNQ形态是TCNQ阴离子自由基（TCNQ－）。     

一种新颖的在线监测仪器--离子流动光谱仪

离子流动光谱仪（IMS）体积小，重量轻，耗能少，价格便宜，灵敏度高，适用范围广，能用于在线分析，是一种前景广阔的监测仪器。但有关的报道在国内却很少，本文介绍了它的基本原理、仪器构造、特点，局限性以及与色谱和质谱的连用，向小型化发展的方向。从德国光谱化学与应用光谱学研究所在此方面所作的工作讨论了离子流动光谱仪在爆炸物监控、化学武器鉴定、毒品稽查以及在线工业分析和环境监测中的应用。     

Stereochemistry of New Nitrogen Containing Heterocyclic Aldehydes. II. Novel Bis-Bidentate Azodye Compounds

A novel family of chelating bis-bidentate azodye compounds¹ with Cu(II), Co(II), Ni(II), Fe(II), Hg(II), Pd(II), UO₂(II), Fe(III), Cr(III), La(III), Ru(III) and Zr(IV) has been prepared and characterized on the basis of analytical, magnetic, ¹H and ¹³C NMR, EPR and electronic spectral studies. Tentative structures for the polymeric complexes are proposed. The important IR bands and the main ¹H and ¹³C signals are assigned and discussed relative to the molecular structure. Various EPR parameters for Cμ(II), have been calculated. The ligand acts as a dibasic bis-bidentate chelating agent coordinating through CO, N=N, COOH and OH groups by replacement of a proton from the two latter groups. Considerable interest has also been focused on the synthesis of the azo compound and its polymeric metal complex due to its wide potential applications. The thermal decomposition behavior of the complexes is also discussed.     

海洋真菌Penicillium sp.中的环二肽类化合物

从南海采集的海泥中分离得到的海洋真菌Penicillium sp.中分离得到3种环二肽类化合物。通过理化性质和波谱数据分析鉴定了3种化合物的结构。它们分别是3-异丁基-6-异丙基哌嗪-2,5-二酮(1)、3-另丁基-6-异丁基哌嗪-2,5-二酮(2)、3-另丁基-6-异丙基哌嗪-2,5-二酮(3)。     

Towards the Efficiency of Pharmacologically Active Quinoid Compounds: Electron Transfer and Formation of Reactive Oxygen Species

In this review article, the structure, properties, stability and biological application of redox-active quinones are presented. A series of quinoid molecules is evaluated in terms of their ability to act as electron-transfer active compounds using cyclovoltammetric, electron paramagnetic resonance (EPR) and spin-trapping techniques. Redox potentials and electron distribution of the intermediate radical anions are shown to be decisive factors for the generation of reactive oxygen species (ROS). Mechanisms of ROS generation in dark by biological electron-transfer reaction or under photoexcitation have been proposed and experimentally verified. For site-specific damage of tumors, some quinone derivatives were covalently bound with the luteinizing hormone-releasing hormone (LH–RH or GnRH) that produces specific complexes with receptors on the surface of cancer cells. The properties of obtained conjugates to be bound with the different lines of cancer cells (αT3-1, M2R, LNCaP) were tested. EPR was used for the estimation of efficacy of ROS production by the conjugates in solution and in the complex with cancer cells. The toxicity of these conjugates as well as their stability in the stimulated oxidative stress were tested. The proposed approach could be useful in creating a new family of addressed anticancer drugs, including compounds for the treatment of tumors by photodynamic therapy.     

Judd-Ofelt Analysis of Photoacoustic Spectra of Powdered Neodymium Compounds

Photoacoustic (PA) spectra of powdered neodymium oxide: Nd₂O₃ (A type), neodymium hydrated chloride: NdCl₃-6H₂O and neodymium fluoride: NdF₃ are reported. PA band shifts as compared to their positions in aqueous Nd(III) ion have been used to calculate the nephelauxetic parameters of their compounds. The variation of these parameters and correlation with the nature of metal-ligand bonding have been discussed. A novel method is introduced to determine relative values of Judd-Ofelt parameters and oscillator strengths of powdered samples using PA spectroscopy. It is found that a linear correlation exists between relative values of τ₂ and relative oscillator strengths of hypersensitive transitions of the title compounds. It can be hoped that the new method of PA technique may serve for the Judd-Ofelt quantitative analysis of powdered rare earth compounds.     

氮功能化大环化合物及其Ni(Ⅱ)配合物的合成和谱学研究

以丙酮,乙二胺,溴乙酸乙酯为原料合成了三种新的氮功能化四氮杂大环化合物的配合物,用元素分析,电子光谱,红外光谱,氢核磁共振谱和质谱对它们进行了研究。     

Glass Transition Temperatures of Epoxy Modified with Pendent Nano‐Organic Rigid‐Rod Compounds

Pendent nanoscale organic rigid‐rod compounds are molecular fiber‐like materials that can be used to reinforce the polymer matrix. In this study, 4,4′‐diphenylmethane diisocyanate (MDI) was used to covalently connect a number of organic rigid‐rod compounds [4′‐hydroxyphenyl‐4‐hydroxy‐benzoate (HPHB), phenyl 4‐hydroxybenzoate (HPB), 4,4′‐isopropylidenediphenol (BSPA), and 2‐naphthol (NPT)] to the secondary hydroxyl groups of the epoxy resin. These reactions were monitored using Fourier transform infrared (FT‐IR) spectroscopy; the products were characterized using nuclear magnetic resonance (NMR) spectroscopy. The glass transition temperatures of the organic rigid‐rod compounds modified epoxy resins were investigated through differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Thermogravimetric analysis (TGA) was used to detect the values of Td and the thermal stabilities of the polymers.     

己氧基对含二苯乙烯基发色团化合物荧光性能的影响

合成了两种新型甲基丙烯酸酯类化合物：4-甲基丙烯酰氧基-4’-硝基二苯乙烯(NS)和4-甲基丙烯酰氧己氧基-4’-硝基二苯乙烯(HNS),通过红外光谱、核磁、高效液相色谱、紫外吸收光谱等对化合物结构进行了表征。研究了两化合物的荧光发射光谱,考察了浓度、溶剂极性等对化合物荧光发射光谱的影响。结果表明,化合物NS、HNS均存在浓度自猝灭效应,其荧光最大发射波长均随着溶剂极性增大而红移;且HNS由于供电子己氧基的引入在分子内形成了推-拉电子结构,使得其荧光最大发射波长较NS红移了72nm,化合物在DMF溶液中产生的荧光由黄光转变为橙红色光。