激光诱导纳秒时间分辨荧光法原位测定吸附于红树叶片表面的菲

实现吸附于植物叶片表面多环芳烃(Polycyclic aromatic hydrocarbons,PAHs)的现场原位测定,是该研究领域的发展方向之一。本实验利用激光诱导纳秒时间分辨荧光(Laser-induced nanosecond time-resolved fluorescence,LITRF)系统,建立了原位测定吸附于秋茄(Kandelia obovata,Ko)、木榄(Bruguiera gymnorhiza,Bg)和桐花树(Aegiceras corniculatum,Ac)3种红树叶片表面菲(Phenanthrene,Phe)的新方法。本方法测定吸附于Ko、Bg和Ac叶片表面Phe的线性范围分别为2~1400 ng/spot,1~1000 ng/spot和4~2000 ng/spot,检测限分别为0.20,0.14和0.42 ng/spot,加标回收率为89.6%~108.1%,78.2%~92.4%和93.2%~112.9%,且方法的相对标准偏差小于6.0%(n=9)。将方法用于实验室暴露样品的原位测定,并与光纤荧光法对比,其灵敏度、线性范围改善显著,更有利于实现植物叶片上PAHs的现场原位测定。     

光纤荧光法对吸附于红树叶片表面上荧蒽的测定

利用光纤荧光法实现了吸附于白骨壤(Am)、海漆(Ea)、秋茄(Kc)、桐花树(Ac)和老鼠簕(Ai)叶片表面上荧蒽(Fla)的定量测定.所建方法测定吸附于Am、Ea、Kc、Ac和Ai叶片表面上Fla的线性范围分别为2.5 ～500、2.0 ～600、4.5 ～1 100、15 ～600、3.5 ～450 ng/spot,相应的检出限分别为0.91、0.63、1.12、3.52、1.40 ng/spot,方法的相对标准偏差小于7.8%(n=15),加标回收率分别为97% ～108%、78% ～95%、77% ～90%、84% ～108%和78% ～102%.利用所建方法考察了5种红树叶片正反面吸附不同量Fla的信号强度随时间的变化情况.结果表明:在200 min内,叶片正反面上Fla的信号均发生不同程度的衰减,且反面的信号衰减率大于正面;5种红树叶片正反面对Fla的吸附特性均不同;吸附于叶片正面的Fla多残留在叶片表面,而吸附于叶片反面的Fla易向叶片内部迁移.     

固体表面荧光法测定吸附于白骨壤和木榄叶片上的葸

以新鲜白骨壤和木榄叶片为基质,建立了直接测定吸附于叶片表面蒽（An）的固体表面荧光分析法（SSF）。考察了白骨壤和木榄叶片上An的吸附量随An暴露浓度、暴露时间等因素的变化情况。方法测定吸附于白骨壤叶片上An的线性范围为0．92～8．71μg/g,检出限为5．77ng/g,加标回收率为79．2％～85．9％;测定吸附于木榄叶片上An的线性范围为89．5～698．2ng／g,检出限为1．79ng/g,加标回收率为75．1％～102．3％;对于两种叶片,方法的相对标准偏差都小于10％。     

固体表面荧光法测定吸附于白骨壤和木榄叶片上的蒽

以新鲜白骨壤和木榄叶片为基质,建立了直接测定吸附于叶片表面蒽(An)的固体表面荧光分析法(SSF).考察了白骨壤和木榄叶片上An的吸附量随An暴露浓度、暴露时间等因素的变化情况.方法测定吸附于白骨壤叶片上An的线性范围为0.92～8.71μg/g检出限为5.77 ng/g,加标回收率为79.2%～85.9%;测定吸附于木榄叶片上An的线性范围为89.5～698.2 ng/g,检出限为1.79 ng/g,加标回收率为75.1%～102.3%;对于两种叶片,方法的相对标准偏差都小于10%.     

激光热透镜光度法测定痕量锑

利用He-Ne激光,观测了锑-孔雀绿络合物的激光热透镜效应。其在苯中最低检测浓度为10ng/ml Sb,测定线性浓度范围为1～120ng/ml,测定的相对标准偏差为6.5％。本方法比常规光度法的测定灵敏度高12倍,相当于吸光度3.3×10~(-4)。     

浊点萃取-分光光度法测定水样中痕量结晶紫

提出了浊点萃取-分光光度法测定水样中结晶紫的新方法,研究了非离子表面活性剂Triton X-114浊点萃取的最佳条件,如pH、试剂用量、平衡时间和温度等。结晶紫的最大吸收波长为579 nm,标准曲线的线性范围是32～700 ng/mL,检出限是9.8 ng/mL,富集倍率为20。结晶紫的浓度在0.2和0.5μg/mL时的相对标准偏差分别为2.5%和1.7%(n=8)。应用本方法测定水样中的痕量结晶紫,平均回收率95.2%～98.1%。     

表面增强拉曼光谱法同时检测奶粉中三聚氰胺和二聚氰胺

本文建立了奶粉中同时检测三聚氰胺及二聚氰胺的表面增强拉曼光谱法.奶粉样品经15％三氯乙酸溶液提取,中性氧化铝吸附杂质后进行拉曼光谱检测.三聚氰胺线性范围为0.0050～0.075 mg/L,检出限为0.0015 mg/L,回收率在79.5％～124％之间,相对标准偏差小于8.8％(n=5);二聚氰胺线性范围为0.50～l0mg/L,检出限为0.15 mg/L,回收率在76.5％～112％之间,相对标准偏差小于9.4％(n=5).该方法相比常规表面增强拉曼光谱法,仅通过一种样品前处理手段即可对奶粉中的三聚氰胺或二聚氰胺进行定性检出及定量分析,相比色谱等检测方法具有样品前处理过程简单、耗时短等优点,在奶粉质量监控方面具有良好的应用前景.     

4种喹诺酮类药物滤纸基质室温光法研究

提出了以滤纸为基质的环丙沙星、氟罗沙星、洛美沙星和氧氟沙星4种喹诺酮类药物的滤纸基质室温光(PS-RTP)分析的新方法. 方法取样量少(1.5 μL).其线性动力学范围依次为0.11～55.2、0.35～211、2.10～526 、1.03～411(ng/斑点);灵敏度高,其检出限分别为0.082、0.070、0.080、0.123(ng/ 斑点);标准回收率在97.70%～102.2%之间.相对标准偏差RSD＜1.8%.     

桑色素荧光分光光度法测定水和保健饮料中痕量锗

本文提出了测定水和保健饮料中痕量锗的桑色素荧光分光光度法。检出限分别为0.2μg/L和0.7μg/L,线性范围分别为1.0～25μg/L和5.0～30μg/L,平均回收率分别为97.2％～104.5％和98.8％～104.8％,相对标准偏差分别为3.66％。2.87％方法简便,准确高度,精密度好,共存离子干扰小。     

两种离子液体-分散液液微萃取方法富集水中4种胺类化合物的比较

建立了温度控制/超声辅助-离子液体-分散液液微萃取-超高效液相色谱-串联质谱检测水中4种胺类化合物的方法,并对两种前处理方法的优化参数进行了详细比较,最终证明超声辅助方法具有更高的回收率.水样在调节pH之后加入[C8MIM][PF6]和乙腈,通过水浴控温/超声辅助的方法促进萃取,冷却后离心分离,即可进入超高效液相色谱串联质谱检测.超声辅助方法中,4种胺类物质线性良好,相关系数范围在0.9969 ～0.9991,检出限范围为5.0～50 ng/L.在3个浓度水平6次平行加标实验中,4种胺类物质平均回收率为81.5％ ～106.9％.日内相对标准偏差和日间相对标准偏差分别为7.6％ ～15.7％和14.7％ ～ 22.9％.本方法操作简便,灵敏度高,适用于大批量样品的快速分析.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.