紫外分光光度法快速测定发酵液中的L-色氨酸

建立了一种紫外分光度法测定发酵液中L-色氨酸的方法。L-色氨酸和甲酸在HCl介质中生成蓝紫色化合物,该化合物最大吸光度为364 nm,L-色氨酸测定范围为0~2.5mg/mL,工作曲线为Y=0.382X+0.0278,R2=0.9999,其它氨基酸均不干扰L-色氨酸的测定。该方法与氨基酸分析仪测定结果一致,测定改造色氨酸合成酶酶促合成的L-色氨酸浓度达到46mg/mL。     

β-环糊精增敏荧光猝灭法对粮食样品中L-色氨酸的分析研究

研究了Se(Ⅳ)-丁基罗丹明B与L-色氨酸结合物在β-环糊精(β-CD)介质中的荧光光谱行为.加入L-色氨酸可使Se(Ⅳ)-丁基罗丹明B体系发生荧光猝灭,β-CD的加入导致溶液中荧光猝灭值ΔIF增加,且L-色氨酸的质量浓度与ΔIF呈良好的线性关系,据此建立了荧光猝灭测定L-色氨酸的新方法.优化了实验条件,结果表明:β-CD对测定具有增敏作用,色氨酸的质量浓度在1.0 ～30.0 mg/L范围内与荧光强度呈线性关系,回归方程为ΔIF =399.1ρ(mg/L)+258.9,相关系数r=0.999 3,检出限为0.21 mg/L.将方法用于粮食样品中L-色氨酸的测定,结果令人满意.     

色氨酸在普鲁士蓝修饰玻碳电极上的电化学行为研究

采用电沉积法制备了普鲁士蓝修饰玻碳电极(PB/GCE),使用循环伏安法(CV)研究了色氨酸(Trp)在修饰电极上的电化学特性,并建立了一种电化学检测色氨酸的新方法。实验结果表明,在优化实验条件下,色氨酸在8.0×10-6～5.0×10-4mol·L-1浓度范围内与峰电流呈良好线性关系,线性回归方程为Ip(μA)=5.8954c(μmol·L-1)-32.91,相关系数r=0.9999(n=8),方法检出限(S/N=3)为3.5×10-7mol·L-1。将该修饰电极用于色氨酸样品的测定,结果满意。初步的反应机理探讨表明,色氨酸在普鲁士蓝电极上的反应可能是以两步进行的两电子氧化过程。     

同时测定中草药中痕量铅和汞的氢化物原子荧光法

提出了同时测定痕量铅和汞的氢化物发生原子荧光法 ;采用断续流动氢化物发生器 ,以碱性铁氰化钾为氧化剂 ,在柠檬酸介质中产生铅烷和汞蒸气 ;讨论了氧化剂和络合剂对铅烷和汞蒸气生成的作用机理 ,考察了共存元素的干扰情况;在选定最佳工作条件下 ,测得铅和汞的检出限(3σ)分别为0.21μg·L-1 和0.026μg·L-1,相对标准偏差(对20μg·L-1Pb和2μg·L-1Hg,n=11)分别为1.2 %和0.71 % ;该法应用于中草药中痕量铅和汞的同时测定 ,结果令人满意     

电感耦合等离子体原子发射光谱法测定易切钢中铅含量

采用电感耦合等离子体原子发射光谱法对易切钢中铅的含量进行测定,样品经硝酸-盐酸(1+1)混合酸溶解,选择220.353 nm波长为测定铅的分析线,铅的质量浓度在2.00～20.00 mg·L-1范围内与其谱线强度呈线性关系,测定下限(10S/N)为0.03 mg·L-1.该方法用于两个标准样品(GSBH 40064-93和GSBH 40061-93)中铅含量的测定,加标回收率在97.1%～99.1%之间,相对标准偏差(n=11)小于0.8%.     

流动注射-火焰原子吸收光谱法测定痕量铅——磷酸盐沉淀吸附在线富集

在流动注射-火焰原子吸收光谱法(FI-FAAS)测定铅(Ⅱ)的流路中设计了铅(Ⅱ)的磷酸盐沉淀在线富集的编结反应器,痕量铅(Ⅱ)与2.0×10-9mol·L-1磷酸二氢钾溶液在微酸性条件下在反应器中反应.当试样溶液的进样体积固定为8.00 mL,采用的富集流速为4.4 mL·min-1,富集时间为90 S,生成的铅(Ⅱ)的磷酸盐沉淀吸附于聚四氟乙烯反应管的内壁,毋需过滤,直接用2.0 mol·L-1硝酸流入管内使铅(Ⅱ)的沉淀溶解,溶液中铅(Ⅱ)按选定条件进行FAAS检测.按上述条件,可使增强系数(N)达到20,铅(Ⅱ)的检出限(3σ)达到23μg·L-1.对铅(Ⅱ)0.50 mg·L-1的标准溶液平行测定6次,算得测定结果的相对标准偏差为3.1%.用此方法分析了2件粉饼样品,测定值的相对标准偏差(n=6)分别为2.2%和4.1%.以此样品作基体进行回收试验,测得平均回收率为91%.     

微分电位溶出法连续测定饮料中的铜铅镉锌

建立了微分电位溶出法连续测定饮料中痕量铜、铅、镉、锌的新方法。在HAc- Na Ac( p H4 .5)～ 3.5× 1 0 -2 mol·L-1KCl～ 2 .6× 1 0 -5 mol· L-1Hg2 +介质中测定锌 ,然后调节底液为 0 .0 1 mol·L-1HCl,连续测定铜、铅、镉。铜、铅、镉、锌 ,检出限分别为 4 ,0 .1 ,2 ,4 μg· L-1,线性测定范围 Zn2 +:0～ 30 0 μg·L-1,Cu2 +、Pb2 +、Cd2 +:0～ 2 2 0μg· L-1,回收率为 83.4 %～ 1 0 3.3% ,RSD<3.4 % ( n=7)。该法较好解决了金属互化物的影响 ,样品不需消化便可直接测定。     

流动注射微柱预富集-火焰原子吸收光谱法测定海水中铅(Ⅱ)

应用流动注射技术,用D412螯合树脂微柱富集海水中的铅(Ⅱ),并与火焰原子吸收光谱法相结合测定海水中铅(Ⅱ)。20mL海水样品以3mL.min-1流量进柱,被树脂螯合吸附富集,以0.2mol.L-1乙酸铵溶液5mL淋洗柱体去除干扰物,以4mol.L-1硝酸溶液4mL为洗脱剂(流量为7mL.min-1),洗脱液直接引入火焰原子吸收光谱仪雾化器,在线检测。当海水样进样20mL时,铅(Ⅱ)测定灵敏度可提高约35倍;检出限(3s)为1.3μg.L-1。实际应用于海水样品分析,加标回收率为94.5%,测定值的相对标准偏差(n=6)为2.2%。     

微波消化-在线固相萃取富集高效液相色谱法测定饲料用灌木中痕量铅镉汞

研究了用微波消化样品,WatersXterraTMRP18(3.9mm×20mm)色谱柱在线固相萃取富集,二极管矩阵检测器检测,高效液相色谱测定饲料用灌木中痕量铅、镉、汞的方法。铅、镉和汞含量在0.1～100μg·L-1范围内与峰面积呈线性关系,方法检出限(S/N=3)为:铅2.0ng·L-1,镉1.5ng·L-1和汞2.0ng·L-1,方法相对标准偏差为2.0%～3.1%,标准回收率为94%～103%,该方法用于测定饲料用灌木中低含量的铅、镉、汞,结果满意。     

分散液相微萃取-石墨炉原子吸收光谱法测定水样中痕量铅北大核心CSCD

基于分散剂乙醇(0.5mL)和萃取剂四氯化碳(30μL)的协同作用,可使水样(5.0mL)中痕量铅(Ⅱ)与吡咯烷基二硫代氨基甲酸铵(APDC,0.012g·L-1)所形成的螯合物,在pH 7.0及55℃的条件下迅速借分散液相微萃取(DLLME)进入四氯化碳的液滴中,从而达到样品中痕量铅的分离与富集。其含量用连续光源石墨炉原子吸收光谱法予以测定。铅的线性范围在1.00~40.00μg·L-1之间,其检出限(3s/k)为0.15μg·L-1。应用本法测定了自来水和河水中痕量铅,加标回收率在96.8%~105%之间,测定值的相对标准偏差(n=10)均小于5%。     

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.