毛细管电泳-电化学检测法测定硫酸铜-维生素C反应体系中的羟基自由基和菊花的抗氧化活性

采用毛细管电泳-电化学检测方法,以对羟基苯甲酸为自由基捕捉剂,测定了硫酸铜-维生素C反应体系(pH 7.4)中生成的羟基自由基。研究了电极电位、运行液的pH值、电泳电压及进样时间对体系中反应物和产物分离的影响,得到了最优化的测定条件;讨论了体系中各反应物浓度和反应时间对产物浓度的影响。以直径为300 μm的碳圆盘电极为检测电极,工作电极电位为0.95 V(vs.SCE),目标产物3,4-二羟基苯甲酸在1.5×10-4~6.0×10-6 mol/L范围内线性关系良好,检测限（S/N=3）为1.5×10-6 mol/L。应用该方法,研究测定了不同品种菊花的抗氧化活性。     

在碘酸钾存在下铝与茜素S的络合吸附波研究

在pH7.6的三乙醇胺缓冲溶液中,铝-茜素S络合物于-0.90V可产生一个灵敏的极谱波,加入碘酸钾后,极谱波负移至-0.94V,波高迅速增大,灵敏度增大约30倍。导数波高与Al^3 浓度在0.06-～10μg/L范围内呈线性关系,检测限达0.02μg/L。研究了极谱波性质及电极反应机理,证明极谱波为络合吸附催化波,在电极上还原的是络合剂茜素S,电还原的中是产物又被氧化回原状态而形成催化循环,使波高增大。利用本法直接测定了天然水中痕量铝。     

高效液相色谱法测定长柄扁桃仁中的苦杏仁甙

建立了高效液相色谱法测定长柄扁桃仁中的苦杏仁甙的方法.样品中的苦杏仁甙用甲醇超声提取20 min.在Shim-pack VP-ODS(250 mm×4.6 mm i.d.,5 μm)色谱柱上,以V(甲醇):V(水):V(乙腈)＝10:40:50为流动相进行洗脱,检测波长215 nm的条件下,测得长柄扁桃仁中苦杏仁甙的平均质量分数为35.40 mg/g.该法线性范围为0.64～32.0 mg/L,线性相关系数r=0.9997,检出限为1.1 μg/L,平均回收率为94%(N=3).此法可为果仁中苦杏仁甙的测定提供参考.     

高效液相色谱-二极管阵列检测-电化学检测联用技术同时测定三精双黄连口服液中的4种化合物

建立了应用高效液相色谱-二极管阵列检测-电化学检测(HPLC-DAD-ECD)联用技术同时测定三精双黄连口服液中的绿原酸、咖啡酸、黄芩甙和木樨草素的方法。以Zorbax SB-C18柱(150 mm×4.6 mm i.d., 5.0 μm)为色谱柱,柱温为30 ℃，流动相为(A)甲醇和(B)甲醇-水-冰醋酸(体积比为50∶50∶1),其梯度洗脱程序为2%A3 min3%A12 min25%A5 min80%A。流速为0.8 mL/min。二极管阵列检测波长为275 nm。电化学单安培检测器的工作电压为0.7 V。在上述条件下实现了绿原酸、咖啡酸、黄芩甙和木樨草素的分离检测。上述4种化合物的回收率为96.6%～99.6%,相对标准偏差(RSD)为2.5%～4.1%,检测限依次为1,0.2,9和7 mg/L。该方法简便、快速,重现性和准确度较好,可作为测定双黄连口服液中绿原酸、咖啡酸、黄芩甙和木樨草素的有效方法。     

黄芩甙在玻碳电极上的电化学行为及其应用

用线性扫描伏安法(LSV)、循环伏安法(CV)和常规脉冲伏安法(NPV)等多种电化学方法研究了黄芩甙在玻碳电极上的电化学行为,并建立了尿样和血清样品中黄芩甙的微分脉冲伏安(DPV)测定法。实验结果表明:黄芩甙在玻碳电极上的吸附符合Frumkin吸附等温式,吸附自由能为-35.01kJ mol。采用整体电解法求得电极反应电子数为2,并结合Nernst方程式推导了反应机理。黄芩甙在玻碳电极上预富集后,在4.20×10-10～1.05×10-5mol L范围内分段呈线性关系,对5.60×10-7mol L黄芩甙溶液连续6次测定的RSD=2.0%,检出限为2.8×10-10mol L。     

微分电位溶出分析法应用于金膜电极的研究

本文介绍将微分电位溶出分析法应用于金膜电极,建立了相应的理论体系和应用条件。可使用的金膜厚度在1.8×10~(-7)～4.3×10~(-7)cm范围。检测限较原法降低近两个数量极。用本法测定花生乳中的铜,回收率在94～102%间。     

黄芩及其制剂中黄芩素和黄芩甙的

用毛细管区带电泳 -电化学检测法测定了黄芩及其制剂中黄芩素和黄芩甙的含量。研究了电极电位、电解液酸度和浓度、电泳电压及进样时间等对电泳的影响 ,得到了较为优化的测定条件。以直径为300μm的碳圆盘电极为检测电极 ,电极电位为0.90V(vsSCE) ,在100mmol/L硼酸盐缓冲液(pH9.0)中 ,上述两组分在8min内完全分离。黄芩素和黄芩甙浓度与电泳峰电流分别在5.0×10 -7～1.0×10 -3mol/L和1.0×10 -6～1.0×10 -3mol/L范围内呈良好线性 ,检出限分别为2.24×10 -7mol/L和5.48×10 -7mol/L。7次测定分别含5.0×10 -4mol/L黄芩素和黄芩甙试样溶液 ,峰高的相对标准偏差分别为3.53%和4.03%。     

用高铼酸根离子选择电极测定铼

本文叙述了用自制的ReO_4选择电极和硫酸铵-柠檬酸铵-醋酸铵-醋酸离子液,采用直接电势法测定大量Mo、SO_4~(2-)、PO_4~(3-)、CO_3~(2-)、Cl~-、As等存在下的铼。方法快速、简便。试样中残存的少量有机溶剂不干扰测定。对于测定每升含铼毫克量级的试样优于通常采用的极谱法和光度法。方法的精密度优于±5％,回收率为92—111％。检测限约为1 mgl~(-1)。测定结果与极谱法结果吻合。本文还讨论了某些还原性物质(如Sn~(2+)严重干扰测定的原因及其消除方法。     

阳极溶出伏安法测定痕量汞的研究

痕量汞的测定方法有很多[1 ] 。原子吸收法虽然具有较高的灵敏性 ,但是仪器设备昂贵 ,分析步骤较繁琐。近年来 ,化学修饰电极阳极溶出伏安法在对汞痕量分析方面的研究报道也不少[2～3] ,测定的检测限一般在 1 0 - 6～ 1 0 - 9ｇ·ｍｌ- 1 ,但它容易产生记忆效应 ,洗脱不良。本文以玻碳电极为工作电极 ,在ＨＣｌ ＮａＣｌ Ｃｄ2 +中 ,示差脉冲阳极溶出伏安法 (ＤＰＳ)测定痕量汞 ,汞的平均回收率达80 %。1　实验部分1 1　主要仪器与试剂ＰＡＲ— 384极谱仪 (美国 ) ;三电极系统 :工作电极为玻碳电极 ,参比电极为Ａｇ/ＡｇＣｌ电极 ,对电极为…     

黄芩甙的线性扫描伏安法测定研究

研究了黄芩甙在多壁碳纳米管修饰电极上的伏安行为。结果表明 ,该修饰电极对黄芩甙产生较强的吸附催化作用 ,催化电流与黄芩甙浓度在 1 .0× 1 0 - 7～ 6.0×1 0 - 5mol·L- 1范围内呈线性关系。利用本法测定了中药黄芩中的黄芩甙的含量 ,效果良好     

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.