热解吸-电喷雾离子源-三重四极杆质谱法快速筛查火锅底料和肉汤中非法添加罂粟壳

通过简单的金属探针直接接触火锅底料和肉汤表面采集待测物,经热解吸离子源进一步热解吸和电喷雾离子化,最终进入三重四极杆质谱检测器在多反应监测模式下进行定性分析,实现了火锅底料和肉汤中罂粟壳的现场实时快速检测。结果表明,设置热解吸温度为260℃,以0.1%甲酸水溶液（含10 mmol/L甲酸铵-乙腈（1:1,v/v）作为注射溶剂、注射泵流速为200 μL/h时,仪器响应值最优,灵敏度最高;5种生物碱中罂粟碱、那可丁、蒂巴因在火锅底料和肉汤中的检出限均为2 μg/kg,可待因、吗啡在火锅底料中的检出限为10 μg/kg,在肉汤中的检出限为5 μg/kg。该法与罂粟壳胶体金卡片快检试剂盒相比,灵敏度具有明显优势。应用该法对50批次市售火锅底料、肉汤等样品进行检测,发现1批次鸡汤含有那可丁、罂粟碱、蒂巴因和吗啡4种生物碱,与高效液相色谱-三重四极杆质谱法的检测结果一致。由此说明该方法具有无需样品制备和色谱分离的特点,是一种快速、绿色、环保的分析方法,能够满足对食品中罂粟壳的快速定性分析。     

实时直接分析-串联质谱法快速筛查火锅底料、牛肉面汤及调味料中罂粟壳生物碱

建立了采用实时直接分析-串联质谱(DART-MS/MS)对火锅底料、牛肉面汤及调味料中5种非法添加的罂粟壳生物碱进行快速筛查的方法。样品经乙腈提取净化后,在离子化温度为300℃、栅极电压为150 V、进样速率为0.8 m m/s的DART离子源正离子模式条件下进样,以电喷雾离子源正离子多反应监测(MRM)模式进行检测,实现了样品经简单预处理后使用DART-MS/MS进行检测的新方法。该方法简便、快速,能满足大批量非法添加样品的快速筛查分析要求。     

多功能柱净化-高效液相色谱法检测谷物中的玉米赤霉烯酮

建立了玉米和小麦中玉米赤霉烯酮（ZEN）的多功能柱净化-高效液相色谱检测方法。样品经乙腈-水混合溶剂（V（乙腈）：V（水）=84：16）提取,通过多功能净化柱（MFC）进行一次性净化,以Symmetry^R C18柱为分离柱,甲醇-水（V（甲醇）：V（水）=68：32）为流动相进行高效液相色谱分离和检测。玉米赤霉烯酮的质量浓度在0．01～4．0μg／mL范围内呈良好线性,相关系数为0．9996。检出限为0．04μg／g,在0、04—5．0mg／kg添加范围内的回收率为87．5％～98．6％,相对标准偏差为1．5％～8．3％。     

高效液相色谱法对吗啡、杜冷丁、安定的同步测定

利用高效液相色谱法同时分析测定了血液中吗啡、杜冷丁、安定的质量浓度。分析柱为C18,流动相为V（甲醇）：V（25mmol／LKH2PO4）＝90：10,检测波长为285nm。样品血液pH8．5～9．4时,用V（氯仿）：V（异丙醇）＝9：1溶液提取,以氮气吹干有机溶剂后用流动相溶解残渣进样分析。线性范围为0．05～50mg／L,最小检出质量浓度为0．05mg／L,日内与日间精密度CV＜6％。     

使用限进介质色谱柱的柱切换高效液相色谱法直接进样测定大鼠血浆中舒必利

提出一种直接进样测定大鼠血浆中舒必利浓度的高效液相色谱方法,使用限进介质色谱柱作为预柱在线去除血浆蛋白后,将舒必利通过柱切换转移到分析柱中进行分析。限进介质色谱柱为CAPCELLPAKMFSCX阳离子交换柱（20×4．0mmi．d．,5μm）,分析柱为Kromasil C18柱（150×4．6mm i．d．,5μm）,限进介质柱预分离时流动相为PH=6．88的50mmol／L磷酸盐缓冲液乙腈（100：5,V／V）,切换后分析流动相为PH=6．83的50mmol／L磷酸盐缓冲液-乙腈（100：10,V／V）。流速均为1mL／min,检测波长为240nm。该方法检出限为17ng／mL,定量限为50ng／mL。舒必利在50～1400ng／mL之间线性良好（r=0．9997）,高中低浓度的日内、日间相对标准偏差分别为1．5％～4．2％及2．0％～5．2％,方法回收率为98．8％～104．1％．     

高效液相色谱法同时测定快安抗感冒液中5种组分的含量

采用高效液相色谱法（HPLC）同时测定快安抗感冒液中对乙酰氨基酚、咖啡因、盐酸甲基麻黄碱、马来酸氯苯那敏和愈创木酚甘油醚的含量。色谱柱为NOVA－PAKC_18柱,流动相为V（已腈）：V（0．03mol／L磷酸氢二铵）：V（0．004mol／L庚烷磺酸钠）：V（三乙胺）=12：44：43．5：0．5,并用磷酸调节pH值至3．0;检测波长220nm,柱温35℃。在此色谱条件下,各组分均获得良好分离。平均回收率为98．0％～100．3％,相对标准偏差小于1．8％。     

高效液相色谱法测定萨拉沙星

采用高效液相色谱法测定了萨拉沙星。色谱柱为μ－BondapakTMC18柱（3．9mm×300mm）,流动相为V（乙腈）：V（甲醇）：V（2mmol／L磷酸,用三乙胺调pH3．5）＝30：5：65,用二极管阵列检测器检测,检测波长278nm,得到了满意的分离效果。     

高效液相色谱法同时测定快安抗感冒液中5种组分的含量

 采用高效液相色谱法（HPLC）同时测定快安抗感冒液中对乙酰氨基酚、咖啡因、盐酸甲基麻黄碱、马来酸氯苯那敏和愈创木酚甘油醚的含量。色谱柱为NOVA－PAKC_18柱,流动相为V（已腈）：V（0．03mol／L磷酸氢二铵）：V（0．004mol／L庚烷磺酸钠）：V（三乙胺）=12：44：43．5：0．5,并用磷酸调节pH值至3．0;检测波长220nm,柱温35℃。在此色谱条件下,各组分均获得良好分离。平均回收率为98．0％～100．3％,相对标准偏差小于1．8％。     

反相高效液相色谱同时测定铼与钼的方法研究

以二乙基二硫代氨基甲酸钠（NaDDTC）为柱前衍生试剂,采用高效液相色谱法（HPLC）建立了钼与铼2种金属离子最佳分离条件及定性定量分析方法．结果表明：在C18色谱柱上,以甲醇-水（15：85V/V,含有10mmol／LpH5乙酸-乙酸钠缓冲溶液）作为流动相,能有效的分离2种金属离子,检出限分别为2．1ng／mL和1．3ng／mL,线性范围和线性关系满足定量分析的要求．     

基于气相色谱-质谱和网络药理学探讨紫斑罂粟壳挥发油镇咳祛痰平喘的作用机制

为研究紫斑罂粟壳挥发油镇咳化痰平喘的活性成分及作用机制,采用气相色谱-质谱（GC-MS)联用法分析罂粟壳挥发油成分,并结合Pubchem和Swiss Target Prediction数据库筛选活性成分靶点. 其中,在GeneCards数据库中检索镇咳、祛痰、平喘相关的靶点,利用在线Venn取交集基因,Cytoscap 3.7.1软件构建成分-靶点-疾病网络图筛选关键成分,String数据库构建蛋白互作网络筛选核心作用靶点,DAVID数据库进行GO功能和KEGG通路富集分析. 结果表明,GC-MS鉴别出紫斑罂粟壳挥发油中28个化学成分,虚拟筛选获得20个活性成分对应的259个靶点. 网络药理学预测紫斑罂粟壳挥发油通过肿瘤坏死因子（TNF）、磷酸化蛋白激酶（AKT1）、SRC蛋白激酶（SRC）、表皮生长因子受体（EGFR）和丝裂原活化蛋白激酶 1（MAPK1）等关键靶点,进而协同调控肿瘤通路,神经配体-受体相互作用、PI3K-Akt信号通路等多条信号通路发挥镇咳祛痰、平喘的治疗作用. 研究为后续试验研究罂粟壳挥发油的药效物质及作用机制提供参考.     

4-(5-溴-2-噻唑偶氮)间苯二酚反相阳离子对HPLC测定痕量铌、钒、铑、铬

本文报道新试剂4-(5-溴-2-噻唑偶氮)间苯二酚(5-Br-TAR)为柱前衍生试剂,以阳离子表面活性剂作为对离子试剂,用含15 mmol／L的pH 5.8的乙酸-乙酸钠缓冲溶液、0.05 mmol／L溴化钠、10 mmol／L TBA·Br的乙腈-甲醇-水(42 : 13：45,V／V／V)三元体系为流动相,在C8柱上25min内HPLC测定了Nb(V)、V(V)、Rh(Ⅲ)和Cr(Ⅵ)的5-BR-TAR螯合物。当SNR=2时,检出限分别为Nb(V)1.0、V(V)1.6、Rh(Ⅲ)0.9和Cr(Ⅵ)1.9μg／L。该方法用于测定污水中的铬和钒,结果良好。     

Optical fibre chemical sensor for trace vanadium(V) determination based on newly synthesized palm based fatty hydroxamic acid immobilized in polyvinyl chloride membrane

Fatty hydroxamic acid (FHA) immobilized in polyvinyl chloride (PVC) has been studied as a sensor element of an optical fibre chemical sensor for V(V). By using this instrument, V(V) in solution has been determined in the log concentration range of 0-2.5 (i.e. 1.0-300 mg/L). The detection limit was 1.0 mg/L. The relative standard deviation (R.S.D.) of the method for the reproducibility study at V(V) concentration of 200 mg/L and 300 mg/L were calculated to be 2.9% and 2.0%, respectively. Interference from foreign ions was also studied at 1:1 mole ratio of V(V):foreign ions. It was found that, Fe(III) ion interfered most in the determination of vanadium(V). Excellent agreement with ICP-AES method was achieved when the proposed method was applied towards determination of V(V).     

NMR and theoretical investigations on the structures and dynamics of octahedral bis(chelate)dichloro V(III) compounds isolated by an unusual reduction of non-oxo V(IV) species

Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism.     

Syntheses, Structures and Characterizations of Two New Vanadium(V) Complexes: [PyH][V~vO_2(C_(14)H_9N_2O_3Br)] and [V~vO(C_(14)H_9N_2O_3Br)(OCH_3)]

<正>The new oxovanadium (V) complex, [PyH][VO2(L)] 1 (salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L; Hpy is protonated pyridine) was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-pyridine. Similarly, another new complex, [VO(L)(OCH3)] 2 was synthesized by refluxing VOSO4 and H2L in methanol-pyridine. Crystal data for 1: C19H15N3O5BrV, Mr= 496.2, monoclinic, P21/n, a = 7.1885(3), b = 9.2718(3), c = 28.803(1) A, β = 96.185(1)°, Z = 4 and V = 1908.6(1) A3; for 2: C15H12N2O5BrV, Mr= 431.1, monoclinic, P2,/n, a = 12.202(2), b = 8.045(2), c = 16.604(3) A, β = 101.29(3)°, Z = 4 and V = 1598.4(2) A3. The structures of 1 and 2 have been determined by X-ray analyses and reveal that the coordination environments of V atoms in both complexes are of square-based pyramid. Three of the four based donor atoms are from the tridentate "ONO" donor ligand while the fourth is one terminal oxygen atom with the V(1) - O(3) distance 1.646(4) A for 1 and one -OCH3 group with the V     

Emulsion liquid membrane separation of As(III) and As(V)

Emulsion liquid membranes (ELM) consisting of L113A (surfactant), liquid paraffin (stabilizer) and kerosene (solvent), with HCl solution acting as the external phase and KOH solution acting as the internal phase, were applied to the prior separation of arsenic(III) and arsenic(V) with subsequent spectrophotometric determination by AgDDTC. The effect of various parameters on the recovery of arsenic(III) were investigated. 8 mol/L HCl was required for 95% As(III) recovery. After reduction of As(V) to As(III) with sufficient KI, total arsenic could be determined. The RSD of As(III) and As(total) were both less than 3%. The procedure was applied to aqueous samples with a recovery of 93.5%–101%. Received: 22 March 1998 / Revised: 12 September 1998 / Accepted: 17 September 1998     

Emulsion liquid membrane separation of As(III) and As(V)

Emulsion liquid membranes (ELM) consisting of L113A (surfactant), liquid paraffin (stabilizer) and kerosene (solvent), with HCl solution acting as the external phase and KOH solution acting as the internal phase, were applied to the prior separation of arsenic(III) and arsenic(V) with subsequent spectrophotometric determination by AgDDTC. The effect of various parameters on the recovery of arsenic(III) were investigated. 8 mol/L HCl was required for 95% As(III) recovery. After reduction of As(V) to As(III) with sufficient KI, total arsenic could be determined. The RSD of As(III) and As(total) were both less than 3%. The procedure was applied to aqueous samples with a recovery of 93.5%–101%. Received: 22 March 1998 / Revised: 12 September 1998 / Accepted: 17 September 1998     

Determination of inorganic arsenic(III) in ground water using hydride generation coupled to ICP-AES (HG-ICP-AES) under variable sodium boron hydride (NaBH4) concentrations

The determination of inorganic arsenic species in ground water matrices using hydride generation coupled online to ICP-AES (HG-ICP-AES) is suggested on the fact that the As(III)-species shows significantly higher signal intensities at low sodium boron hydride (NaBH₄) concentrations than the As(V)-species. The sodium boron hydride concentration used for the determination of As(III) without any considerable interferences of As(V) was at 13.2 mmol/L NaBH₄ (0.05 wt/v%), whereas the concentration for the total As determination was at 158.4 mmol/L NaBH₄ (0.6 wt/v%). The interferences of As(V) during the As(III) measurements were very small: at concentrations below 100 μg/L of total arsenic, the interferences of As(V) were smaller than 2%. An amount of As(III) higher than 10% of the total As amount could be determined exactly and reliably. The total amount of arsenic is measured after reducing the sample with 20 mmol/L L-cysteine (C₃H₇NO₂S). Finally, the amount of the As(V)-species is calculated by the difference between the As(III)-species and the total arsenic. Therefore, this analytical method requires the absence of organic arsenic species, but if they still appear, they could be frozen out with liquid nitrogen after the hydride generation system. The linearity of calibration reaches from 2 μg/L up to 1000 μg/L with a detection limit routinely of about 1 μg/L for each species. The advantages of this method in comparison to AAS measurements are the higher extent of the linear calibration range (3 orders of magnitude) and a higher sensitivity. Additional merits of the method developed are easy handling and high sampling rates.     

含氮配体Co、Fe配合物的合成、结构及性质

报导了四个单核Co（Ⅱ）和Fe（Ⅱ）的配合物[Co（L1）2]（ClO4)2·（CH3CN）（1）,[Fe（L1）2]（ClO4）2·（H2O）（2）,[Co（L2）]（ClO4）2（3）,以及[Fe（L2）]（ClO4）2·2H2O（4）,（其中L1＝4’-苯基-2,2’：6’,2”-三联吡啶,L2＝N,N,N-三-（2-（2-吡啶甲叉氨基）乙基）胺）的合成和性质,以及配合物1、3的晶体结构．配合物1和3的晶体都属于单斜晶系．它们的晶胞参数分别为：1a＝1．0855（4）nm,b＝1．6201（5）nm,c=2.5236（5）nm,β＝92．63（2）°,V＝4．433（1）nm3;3a=2.8351（8）nm,b＝1．0670（3）nm,c＝1．9255（5）m,β＝101．03（4）°,V＝5717（2）nm3．2和4的氧化还原电位分别为E＝0．78V和0．63V‘它们的d-d跃迁吸收最大值分别位于565和521nm处．     

高效液相色谱法测定血清中头孢噻肟浓度

用固相萃取法处理样品,以扑热息痛为内标物、甲醇－醋酸钠／醋酸缓冲溶液作流动相,采用反相高效液相色谱法测定血清中头孢噻肟的浓度。头孢噻肟和内标物的平均回收率分别为９６．７％和９７．７％,头孢噻肟血清浓度在１０ｍｇ／Ｌ至１５０ｍｇ／Ｌ范围内有良好线性关系,最低检测浓度为２ｍｇ／Ｌ,日内和日间相对标准偏差分别在３．０％和４．１％以内。结果表明方法准确、简便。