黄芪口服液中8种重金属元素含量的测定

在2015年版《中国药典》的基础上,采用原子荧光光谱法和电感耦合等离子体质谱法对黄芪口服液中的铅、砷、镉、汞、铜、锌、镍和铬进行测定,并对所用试剂、器皿,赶酸时间,内标的种类和加入方式进行了优化。结果表明,在样品处理前对器皿采用硝酸(30%)处理,赶酸时间在1.5h以上,以手动方式加入单内标103 Rh溶液,可以得到较准确、稳定的测定结果,8种元素测定的相对标准偏差(RSD)均小于4%,Hg、As、Cu、Pb、Zn、Cd、Ni、Cr的检出限分别为0.089、0.21、0.45、0.15、0.45、0.025、0.35和0.39μg/L,8种元素的加标回收率在92.0%～114%。方法对于黄芪口服液中痕量元素的检测,结果稳定,过程简单,引入污染小。     

电感耦合等离子体原子发射光谱法(ICP-AES)测定金鸡胶囊中的7种无机元素

建立了测定金鸡胶囊中Ca、Mg、Mn、Fe、Cu、Zn和Sr 7种无机元素含量的分析方法.采用浓硝酸和高氯酸(8+2)的混合酸溶解样品,利用电感耦合等离子体原子发射光谱法(ICP-AES)对各种元素进行测定.金鸡胶囊含有丰富的对人体有益的无机元素,对待测样品的测定结果表明,Ca、Mg、Fe、Mn、Zn、Sr和Cu的含量...     

Ultrafast Vibrational Population Transfer Dynamics in 2‐Acetylcyclopentanone Studied by 2D IR Spectroscopy

2‐Acetylcyclopentanone (2‐ACP), which is a β‐dicarbonyl compound, undergoes keto–enol isomerization, and its enol tautomers are stabilized by a cyclic intramolecular hydrogen bond. 2‐ACP (keto form) has symmetric and asymmetric vibrational modes of the two carbonyl groups at 1748 and 1715 cm^?1, respectively, which are well separated from the carbonyl modes of its enol tautomers in the FTIR spectrum. We have investigated 2‐ACP dissolved in carbon tetrachloride by 2D IR spectroscopy and IR pump–probe spectroscopy. Vibrational population transfer dynamics between the two carbonyl modes were observed by 2D IR spectroscopy. To extract the population exchange dynamics (i.e., the down‐ and uphill population transfer rate constants), we used the normalized volumes of the cross‐peaks with respect to the diagonal peaks at the same emission frequency and the survival and conditional probability functions. As expected, the downhill population transfer time constant (3.2 ps) was measured to be smaller than the uphill population transfer time constant (3.8 ps). In addition, the vibrational population relaxation dynamics of the two carbonyl modes were observed to be the same within the experimental error and were found to be much slower than vibrational population transfer between two carbonyl modes.     

Ions Can Move a Proton‐Coupled Electron‐Transfer Reaction into Tunneling Regime

The effects of charged species on proton‐coupled electron‐transfer (PCET) reaction should be of significance for understanding/application of important chemical and biological PCET systems. Such species can be found in proximity of activated complex in a PCET reaction, although they are not involved in the charge transfer process. Reported here is the first study of the above‐mentioned effects. Here, the effects of Na⁺, K⁺, Li⁺, Ca²⁺, Mg²⁺, and Me₄N⁺ observed in PCET reaction of ascorbate monoanions with hexacyanoferrate(III) ions in H₂O reveal that, in presence of ions, this over‐the‐barrier reaction entered into tunneling regime. The observations are: a) dependence of the rate constant on the cation concentration, where the rate constant is 71 (at I = 0.0023), and 821 (at 0.5M K⁺), 847 (at 1.0M Na⁺), and 438 M ^?1 s^?1 (at 0.011M Ca²⁺); b) changes of kinetic isotope effect (KIE) in the presence of ions, where k_H/k_D=4.6 (at I = 0.0023), and 3.4 (in the presence of 0.5M K⁺), 3.3 (at 1.0M Na⁺), 3.9 (at 0.001M Ca²⁺), and 3.9 (at 0.001M Mg²⁺), respectively; c) the isotope effects on Arrhenius pre‐factor where A_H/A_D=0.97 (0.15) in absence of ions, and 2.29 (0.60) (at 0.5M Na⁺), 1.77 (0.29) (at 1.0M Na⁺), 1.61 (0.25) (at 0.5M K⁺), 0.42 (0.16) (at 0.001M Ca²⁺) and 0.16 (0.19) (at 0.001M Mg²⁺); d) isotope differences in the enthalpies of activation in H₂O and in D₂O, where ΔΔH^?(D,H)=3.9 (0.4) kJ mol^?1 in the absence of cations, 1.3 (0.6) at 0.5M Na⁺, 1.8 (0.4) at 0.5M K⁺, 1.5 (0.4) at 1.0M Na⁺, 5.5 (0.9) (at 0.001M Ca²⁺), and 7.9 (2.8) (at 0.001M Mg²⁺) kJ mol^?1; e) nonlinear proton inventory in reaction. In the H₂O/dioxane 1 : 1, the observed KIE is 7.8 and 4.4 in the absence and in the presence of 0.1M K⁺, respectively, and A_H/A_D=0.14 (0.03). The changes when cations are present in the reaction are explained in terms of termolecular encounter complex consisting of redox partners, and the cation where the cation can be found in a near proximity of the reaction‐activated complex thus influencing the proton/electron double tunneling event in the PCET process. A molecule of H₂O is involved in the transition state. The resulting ‘configuration’ is more ‘rigid’ and more appropriate for efficient tunneling with Na⁺ or K⁺ (extensive tunneling observed), i.e., there is more precise organized H transfer coordinate than in the case of Ca²⁺ and Mg²⁺ (moderate tunneling observed) in the reaction.     

Parameterization of Org27569: An allosteric modulator of the cannabinoid CB1 G protein‐coupled receptor

The cannabinoid CB₁ receptor is a class A G protein‐coupled receptor (GPCR) that is the most widely expressed GPCR in the brain. Many GPCRs contain allosteric binding sites for endogenous and/or synthetic ligands, which are topographically distinct from the agonist‐binding site that is known as the orthosteric site. While both endogenous and synthetic ligands that act at the CB₁ orthosteric site have been known for some time, compounds that act at a CB₁ allosteric site have only recently been discovered. The most studied of these is 5‐chloro‐3‐ethyl‐1H‐indole‐2‐carboxylic acid [2‐(4‐piperidin‐1‐ylphenyl)ethyl]amide (Org27569). Because allosteric ligands are thought to act through conformational changes in the receptor that are transmitted from the allosteric to the orthosteric site, computational studies of the structural and dynamic interactions of Org27569 with the CB₁ receptor are crucial to achieve a molecular level understanding of the basis of action of this important new class of compounds. To date, such computational studies have not been possible due to the lack of a complete set of molecular mechanics force field parameters for Org27569. Here, we present the development of missing CHARMM force field parameters for Org27569 using previously published methods and the validation and application of these new parameters using normal mode analysis and molecular dynamics simulations combined with experimental infrared measurements. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Analysis of fish otoliths by electrothermal vaporization inductively coupled plasma mass spectrometry: aspects of precipitating otolith calcium with hydrofluoric acid for trace element determination

A method is developed for determination of trace elements, including Ag, As, Cd, Co, Cr, Cu, Mn, Ni, Se, Tl and Zn, in fish otoliths by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). Hydrofluoric acid was used to precipitate calcium resulting from acid dissolution of otolith calcium carbonate. Initial acidity of the sample solution influenced the precipitation efficiency of calcium fluoride. Up to 99.5% of Ca was precipitated in solutions that contained less than 2% (v/v) HNO₃. Recoveries of the elements obtained from spiked artificial otolith solutions were between 90 and 103%. Stabilization of the elements within the ETV cell was achieved with 0.3 μg Pd/0.2 μg Rh chemical modifier that also afforded optimum sensitivity for multielement determination. The method was validated by the analysis of a fish otolith reference material (CRM) of emperor snapper, and then applied to the determination of the trace elements in otoliths of several fish species captured in Raritan Bay, New Jersey. Results indicated that fish physiology and biological processes could influence the levels of Cu, Mn, Se and Zn in the otoliths of fish inhabiting a similar aqueous environment. Otolith concentrations of Cr and Ni did not show any significant differences among different species. Concentrations for Ag, As, Cd, Co and Tl were also not significantly different, but were very low indicating low affinity of otolith calcium carbonate to these elements.     

Transport efficiency in femtosecond laser ablation inductively coupled plasma mass spectrometry applying ablation cells with short and long washout times

Relative mass transport efficiencies of near infrared (λ = 795 nm) femtosecond laser generated brass aerosols in helium were measured by ICP-MS applying different ablation cells with short and long washout times. It was found that the transport efficiencies are independent of the cell used within the mutual experimental uncertainties. This finding was confirmed by additional measurements providing the absolute particle mass transport efficiencies of femtosecond laser ablation in He. Here, the transport efficiencies were determined by weighing the samples before and after ablation with a micro-balance, collecting the particles by low-pressure impaction, and evaluating the impacted masses quantitatively by total reflection X-ray fluorescence. Within the experimental uncertainties (± 9–19%) the same absolute transport efficiency (about 77%) was found for all cells applied. This efficiency value can be regarded as a lower limit of the absolute mass transport efficiency since mass losses in the impactor are difficult to quantify.     

电感耦合等离子体光谱/质谱联机同时测定多金属结核中常量、微量、痕量元素

采用电感耦合等离子体质谱(ICP-MS)与等离子体光谱(ICP-OES)联机同时测定多金属结核样品中常量、微量、痕量元素。样品经高压密封溶样弹消解后,一次气动雾化进样,ICP-OES测定常量和微量元素,ICP-MS测定微量和痕量元素。详细探讨了不同浓度范围元素的测定方式、元素分析信号的采集模式、多原子离子干扰的校正因子。采用ICP-MS与ICP-OES二种方式同时测定Co、Cu、Ni、Zn、V、Ba、Sr,分析结果表明具有较好的一致性。所建立的ICP-MS与ICP-OES联机检测技术用于多金属结核标准样品的分析(Nod-A-1,GSPN-1,GSPN-2,GSPN-3),分析结果与推荐值符合,相对标准偏差小于10％。     

Cadmium (II) imprinted 3-mercaptopropyltrimethoxysilane coated stir bar for selective extraction of trace cadmium from environmental water samples followed by inductively coupled plasma mass spectrometry detection

Cd(II) imprinted 3-mercaptopropyltrimethoxysilane (MPTS)-silica coated stir bar was prepared by sol–gel technique combining with a double-imprinting concept for the first time and was employed for stir bar sorptive extraction (SBSE) of trace Cd(II) from water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. A tetramethoxysilane (TMOS) coating was first in situ created on the glass bar surface. Afterward, a sol solution containing MPTS as the functional precursor, ethanol as the solvent and both Cd(II) and surfactant micelles (cetyltrimethylammonium bromide, CTAB) as the template was again coated on the TMOS bar. The structures of the stir bar coating were characterized by FT-IR spectroscopy. Round-bottom vial was used for the extraction of Cd(II) by SBSE to avoid abrasion of stir bar coatings. The factors affecting the extraction of Cd(II) by SBSE such as pH, stirring rate and time, sample/elution volume and interfering ions have been investigated in detail, and the optimized experimental parameters were obtained. Under the optimized conditions, the adsorption capacities of non-imprinted and imprinted coating stir bars were found to be 0.5 μg and 0.8 μg bar⁻¹. The detection limit (3σ) based on three times standard deviations of the method blanks by 7 replicates was 4.40 ng L⁻¹ and the relative standard deviation (RSD) was 3.38% (c = 1 μg L⁻¹, n = 7). The proposed method was successfully applied for the analysis of trace Cd(II) in rain water, East Lake and Yangtze River water. To validate the proposed method, certified reference material of GSBZ 50009-88 environmental water was analyzed and the determined value is in a good agreement with the certified value. The developed method is rapid, selective, sensitive and applicable for the analysis of trace Cd(II) in environmental water samples.     

High-throughput quantification of palladium in water samples by ion pair based-surfactant assisted microextraction

A novel method for the determination of palladium as a metal ion model was developed by ion pair based surfactant-assisted microextraction (IP-SAME) and inductively coupled plasma-optical detection (ICP-OES). In this methodology, a cationic surfactant was used in extraction process. It has two fundamental functions: (1) the formation of an emulsified phase and (2) the ion pair formation with Pd(II) in the presence of iodide ions and making PdI₄²⁻$\text{Pd}{{\text{I}}_4}^{2-}$ extractable into organic phase (active microextraction). The effective parameters on the extraction recovery such as the types of extraction solvent and the surfactant, surfactant concentration, KI amount and HCl concentration of the sample were investigated and optimized. In the proposed approach, tetradecyl trimethyl ammonium bromide (TTAB) was used as emulsifier and ion pairing agent, and 1-octanol was selected as extraction solvent. Under the optimum conditions, the enhancement factor as large as 146 was obtained. The detection limit for palladium was 0.2 μg L⁻¹, and the relative standard deviation (RSD) was 4.1% (n = 5, C = 10.0 μg L⁻¹). The proposed method was applied for extraction and determination of palladium in different water samples.