质谱分析计

14.1原理与构造:所谓质谱分析,就是用由离子源、质谱测定单元、检测器等部件构成的质谱分析装置,由离子源将化合物离子化或分解,从所生成的分子离子或碎片离子等的质谱图[由质量/电荷数(M/Z)的波峰位置可知各离子的质量数,由波高可知各离子量]分析化合物的方法。图14—1为最一般也是最常用的单聚束磁场偏向型质谱仪的原理图。由试样注入单元导入试样分子(M°),在离子化室进行如下式所示的离子化作用:

Role of potassium in acid secretion

Potassium (K+) ions are critical for the activation and catalytic cycle of the gastric H+,K+-ATPase, resulting in the secretion of hydrochloric acid into the parietal cell canaliculus. As both symptom, severity and esophageal mucosal damage in gastro-esophageal reflux disease (GERD) are related to the degree of acid exposure, K+ is a logical target for approaches to inhibit acid production.The probable K+ binding site on the gastric H+,K+-ATPase has recently been described and studies are elucidating how K+ activates the enzyme. K+ channels in the apical membrane of the parietal cell are implicated in the recycling of K+ and, to date, three potential K+ channels (KCNQ1, Kir2.1 and Kir4.1) have been identified. The channels represent theoretical sites for agents to control acid secretion but it will be difficult to develop selective blockers. An alternative strategy is to prevent K+ from activating gastric H+,K+-ATPase; the potassiumcompetitive acid blocker (P-CAB) class inhibits acidsecretion by binding at or near the K+ binding site.Ongoing research is further defining the role of K+ in the functioning of the gastric H+,K+-ATPase, as well as determining the clinical utility of agents directed toward this important cation.

Mechanism analysis of ions interaction in MgCl_2/LiCl solution and effect of lithium on ammonia precipitation products

Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.

Blanc Reaction of Aromatic Compounds Catalyzed by Ionic Liquids

Ionic liquids have been used as catalysts for Blanc reaction of toluene. The effects of reaction temperature, reaction time and dosage of the ionic liquid catalyst have been investigated, and the catalytic performance of different ionic liquid catalysts for toluene chloromethylation was also studied. The reaction was found to proceed under mild conditions with excellent conversion （up to 90%） in the absence of Lewis acids. The ionic liquids could be recycled and reused without loss of their catalytic activities.

Promotion of activation ability of N vacancies to N2 molecules on sulfur-doped graphitic carbon nitride with outstanding photocatalytic nitrogen fixation ability

Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.

Relativistic Configuration Interaction Calculations on Kα X-Ray Satellites of Manganese

With contributions from Breit interaction, quantum electrodynarnics （QED） corrections and nuclear mass corrections to the initial and final levels are taken into account. The transition energies, transition probabilities, and absorption oscillator strengths of Kα x-ray from Mn XVII to Mn XXIV have been calculated by using relativistic configuration interaction （RCI） and multi-configuration Dirac Fock （MCDF） method in the active interaction approach. Compared with the only available experimental transition data on He-like and Li-like manganese, the present results are in good agreement with them, and the rest of transition data of the present results are new ones. These wide range data can provide useful parameters for the study of the manganese plasma.

Ionization Potentials and Quantum Defects of 1s^2np^2p Rydberg States of Lithium Atom

Abstract In this work, ionization potentials and quantum effects of ls^2 np^2 P Rydberg states of lithium are calculated based on the calibrated quantum defect function. Energy levels and quantum defects for ls^2np^2P bound states and their adjacent continuum states are calculated with the R-matrix theory, and then the quantum defect function of the ls^2np （n ≥ 7） channel is obtained, which varies smoothly with the energy based on the quantum defect theory. The accurate quantum defect of the ls^2 7p^2P state derived from the experimental data is used to calibrate the original quantum defect function. The new function is used to calculate ionization potentials and quantum effects of ls^2np ^2P （n ≥ 7） Rydberg states. Present calculations are in agreement with recent experimental data in whole.

Effect of anions on preparation of ultrafine α-Al_2O_3 powder

Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃ for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the morphology, particle size, surface area and configuration of the precursors were studied. The results show that the reactions of urea with aluminium nitrate and aluminium chloride result in agglomerates gels with bad filtering performance, the morphology is fibrillar. Aluminium sulphate-urea reactions result in the direct formation of amorphous powders with good filtering performance, of which morphology are regular spherical particles with larger granularity and smaller surface area. The reaction of mutual compound of aluminium sulphate and aluminium nitrate with molar ratio of 40:60 with urea can produce precursor with good filtering performance, spherical morphology, and uniform granularity distribution in the particle size range of 2-3 μm.

Adsorption of ruthenium ions on activated charcoal: influence of temperature on the kinetics of the adsorption process

Influence of temperature on ruthenium adsorption on activated charcoal from 3 mol/L HNO3 solutions was inves- tigated in the temperature range of 288 K to 308 K. It was observed that the rise in temperature increases the adsorption of ru- thenium ions on activated charcoal and follows the kinetics of first order rate law with rate constant values 0.0564?0.0640 min?1 in the temperature range of 288 K to 308 K respectively. The activation energy for the adsorption process was found to be 1.3806 kJ/mol. Various thermodynamics quantities namely ?H, ?S and ?G were computed from the equilibrium constant KC values. The results indicated a positive heat of adsorption, a positive ?S and a negative ?G.

Synthesis and electrochemical properties of SnO_2-polyaniline composite

The SnO2-polyaniline(SnO2-PAn) composite was prepared by microemulsion polymerization method using aniline,ammonium peroxodisulfate and SnO2 as starting materials.The SnO2-PAn composite was characterized by X-ray diffractometer,scanning electron microscope and electrochemical techniques.The results show that PAn in the composites is amorphous.PAn formed in the reaction is deposited preferentially on the SnO2 particles,giving a SnO2-PAn composite,in which SnO2 is coated with PAn.SnO2-PAn composite shows a reversible capacity of 657.6 mA·h/g and the capacity loss per cycle is only 0.092% after 80 cycles,suggesting that SnO2-PAn composite is a promising anode material for lithium ion batteries.

Hydrolysis of Aluminum Ions in Kaolinite and Oxisol Suspensions as Influenced by Organic Anions

To evaluate the role of kaolinite and variable charge soils on the hydrolytic reaction of Al, the hydrolysis of Al ions in suspensions of a kaolinite and an Oxisol influenced by organic anions was investigated using changes of pH, Al adsorption, and desorption of pre-adsorbed Al. Kaolinite and the Oxisol promoted the hydrolytic reaction of Al above a certain initial Al concentration (0.1 mmol L-1 for kaolinite and 0.3 mmol L-1 for the Oxisol). The Al hydrolysis accelerated by kaolinite and the Oxisol increased with an increase in initial concentration of Al and was observed in the range of pH from 3.7 to 4.7 for kaolinite and 3.9 to 4.9 for the Oxisol. The acceleration of Al hydrolysis also increased with the increase of solution pH, reached a maximum value at pH 4.5, and then decreased sharply. Al hydrolysis was promoted mainly through selective adsorption for hydroxy-Al. Soil free iron oxides compensated a portion of the soil negative charge or masked some soil surface negative sites leading to a decrease in Al adsorption, which retarded acceleration to some extent. For the Oxisol organic anions increased the proportion of adsorbed Al3+ in total adsorbed Al with the increase in soil negative surface charge and eliminated or reduced the acceleration of Al hydrolysis. Different organic anions inhibited the hydrolysis of Al in the order: citrate > oxalate > acetate (under initial pH of 4.5). The formation of Al-organic complexes in solution also inhibited the hydrolysis of Al.

PURIFICATION OF L-METHIONINE AND N-ACETYL-D-METHIONINE FROM THE MIXTURE OF ENZYMATICALLY DEACYLATED N-ACETYL-DL-METHIONINE

N-acetyl-D-methionine, NaAc and the remains of N-acetyl-L-methionine dramatically affect the purification of L-methionine when purified from the mixture of enzymatically deacylated N-acetyl-DL-methionine, leading to a low yield conventionally. Here, this paper reports a successful separation and purification of both L-methionine and N-acetyl-D-methionine by an H ion-exchange column. The pH, L-Met concentration and the ratio between the content of sodium cation and the ion-exchange capacity were optimized to obtain the maximum yield. Experimental results indicate that, under the optimized conditions, the yields of L-methionine and N-acetyl-D-methionine can reach as high as 85% and 75%, respectively.

Low Pressure Cold Plasma as an Alternative Method for Black Pepper Sterilization

It was found out that spices straight from the package are not sterile. The only way to receive sterile spices is to use radiation technology which means to irradiate spices with ionizing radiation. However, this method is quite expensive and raises great resistance of public. And this is the reason why we are interested in implementing plasma technology. The first step of the research was to choose the most appropriate spice. The range of available spices is nearly unlimited, however, we took into account the following ones： sweet paprika, basil, rosemary, saffron, marjoram, thyme and black pepper. Finally, we chose black pepper because it is most often used by butchers to make meat products. It is also called the ＂King of Spices＂ or the ＂Black Gold＂. Black pepper is one of the most often used spices in the United States and in Europe. It is important to have sterile black pepper when we aim at ripening products for example ripening sausages or some kinds of cheeses. What is more, it was found out that black pepper has antimicrobial properties, antioxidant effects and also antipyretic and analgesic properties. The aim of the research was to receive sterile spices using low pressure cold plasma with oxygen, nitrogen, air, argon and hydrogen peroxide.

The development of MOFs-based nanomaterials in heterogeneous organocatalysis

Metal-organic framework(MOF) is a class of inorganic-organic hybrid material assembled periodically with metal ions and organic ligands. MOFs have always been the focuses in a variety of frontier fields owing to the advantageous properties, such as large BET surface areas, tunable porosity and easyfunctionalized surface structure. Among the various application areas, catalysis is one of the earliest application fields of MOFs-based materials and is one of the fastest-growing topics. In this review, the main roles of MOFs in heterogeneous organocatalysis have been systematically summarized, including used as support materials(or hosts), independent catalysts, and sacrificial templates. Moreover, the application prospects of MOFs in photocatalysis and electrocatalysis frontiers were also mentioned.Finally, the key issues that should be conquered in future were briefly sketched in the final parts of each item. We hope our perspectives could be beneficial for the readers to better understand these topics and issues, and could also provide a direction for the future exploration of some novel types of MOFs-based nanocatalysts with stable structures and functions for heterogeneous catalysis.

Fabricating low-temperature-tolerant and durable Zn-ion capacitors via modulation of co-solvent molecular interaction and cation solvation

Aqueous Zn-based energy-storage devices have aroused much interest in recent years.However,uncontrollable dendrite growth in the Zn anode significantly limits their cycle life.Moreover,the poor low-temperature performance arising from the freezing of aqueous electrolytes at sub-zero temperatures restricts their practical applications in cold regions.Here,we fabricated low-temperature-tolerant and durable Zn-ion hybrid supercapacitors(ZHSCs)via modulating a co-solvent water/ethylene glycol electrolyte.The interaction of intermolecular hydrogen bonds between water and ethylene glycol as well as cation solvation was systematically investigated by tuning the co-solvent composition.The results illustrate that the ZnSO_(4)/water/ethylene glycol(65%)electrolyte possesses high ionic conductivity at low temperatures and effectively prevents the dendrite formation of the Zn anode.The as-fabricated ZHSCs exhibit long-term cyclability and are capable of working at sub-zero temperatures as low as -40℃.The present ZHSCs are anti-freezing and cost-effective,which may find new applications in the fields of next-generation electrochemical energy storage devices.

Computational studies of the structure and cation-anion interactions in 1-ethyl-3-methylimidazolium lactate ionic liquid

Quantum chemical calculations of the structures and cation-anion interaction of 1-ethyl-3-methylimidazolium lactate ([Emim][LAC]) ion pair at the B3LYP/6-31++G** theoretical level were performed. The relevant geometrical characteristics, energy properties, intermolecular H-bonds (H-bonds), and calculated IR vibrations with respect to isolated ions were systematically discussed. The natural bond orbital (NBO) and atoms in molecule (AIM) analyses were also employed to understand the nature of the interactions between cation and anion. The five most stable geometries were verified by analyzing the relative energies and interaction energies. It was found that the most of the C-H···O intermolecular H-bonds interactions in five stable conformers have some covalent character in nature. The elongation and red shift in IR spectrum of C-H bonds which involve in H-bonds is proved by electron transfers from the lone pairs of the carbonyl O atom of [LAC] to the C-H antibonding orbital of the [Emim]+. The interaction modes are more favorable when the carbonyl O atoms of [LAC] interact with the C2-H of the imidazolium ring and the C-H of the ethyl group through the formation of triple H-bonds.

Fe3O4 Octahedral Colloidal Crystals

We present a facile and controllable method for the large-scale fabrication of highly-ordered octahedral Fe3O4 colloidal ＂single crystals＂ without the assistance of a substrate. Oleic acid is used to reduce the solubility of the nano-building blocks in colloidal solution and to induce a ＂crystallization＂ process. Our colloidal crystals are of multimicron size and show typical crystallographic characteristics. They have a very robust structure and can serve as a novel ordered magnetic mesoporous material with a relatively narrow pore size distribution. The sample possesses an extremely high Verwey transition temperature （Tv） of 100 K and a high saturation magnetization （Ms） of 86 emu/g at 5 K based on its good crystallinity, as well as the interparticle dipolar interaction behavior arising from its unique structure. Electrochemical measurements have demonstrated the excellent capacity of the mesoporous colloidal crystals when used in lithium-ion batteries.

Interaction of multi-walled carbon nanotubes and zinc ions enhances cytotoxicity of zinc ions

More and more nanomaterials enter the environment along with their production, application and deposal. They may alter the biological effect of pollutants already existing in the real environment by different interactions. Therefore efforts should also be paid to investigate the combined toxicity of nanomaterials and pollutants. Herein, we studied the combined toxicity of oxi- dized multi-walled carbon nanotubes （O-MWCNTs） and zinc ions on ceils. It is found that cytotoxicity of the combined O-MWCNTs and zinc ions elevates significantly, compared with O-MWCNTs or zinc ions alone. This result comes from the assays of cell morphology, cell viability and proliferation, cell membrane integrity, mitochondrial membrane potential and cell apoptosis. Mechanism studies indicate that O-MWCNTs absorb zinc ions and form slight aggregation. These enhance remark- ably the cellular uptake of O-MWCNTs, and thus induce the death of cells by bringing in more zinc ions into cells. Our study indicates that the existence of nanomaterials could change the bioconsequence of other pollutants and emphasizes the im- portance of the combined toxicity research in the presence of nanomaterials.

multi-solitons interaction multicomponent plasma extended Poincare–Lighthill–Kuo method head-on collision

The propagation and interaction between ion acoustic multi-solitons in an unmagnetized multicomponent plasma consisting of fluid hot ions, positrons and both hot and cold electrons, are investigated by employing the extended Poincare–Lighthill–Kuo（PLK） method. Two different Kortewege-de Vries（K-dV） equations are derived. The Hirota＇s method is applied to get the K-dV multi-solitons solution. The phase shift due to the overtaking and head- on collision of the multi-solitons is obtained.

Synergetic effects of blended materials for Lithium-ion batteries

LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, LiMn_2O_4 and LiCoO_2 are paired to make the blended materials for the cathode of lithium-ion batteries. The factors impacting on the characteristics of blended materials are studied using constant current charge/discharge measurement and electrochemical impedance spectroscopy. The results show that the three pairs of blended materials exhibit very different synergetic effects in high C-rate discharging. The mechanism of particle synergetic effect has a physical root on the compensating material property of blending components, which fundamentally correlates with their similarity and difference in crystalline and electronic structures. The AC impedance show the obvious changes that alternate the high C-rate performance, due to reduced particle impedance in blended materials. The pairs of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2-LiMn_2O and LiCoO_2-LiMn_2O_4 present obvious increases in high C-rate reversible capacities than does the pair LiCoO_2-LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2.