Electrospray ionization mass spectrometry of tetracycline, oxytetracycline, chlorotetracycline, minocycline, and methacycline

The effects of mobile-phase additives and analyte concentration on electrospray ionization mass spectra of a series of tetracyclines were investigated in both positive and negative ion modes. Only [M + H](+) and [M - H](-) ions were observed. The greatest sensitivity as [M + H](+) ions was obtained with 1% acetic acid and the greatest sensitivity as [M - H](-) ions was obtained using 50 mM ammonium hydroxide. Sensitivities in the positive ion mode were greater than those in the negative ion mode. The sensitivity as [M + H](+) showed no systematic variation with pH; however, the sensitivity as [M - H](-) did increase with increasing pH. A larger linear range was observed for [M - H](-) than for [M + H](+) ions. Both [M + Na](+) and [M + H](+) ions were observed with 0.5 mM sodium acetate and sodium iodide, but no adduct ions were observed with ammonium acetate. Some M(2)H(+) ions were observed at higher concentrations. Cluster ions, Na(NaOAc)(n)(+) or Na(NaI)(n)(+), but no sample ions were observed using 5 mM salts. The data suggest that mechanisms in addition to solution ionization are involved in the formation of the ESI sample ions. The utility of mobile phases containing 1% HOAc or 50 mM NH(4)OH was demonstrated for chromatographic separations.     

Effects of mobile-phase additives, solution pH, ionization constant, and analyte concentration on the sensitivities and electrospray ionization mass spectra of nucleoside antiviral agents

The effects of various mobile-phase additives, solution pH, pKa, and analyte concentration on electrospray ionization mass spectra of a series of purine and pyrimidine nucleoside antiviral agents were studied in both positive and negative ion models. The use of 1% acetic acid resulted in good HPLC separation and the greatest sensitivity for [M + H]+ ions. In the negative ion mode, 50 mM ammonium hydroxide gave the greatest sensitivity for [M - H]- ions. The sensitivities as [M + H]+ ions were significantly larger than the sensitivities as [M - H]- ions for purine antiviral agents. Vidarabine monophosphate and pyrimidine antiviral agents, however, showed comparable or greater sensitivities as [M - H]- ions. The sensitivity as [M + H]+ showed no systematic variation with pH; however, the sensitivity as [M - H]- did increase with increasing pH. At constant pH, the ion intensity of the protonated species increased with increasing pKa. At higher analyte concentrations, dimer (M2H+) and trimer (M3H+) ions were observed. [M + Na]+ adducts were the dominant ions with 0.5 mM sodium salts for these compounds. The spectra of the more basic purine antiviral agents showed no [M + NH4]+ adduct ions, but [M + NH4]+ ions were the major peaks in the spectra of the less basic pyrimidine antiviral agents with ammonium salts. The ammonium adduct ion was formed preferentially when the proton affinity of the analyte was close to that of NH3. Abundant [M + OAc]- ions were observed for all of the antiviral agents except vidarabine monophosphate from solutions with added HOAc, NaOAc, and NH4OAc. The utility of mobile phases containing 1% HOAc or 50 mM NH4OH was demonstrated for chromatographic separations.     

Ionization and scintillation produced by relativistic Au, He and H ions in liquid argon

We have measured ionization and scintillation produced by relativistic ions of Au, He and H in liquid argon. The sum of ionization signal and scintillation signal per unit energy deposition is the same for He and H ions, which is also the same as that for relativistic Ne, Fe and La ions previously measured. We have found that quenching occurs when liquid argon is irradiated by relativistic Au ions and that the sum per unit energy deposition for the Au ions is 70–76% of that for the other ions mentioned above.     

Speciation, stability, and reactions of Np(III–VII) in aqueous solutions

Published data on the structure of Np ions in acid and alkali solutions, on hydrolysis of Np ions and their complexation with anions and cations, on their redox reactions with water and with each other (disproportionation, reproportionation), and on the effect of anions on this process are analyzed. Possible directions of research in chemistry of Np ions are outlined.     

Atomistic mechanisms of ZnO aggregation from ethanolic solution: ion association, proton transfer, and self-organization

We report on atomistic simulations related to the nucleation of zinc oxide nanocrystals from ethanolic solution. The underlying mechanisms are explored from the very initial stage of Zn2+ and OH(-) ion association to the formation of nanometer-sized aggregates counting up to 250 ions. The embryonic aggregates consist of zinc and hydroxide ions, only. At later stages of aggregate growth, proton transfer reactions at the aggregate-solvent interface account for the formation of O(2-) ions and induce the precipitation of zinc oxide. After the association of around 150 ions, ZnO domains were found to nucleate in the central region of the [Znx(OH)yOz]2x-y-2z) aggregates. In the course of further ion association and condensation reactions, progressive self-organization leads to an extended core in which the ions are arranged according to the wurtzite structure.     

Use of doubly charged ions in the determination of certain rare earth elements in neodymium, samarium, europium, and their compounds by inductively coupled plasma mass spectrometry

It is proposed to use doubly charged ions of the rare earth elements (REEs) to be determined in samples of neodymium, samarium, europium, and gadolinium by inductively coupled plasma mass spectrometry (ICP-MS) in order to reduce spectral interferences caused by oxide and hydroxide matrix ions. Optimal conditions for the registration of the doubly charged ions of REEs (resolution, depth of plasma sampling, generator output power, and argon flow in a nebulizer) are developed. The limits of determination for the REEs determined using singly and doubly charged ions in the samples of Nd, Sm, Eu, and Gd are evaluated. It is shown that the use of the signal from the doubly charged ions of odd isotopes allows reducing the limits of determination for Dy, Ho, Tm, and Er in neodymium, samarium, europium, and their oxides by one to two orders of magnitude.     

Development of a selective and sensitive flotation method for determination of trace amounts of cobalt, nickel, copper and iron in environmental samples

A simple, selective and rapid flotation method for the separation-preconcentration of trace amounts of cobalt, nickel, iron and copper ions using phenyl 2-pyridyl ketone oxime (PPKO) has been developed prior to their flame atomic absorption spectrometric determinations. The influence of pH, amount of PPKO as collector, type and amount of eluting agent, type and amount of surfactant as floating agent and ionic strength was evaluated on the recoveries of analytes. The influences of the concomitant ions on the recoveries of the analyte ions were also examined. The enrichment factor was 93. The detection limits based on 3 sigma for Cu, Ni, Co and Fe were 0.7, 0.7, 0.8, and 0.7 ng mL(-1), respectively. The method has been successfully applied for determination of trace amounts of ions in various real samples.     

Ion energy,charge, and mass distributions in nanosecond surface discharge plasma

We have studied the composition of plasma formed during nanosecond high-voltage discharge at the surface of various insulators in vacuum. The flows of ions with velocities on the order of 10² km/s have been revealed. The energy distribution of ions in the plasma extends from several hundred electronvolts to a few kilo-electronvolts.     

钼掺杂铜硅钙石的制备及其抗菌性能和细胞相容性研究

含铜生物材料在高浓度铜离子释放时对细菌有优异的抑制作用, 但同时具有细胞毒性; 而在低浓度铜离子释放时虽然具有良好的细胞相容性, 但其抗菌性能低。因此, 开发一种含铜生物材料, 使其能够在高浓度铜离子释放情况下同时具有优异抗菌性能和良好细胞相容性, 具有重要意义。本研究利用钼和铜之间的拮抗作用原理, 采用溶胶-凝胶法制备了钼掺杂铜硅钙石, 并通过细菌平板实验和细胞活力实验评价了材料的抗菌性能和细胞相容性。实验结果显示, 钼掺杂铜硅钙石释放的高浓度铜离子(高于8.87 μg∙mL ^-1)对金黄色葡萄球菌有良好的抑制性能。同时, 由于铜钼离子的拮抗作用能降低高浓度铜离子对细胞的毒性, 钼掺杂铜硅钙石释放的铜离子在9.65 μg∙mL ^-1的高浓度下依然能保证人脐静脉内皮细胞存活率高达90%。因此, 钼掺杂可以作为含铜生物材料降低其细胞毒性的一种有效途径, 为开发低细胞毒性含铜抗菌生物材料提供了新的路径。     

Nuclear tracks in CR-39 produced by carbon,oxygen, aluminium and titanium ions

This work describes the response of CR-39 (allyl diglycol polycarbonate) to different ions (C, O, Al and Ti) produced by the Instituto de Fisica 3 MV 9SDH-2 Pelletron accelerator and backscattered from a thin Au film on a C support. The ion energies were chosen in series such that the ranges of the different ions in the detector were 2, 3, 4, 5, 6, 7 and 8 microm respectively for each series. Once exposed, the detectors were etched with a solution of 6.25 M KOH at 60 degrees C, and the reading was carried out using a digital image analysis system. An analysis of the measured track diameters of all the types of ions indicates that, for a given range, track kinetics are independent of type of ion, energy and stopping power.     

Removal of radionuclides,macrocomponent metal ions,and organic compounds from solutions by nanofiltration

Removal of Mg²⁺, Сa²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Fe³⁺, and Pr³⁺ ions, tracer amounts of ¹³⁷Cs, ⁸⁵Sr, and ⁶⁰Co radionuclides, and oxalate and ethylenediaminetetraacetate ions from solutions using a polymeric nanofiltration (NF) membrane produced by RM Nanotekh (Russia) was studied. The selectivity (S) of the NF membrane to multicharged metal cations is considerably higher than to single-charged cations. The NF membrane exhibits the highest selectivity (S = 94–97%) to triple-charged Fe³⁺ and Pr³⁺ ions and double-charged Cu²⁺ ions. The selectivity to double-charged Mg²⁺ and Zn²⁺ ions is somewhat lower (90–94% on the average). Among doublecharged cations, the NF membrane exhibits the lowest selectivity (80–88%) to Ni²⁺ and Cа²⁺ ions. The NF membrane shows high performance in retention of tracer amounts of Sr (S = 95%) and Co (S > 99%) radionuclides, and also of oxalate (S = 94.5%) and ethylenediaminetetraacetate (S = 97.5%) ions. Examples of using the nanofiltration method for removing ⁶⁰Co from a model solution simulating NPP bottom residue and for removing transition metal impurities from a LiCl solution are presented.     

Influence of platinum, antimony and iron ions on coloration of alkali-borosilicate optical glass

We studied influence of platinum, antimony and iron ions on the coloration of alkali-borosilicate glass. The optical transmittances of glass specimens with and without antimony were compared, and the cause of absorption in antimony-free glass was studied. It was found in antimony-free glass that a small amount of dissolved Pt²⁺ on the ppm order causes strong absorption at approximately 360 nm resulting in a yellowish color. This absorption was not observed in the specimens melted at temperatures below 1150 °C, or in the colorless specimens containing antimony or iron. It was indicated, in the colorless specimens that platinum exist as Pt⁴⁺, the absorption of which occurs in the UV region. The oxidation state of platinum ions was strongly affected by melting temperature or coexisting multivalent ions such as antimony or iron ions, which act as an oxidant of platinum ions. Keeping the melting temperature low and employing appropriate oxidant ions are effective means of designing colorless antimony-free optical glass.     

Optical properties of aluminophosphate glasses containing silver, tin, and dysprosium

The spectroscopic properties of a Dy³⁺-doped aluminophosphate glass containing silver and tin were reported. Different oxidation and aggregation states of silver were obtained by varying silver concentration and glass thermal history. The addition of silver and tin at the lowest concentration studied results in Dy³⁺ ions emission under nonresonant UV excitation in connection with the appearance of an excitation band around 270 nm, which is associated to isolated Ag⁺ ions and twofold-coordinated Sn centers. The increase in silver and tin concentration leads to a broadening of aforementioned band and to the presence of charged silver dimers as evidenced by the appearance of an excitation band around 330 nm. The data indicated that light absorption might take place at ionic silver species and twofold-coordinated Sn centers, followed by energy transfer to Dy³⁺ ions. After heat treatment, ionic silver species were reduced to atomic Ag by tin with the subsequent formation of Ag nanoparticles (NPs) inside the dielectric host. A quenching effect in Dy³⁺ ions luminescence was shown with the presence of the Ag NPs, most notably for excitation of ⁶H_15/2 → ⁴F_9/2, ⁴I_15/2, ⁴G_11/2 transitions, which were in resonance with the dipole absorption mode of the particles. The silver NPs were believed to provide radiationless pathways for excitation energy loss in Dy³⁺ ions.     

Tandem mass spectrometry characteristics of silver-cationized polystyrenes: internal energy, size, and chain end versus backbone substituent effects

The Ag(+) adducts of polystyrene (PS) oligomers with different sizes (6-19 repeat units) and initiating (alpha) or terminating (omega) end groups mainly decompose via free radical chemistry pathways upon collisionally activated dissociation. This reactivity is observed for ions formed by matrix-assisted laser desorption/ionization as well as electrospray ionization. With end groups lacking weak bonds (robust end groups), dissociation starts with random homolytic C-C bond cleavages along the PS chain, which lead to primary and benzylic radical ions containing either of the chain ends. The primary radical ions mainly depolymerize by successive beta C-C bond scissions. For the benzylic radical ions, two major pathways are in competition, namely, depolymerization by successive beta C-C bond scissions and backbiting via 1,5-H rearrangement followed by beta C-C bond scissions. The extent of backbiting decreases with internal energy. With short PS chains, the primary radical ions also undergo backbiting involving 1,4- and 1,6-H rearrangements; however, this process becomes negligible with longer chains. If the polystyrene contains a labile substituent at a chain end, this substituent is eliminated easily and, thus, not contained in the majority of observed fragments. Changes in the PS backbone structure can have a dramatic effect on the resulting dissociation chemistry. This is demonstrated for poly(alpha-methylstyrene), in which backbiting is obstructed due to the lack of benzylic H atoms; instead, this backbone connectivity promotes 1,2-phenyl shifts in the primary radical ions formed after initial C-C bond homolyses as well as H atom transfers between the incipient primary and benzylic radicals emerging from these homolyses.     

Matrix-assisted laser desorption/ionization coupled with quadrupole/orthogonal acceleration time-of-flight mass spectrometry for protein discovery, identification, and structural analysis

The design and operation of a novel UV-MALDI ionization source on a commercial QqoaTOF mass spectrometer (Applied Biosystem/MDS Sciex QSTAR Pulsar) is described. Samples are loaded on a 96-well target plate, the movement of which is under software control and can be readily automated. Unlike conventional high-energy MALDI-TOF, the ions are produced with low energies (5-10 eV) in a region of relatively low vacuum (8 mTorr). Thus, they are cooled by extensive low-energy collisions before selection in the quadrupole mass analyzer (Q1), potentially giving a quasi-continuous ion beam ideally suited to the oaTOF used for mass analysis of the fragment ions, although ion yields from individual laser shots may vary widely. Ion dissociation is induced by collisions with argon in an rf-only quadrupole cell, giving typical low-energy CID spectra for protonated peptide ions. Ions separated in the oaTOF are registered by a four-anode detector and time-to-digital converter and accumulated in "bins" that are 625 ps wide. Peak shapes depend upon the number of ion counts in adjacent bins. As expected, the accuracy of mass measurement is shown to be dependent upon the number of ions recorded for a particular peak. With internal calibration, mass accuracy better than 10 ppm is attainable for peaks that contain sufficient ions to give well-defined Gaussian profiles. By virtue of its high resolution, capability for accurate mass measurements, and sensitivity in the low-femotomole range, this instrument is ideally suited to protein identification for proteomic applications by generation of peptide tags, manual sequence interpretation, identification of modifications such as phosphorylation, and protein structural elucidation. Unlike the multiply charged ions typical of electrospray ionization, the singly charged MALDI-generated peptide ions show a linear dependence of optimal collision energy upon molecular mass, which is advantageous for automated operation. It is shown that the novel pulsing technique of this instrument that increases the sensitivity for precursor ions scans is applicable to the identification of peptides labeled with isotope-coded affinity tags.     

湿法碳氮硫共掺杂TiO2的制备及其光催化活性

以全硫碳酸铵为掺杂剂,采用湿法由硫酸钛出发制得碳氮硫共掺杂TiO2,通过XRD和XPS对掺杂TiO2进行了表征,并对掺杂TiO2的光催化活性进行了考察。结果表明,微波辅助加热制备的掺杂TiO2中,C元素部分替位取代了TiO2晶格中的Ti 4+;N元素以两种掺杂形式存在,即进入TiO2晶格替位取代O2-产生掺杂和通过化学吸附进入晶格间隙产生掺杂;S元素主要提供S 2p形成S6+取代Ti 4+进入晶格进行掺杂;以甲基橙溶液为对象进行光催化降解,当掺杂量α为1.6、500℃焙烧2h时,掺杂TiO2表现出较高的可见光催化活性,光照70min使浓度为20mg/L的甲基橙溶液的降解率达到99.64%,明显提高了纳米TiO2的光催化活性。     

Adsorption of Cd, Cu, Ni, Pb and Zn on Sphagnum peat from solutions with low metal concentrations

This work investigates adsorption of metal ions on Sphagnum peat from solutions with environmentally relevant concentrations of metals. The peat moss is intended as an alternative, low-cost filter material for contaminated waters. Adsorption of Cd, Cu, Ni, Pb and Zn was studied in batch tests, and adsorption isotherms were determined. The kinetics of adsorption was analyzed using a second-order model and rate constants were calculated. An empirical model for predicting adsorption of metal ions at a given time was derived from these constants. Metal ions were removed in the descending order Pb>Cu>Ni>Cd>Zn. Relationship between the affinities of the metals to the peat active sites with chemical properties for the metals were indicated by the results. In addition, equilibration studies were performed at constant pH and ionic strength. The experimental data fitted the Freundlich equation. Both the uptake of metals and the Freundlich constants increased in line with increasing pH. The Freundlich exponent declined with higher initial concentrations, suggesting adsorption to sites with lower activity.     

Valency states of Yb, Eu, Dy and Ti ions in Li2B4O7 glasses

Absorption and emission spectra of Eu and Dy, Yb and Ti ions in Li₂B₄O₇ glasses grown in oxygen and hydrogen gas atmospheres were measured for valency states and lattice-sites analysis. For the Li₂B₄O₇ glass doped with Eu²⁺, Eu³⁺ and Dy³⁺ ions which were grown in oxidizing and reducing atmospheres, absorption and emission bands due to these ions were investigated before and after γ-irradiation. For the Yb³⁺-doped Li₂B₄O₇ glass, a weak, broad band was observed near the sharp 976.3 nm absorption band. The origin of this band is discussed in comparison with other glasses. Moreover, irradiation experiments using γ-rays were also performed in order to investigate the possibility of valency change of Yb ions. It was found that Ti⁴⁺ ions, which are produced under oxidizing atmosphere, change to Ti³⁺ ions after γ-irradiation with a dose of 10⁵ Gy. An additional absorption band observed at about 500 nm is due to the Ti³⁺ ions accompanied by charge-compensating vacancy and does not give any emission.     

Recent progress on the spectroscopy of rare earth ions in core-shells, nanowires, nanotubes, and other novel nanostructures

Research and development of nanoscale luminescent and laser materials are part of the rapidly advancing nanoscience and nanotechnology. Because of unique spectroscopic properties and luminescent dynamics of f-electron states, doping luminescent rare earth ions into nano-hosts has been demonstrated as an optimistic approach to developing highly efficient and stable nanophosphors for various applications. In this article, we review the most recent progress in spectroscopic measurements of rare earth ion-activated low-dimensional nanostructures including nanolayers, core-shells, nanowires, nanotubes, and nanodisks. Among a large volume of work reported in the literature on many members of the rare earth series including Ce3+, Pr3+, Nd3+, Eu3+, and Er3+, we focus on recent findings in the spectroscopic and luminescence properties of Eu3+ doped nanolayers, core-shells, and nanotubes, because Eu3+ ions have been extensively studied and widely used as an ideal probe for fundamental understanding of nano-phenomena. Specifically, the dependence of the optical properties of rare earth ions on nanostructures is discussed in detail.     

Structural, optical and electrical properties of nitrogen ion implanted ZnO nanorods

This study examined the micro-structural and electrical properties of N+-ion-implanted ZnO nanorods. Nitrogen ions with energies of 10-90 keV and beam fluxes of 10(13)-10(16) ions/cm2 were implanted on vertically-aligned ZnO nanorods. Energy dispersive X-ray spectroscopy measurements showed that N+ ions were spread uniformly over the nanorods. Extended X-ray absorption fine structure measurements revealed that the implanted N+s had partially substituted for the oxygen sites. Photoluminescence measurements showed a neutral-donor bound exciton peak at 3.36 eV and a two-electron-satellite peak at 3.33 eV independent of the ion energy and flux. The I-V characteristic curves showed that the current density was not changed by the N+ ion energy and flux much. These results strongly suggested that the N ions substituted for the oxygen sites were neutral.