Established and emerging atmospheric pressure surface sampling/ionization techniques for mass spectrometry

The number and type of atmospheric pressure techniques suitable for sampling analytes from surfaces, forming ions from these analytes, and subsequently transporting these ions into vacuum for interrogation by MS have rapidly expanded over the last several years. Moreover, the literature in this area is complicated by an explosion in acronyms for these techniques, many of which provide no information relating to the chemical or physical processes involved. In this tutorial article, we sort this vast array of techniques into relatively few categories on the basis of the approaches used for surface sampling and ionization. For each technique, we explain, as best known, many of the underlying principles of operation, describe representative applications, and in some cases, discuss needed research or advancements and attempt to forecast their future analytical utility. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Polyketide Synthase-Mediated O-Methyloxime Formation in the Biosynthesis of the Oximidine Anticancer Agents

Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are modular megaenzymes that employ unusual catalytic domains to assemble diverse bioactive natural products. One such PKS is responsible for the biosynthesis of the oximidine anticancer agents, oxime-substituted benzolactone enamides that inhibit vacuolar H⁺-ATPases. Here, we describe the identification of the oximidine gene cluster in Pseudomonas baetica and the characterization of four novel oximidine variants, including a structurally simpler intermediate that retains potent anticancer activity. Using a combination of in vivo, in vitro and computational approaches, we experimentally elucidate the oximidine biosynthetic pathway and reveal an unprecedented mechanism for O-methyloxime formation. We show that this process involves a specialized monooxygenase and methyltransferase domain and provide insight into their activity, mechanism and specificity. Our findings expand the catalytic capabilities of trans-AT PKSs and identify potential strategies for the production of novel oximidine analogues.     

Development and Validation of Liquid Chromatography-Tandem Mass Spectrometry Methods for the Quantification of Cefquinome,Ceftiofur, and Desfuroylceftiofuracetamide in Porcine Feces with Emphasis on Analyte Stability

Cefquinome and ceftiofur are β-lactam antibiotics used for the treatment of bacterial infections in swine. Although these antimicrobials are administered intramuscularly, the exposure of the gut microbiota to these cephalosporins is not well described. This exposure can contribute to the emergence and spread of antimicrobials in the environment and to the possible spread of antimicrobial resistance genes. To assess the impact of drug administration on the intestinal excretion of these antimicrobials it is essential to measure the amounts of native compound and metabolites in feces. Two (ultra)-high-performance liquid chromatography-tandem mass spectrometry ((U)HPLC–MS/MS) methods were developed and validated, one for the determination of cefquinome and ceftiofur and the other for the determination of ceftiofur residues, measured as desfuroylceftiofuracetamide, in porcine feces. The matrix-based calibration curve was linear from 5 ng g⁻¹ to 1000 ng g⁻¹ for cefquinome (correlation coefficient (r) = 0.9990 ± 0.0007; goodness of fit (gof) = 3.70 ± 1.43) and ceftiofur (r = 0.9979 ± 0.0009; gof = 5.51 ± 1.14) and quadratic from 30 ng g⁻¹ to 2000 ng g⁻¹ for desfuroylceftiofuracetamide (r = 0.9960 ± 0.0020; gof = 7.31 ± 1.76). The within-day and between-day precision and accuracy fell within the specified ranges. Since β-lactam antibiotics are known to be unstable in feces, additional experiments were conducted to adjust the sampling protocol in order to minimize the impact of the matrix constituents on the stability of the analytes. Immediately after sampling, 500 µL of an 8 µg mL⁻¹ tazobactam solution in water was added to 0.5 g feces, to reduce the degradation in matrix.     

Outcome of laryngeal and velopharyngeal biofeedback treatment in children and young adults: A pilot study

A relatively new management strategy for the treatment of voice disorders is the use of laryngeal (LB) and velopharyngeal biofeedback (VB). The main purpose of the present pilot study is to document the outcome of vocal and velopharyngeal performances after a well-defined LB and VB treatment. Four subjects were studied pretreatment (1 week before LB or VB treatment) and posttreatment (1 week after the LB or VB treatment). To measure and compare the effect of LB and VB, objective and subjective assessment techniques were used. Perceptual voice assessment included a perceptual rating of the voice using the GRBAS scale. Furthermore, the vocal quality in this population is modeled by means of the Dysphonia Severity Index. For the objective assessment of nasal resonance, the Nasometer and the Glatzel test were used. A perceptual evaluation of speech, the Gutzmann test, and the tests from Bzoch were used as subjective assessment techniques. Both patients selected for LB and VB treatment showed improvement of their performances. The resulting improvement, as measured by means of an objective approach, is in agreement with the perceived (auditory) improvement of voice and resonance. The use of LB and VB treatment in patients, especially in some subjects who are not responding to traditional voice or velopharyngeal therapy, must be encouraged.     

Crystal structure and chemical bonding of the intermetallic Zintl phase Yb(11)AlSb(9)

High resolution single crystal synchrotron X-ray diffraction data measured at 15(2) K were used to solve the structure of the complex intermetallic Zintl phase, Yb(11)AlSb(9) (space group Iba2), made up of Yb cations and polyanions along with isolated Sb anions. The 15(2) K cell parameters are a = 11.7383(4) ?, b = 12.3600(4) ?, c = 16.6796(6) ?. The temperature dependence of the structure was investigated through high resolution synchrotron powder X-ray diffraction (PXRD) data measured from 90 K to 1000 K. Rietveld refinements of the crystal structure revealed near linear thermal expansion of Yb(11)AlSb(9) with expansion coefficients of 1.49(2) × 10(-5) K(-1), 1.71(3) × 10(-5) K(-1), 1.13(1) × 10(-5) K(-1) for a, b and c, respectively. The chemical bonding in Yb(11)AlSb(9) was analyzed using atomic Hirshfeld surfaces, and the analysis supports the presence of the structural elements of Yb cations, [AlSb(4)](9-) tetrahedra, [Sb(2)](4-) dimers and isolated Sb(3-) anions. However, indications of interatomic interactions between the Zintl anions and the Yb cations were also observed.     

Dynamics or Stochastic Conductance Switching of Phenylene–Ethynylene Oligomers?

Scanning tunneling microscopy (STM) studies of phenylene-ethynylene oligomers inserted in alkanethiolate self assembled monolayers (SAMs) are presented. Spontaneous changes in appearance of bundles of inserted molecules during imaging are observed. The results indicate that the appearance changes are caused by fluctuations of the number of molecules in the bundles, by diffusion and exchange of molecules, in contrast to previous reports which attribute the changes to stochastic conductance switching. The packing density of the SAM around the bundles of inserted molecules influence the fluctuations, as the fluctuations observed at 77 K all take place in bundles inserted at locally less-densely packed SAM areas. At room temperature fluctuations of bundles inserted in well-ordered areas are also observed.     

Stabilities of the C-H...O bonded complexes of the haloforms HCClnF3-n (n = 0-3) with dimethyl ether, oxirane, and acetone: an experimental and theoretical study

Complexation enthalpies of the complexes of the haloforms HCCl(n)F(3-)(n) (n = 0-3) with dimethyl ether, oxirane, and acetone have been determined in liquid krypton and/or liquid argon using infrared spectroscopy. The same quantities were derived starting from ab initio complexation energies, calculated at the MP2=FULL/aug-cc-VTZ level, and by correcting these energies for thermodynamic and solvent contributions. The two sets of data are compared and discussed.     

Liquid-phase microextraction based on carrier mediated transport combined with liquid chromatography-mass spectrometry. New concept for the determination of polar drugs in a single drop of human plasma

Recently, we demonstrated for the first time liquid-phase microextraction (LPME) of polar drugs based on carrier mediated transport. In this new extraction technique, selected analytes were extracted as ion-pairs from small volumes of biological samples, through a thin layer of a water immiscible organic solvent immobilised in the pores of a porous hollow fibre (liquid membrane), and into a microl volume of an acidic aqueous acceptor solution placed inside the lumen of the hollow fibre. In the current paper, this new extraction technique was combined with liquid chromatography-mass spectrometry (LC-MS) for the first time. Carrier mediated LPME was evaluated for several new model drugs (0.01 相似文献