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113.
Sarah Trimpin Ellen D. Inutan 《Journal of the American Society for Mass Spectrometry》2013,24(5):722-732
An astonishingly simple new method to produce gas-phase ions of small molecules as well as proteins from the solid state under cold vacuum conditions is described. This matrix assisted ionization vacuum (MAIV) mass spectrometry (MS) method produces multiply charged ions similar to those that typify electrospray ionization (ESI) and uses sample preparation methods that are nearly identical to matrix-assisted laser desorption/ionization (MALDI). Unlike these established methods, MAIV does not require a laser or voltage for ionization, and unlike the recently introduced matrix assisted ionization inlet method, does not require added heat. MAIV-MS requires only introduction of a crystalline mixture of the analyte incorporated with a suitable small molecule matrix compound such as 3-nitrobenzonitrile directly to the vacuum of the mass spectrometer. Vacuum intermediate pressure MALDI sources and modified ESI sources successfully produce ions for analysis by MS with this method. As in ESI-MS, ion formation is continuous and, without a laser, little chemical background is observed. MAIV, operating from a surface offers the possibility of significantly improved sensitivity relative to atmospheric pressure ionization because ions are produced in the vacuum region of the mass spectrometer eliminating losses associated with ion transfer from atmospheric pressure to vacuum. Mechanistic aspects and potential applications for this new ionization method are discussed. 相似文献
114.
J. Sarah Caygill Stuart D. Collyer Joanne L. Holmes Frank Davis Séamus P. J. Higson 《Electroanalysis》2013,25(11):2445-2452
We describe the use of cobalt phthalocyanine as a mediator to improve the sensitivity for the electrochemical detection of TNT. Commercial screen‐printed electrodes containing cobalt phthalocyanine were employed for determination of TNT. Improved sensitivities compared to screen‐printed carbon electrodes without phthalocyanine were observed, current response for cyclic voltammetric measurements at modified electrodes being at least double that of unmodified electrodes. A synergistic effect between oxygen and TNT reduction was also observed. Correlation between TNT concentrations and sensor output was observed between 0–200 µM TNT. Initial proof‐of‐concept experiments combining electrochemical determinations, with the use of an air‐sampling cyclone, are also reported. 相似文献
115.
Lewis Couchman Sarah L. Belsey Simon A. Handley Robert J. Flanagan 《Analytical and bioanalytical chemistry》2013,405(29):9455-9466
Therapeutic drug monitoring (TDM) requires timely results in order to be clinically helpful. Such assays, when carried out using mass spectrometry-based methods, typically involve a batched sample approach with multipoint calibration. Isotopic internal calibration offers the possibility of open-access mass spectrometric analysis with consequent shortening of turnaround times. We measured plasma clozapine and N-desmethylclozapine (norclozapine) concentrations in (1) external quality assessment (EQA) samples (N?=?22) and (2) patient samples (N?=?100) using liquid chromatography-tandem mass spectrometry with isotopic internal calibration (ICAL-LC-MS/MS). Analyte concentrations were calculated from graphs of the response of three internal calibrators (clozapine-D4, norclozapine-D8, and clozapine-D8) against concentration. Precision (% RSD) and accuracy (% nominal concentrations) for the ICAL-LC-MS/MS method were <5 % and 104–112 %, respectively for both analytes. There was excellent agreement with consensus mean and with ‘spiked’ values on analysis of the EQA samples (R 2?=?0.98 and 0.97, respectively, inclusive of clozapine and norclozapine results). In the patient samples, comparison against traditionally calibrated HPLC-UV and LC-MS/MS methods showed excellent agreement (R 2?=?0.97 or better) with small albeit significant mean differences (<0.041 and <0.042 mg/L for clozapine and norclozapine, respectively). These differences probably reflect discrepancies in the in-house preparation of calibrators and/or interference in the UV method. Internal calibration offers a novel and attractive alternative to traditionally calibrated batch analysis in analytical toxicology. The method described has been validated for use in the high-throughput TDM of clozapine and norclozapine, and allows for (1) same-day reporting of results and (2) significant cost savings. Figure
A typical internal calibration curve produced using three different isotopically-labelled analogues of clozapine and norclozapine (clozapine-D4, norclozapine-D8 and clozapine-D8) and interpolation of the clozapine and norclozapine concentrations from an extracted patient sample (calculated clozapine and norclozapine 0.47 and 0.31 mg/L, respectively) 相似文献
116.
Sarah J. R. Staton Josemar A. Castillo Thomas J. Taylor Pierre Herckes Mark A. Hayes 《Analytical and bioanalytical chemistry》2013,405(1):351-357
A substantial portion of the atmospheric particle budget is of biological origin (human and animal dander, plant and insect debris, etc.). These bioaerosols can be considered information-rich packets of biochemical data specific to the organism of origin. In this study, bioaerosol samples from various indoor environments were analyzed to create identifiable patterns attributable to a source level of occupation. Air samples were collected from environments representative of human high-traffic- and low-traffic indoor spaces along with direct human skin sampling. In all settings, total suspended particulate matter was collected and the total aerosol protein concentration ranged from 0.03 to 1.2 μg/m3. High performance liquid chromatography was chosen as a standard analysis technique for the examination of aqueous aerosol extracts to distinguish signatures of occupation compared to environmental background. The results of this study suggest that bioaerosol “fingerprinting” is possible with the two test environments being distinguishable at a 97 % confidence interval. Figure
Generalized schematic of human debris-based occupation detection. The various human occupation-related aerosolized material are collected via the filtration assembly along with other non-related aerosolized material. The collected material was then analyzed for total protein concentration as well as coarsely separated to generated unique pattern profiles. These profiles are information-rich enough to identify human occupation in an indoor space 相似文献
117.
Sarah A. Hackenmueller 《合成通讯》2013,43(10):1439-1446
Thyroid hormones undergo extensive metabolism to regulate hormone activity. A labeled thyroid hormone would be useful to track hormone metabolism through various pathways. While radiolabeled thyroid hormones have been synthesized and used for in vivo studies, a stable isotope labeled form of thyroid hormone is required for studying thyroid hormone metabolism by LC-MS/MS, an analytical technique that has certain advantages without the complications of radioactivity. Here we report the synthesis of 13C9-15N-T2 and 13C9-15N-T4, two labeled thyroid hormone derivatives suitable for in vivo LC-MS/MS studies. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
118.
Daniel R. Zuidema Sarah L. Williams Katherine J. Wert Karin J. Bosma Abigail L. Smith Robert C. Mebane 《合成通讯》2013,43(19):2927-2931
Aryl ketones are readily deoxygenated to their corresponding aryl alkanes upon treatment with Raney nickel catalyst in boiling 2-propanol.
119.
Hiromu Kurosaki April A. Tucker Sarah E. Iden Shirley M. Sexton Benito D. Gonzalez Govind R. Rao 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(2):1017-1022
Routine monitoring of urine is an effective way to detect occupational intake of radioactive material. Historically, determinations of uranium isotopic ratios have been performed by radiochemical separation followed by alpha spectrometry. With recent advancements in technology, inductively coupled plasma-mass spectrometry (ICP-MS) has become widely available for the determination of trace metals as well as radioactive nuclides with long half-lives, such as 238U in urine. Furthermore, ICP-MS measurements of 238U do not require radiochemical separation since the number of atoms in the sample is determined instead of the number of alpha particles emitted. However, this method does not provide good sensitivity for the determination of 235U due to its shorter half-life. An improved procedure using pre-concentration of uranium and determination by ICP-MS decreases the detection limit by a factor of ten or greater with only slight increase in total analysis time. The method also has the capability of accurately determining the isotopic ratio of the sample, which is very important in cases where enriched or depleted uranium is involved. 相似文献
120.
Rikard Westbom Sarah Josefsson Lennart Mathiasson Erland Björklund 《International journal of environmental analytical chemistry》2013,93(4):259-274
A method for studying PCB desorption behaviour from sediments using supercritical fluid extraction (SFE) and pressurized liquid extraction (PLE) is presented. Four sediments were investigated and extracted with supercritical carbon dioxide employing increasingly harsher extraction conditions ranging from 40°C and 12?MPa to 100°C and 36.5?MPa. To ensure quantitative extractions, the remaining SFE residues were also extracted with PLE. Resulting profiles identified at least three different PCB fractions within the four sediments. Furthermore, a distinct fraction was obtained with extraction for 2?h at 40°C and 36.5?MPa. This fraction has previously been found to correlate well with bioavailable fractions. The dependency of this fraction on sediment total organic carbon (TOC) was investigated, both for sediments examined in this study as well as for previously reported values using the same extraction conditions. It was found that TOC does not correlate to selective SFE, which indicates that the use of TOC to predict bioavailability is questionable. 相似文献