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1.
Sci Justice ; 55(1): 18-26, 2015 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-25577003

RESUMEN

This study presents a dataset, derived from the analysis of 162 bottled and canned beers from around the globe, which may be used for comparison with suspected counterfeit or substitute products. The data comprise δ2H and δ18O compositions of the whole beer and δ13C compositions of the dry residue (mostly sugar) together with the concentrations of five anions (F, Cl, NO3, SO4, PO4) and seven cations (Ca, K, Mg, SiO2, V, Mn, Sr). A strong correlation, consistent with natural waters but offset from the Global Meteoric Water Line, was observed between the δ2H/δ18O composition of the beers. The extent of the offset could be explained by the brewing process and the alcohol and sugars present in the beers. Correlations between inorganic analytes were consistent with the addition of salts in the brewing process. Beers were classified as follows: ale, lager, stout or wheat-beer and the chemical composition was found to be characteristic of the assigned type, with lagers being the most readily classified. A combination of chemical and isotopic data was found to be characteristic of the geographical origin (on a continental scale) and could most easily identify beers from Australasia or Europe. A global map of δ18O data revealed a geo-spatial distribution that mirrored existing maps of the isotopic composition of annual precipitation. This confirmed a commonsense view that local precipitation will be the primary source for the water used in brewing. Using this isoscape (or alcoscape) it may be possible to assess the geographical origins of samples for which genuine comparative samples cannot be obtained.

2.
Food Chem ; 170: 241-8, 2015 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-25306341

RESUMEN

This research has explored the potential of stable isotope and trace metal profiles to distinguish Australian prawns from prawns imported from neighbouring Asian countries. Australian prawns were collected mostly from the Brisbane area. Strong differences in Australian vs. imported prawns were evident from both the isotope and trace element data, with the differences most likely occurring because imported prawns are typically reared in aquaculture facilities and frozen prior to sale in Australia. The aquaculture origins are characterised by comparatively; low δHVSMOW, δ(13)CVPDB values, low concentrations of arsenic, zinc and potassium, and high water contents (>80%). Relatively high arsenic and cadmium contents were found within Australian prawns, but the concentrations did not exceed local human health guidelines.


Asunto(s)
Isótopos/análisis , Mariscos/análisis , Oligoelementos/análisis , Animales , Australia
3.
Anal Bioanal Chem ; 405(14): 4959-62, 2013 May.
Artículo en Inglés | MEDLINE | ID: mdl-23512187

RESUMEN

A method is described to prepare inexpensive organic reference materials for routine stable isotope work. The method blends isotope-enriched and isotope-depleted materials to match closely international measurement standards. Examples are presented showing how (13)C-enriched and (13)C-depleted glucose were blended to match the isotopic compositions of the international carbon isotope standards, NBS 19 and L-SVEC. Preparation of the blended standards was straightforward, and the prepared solutions proved easy to dispense into tin capsules and easy to combust in a conventional isotope analysis system. The blended materials allow a laboratory to perform a two-point calibration for isotopic composition on a daily basis, with the use of an international reference material recommended for routine quality assurance. The blending method can be applied widely to make isotope standards for other elements and compounds.

4.
Anal Bioanal Chem ; 405(9): 2799-814, 2013 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-23274555

RESUMEN

The need for inter-laboratory comparability is crucial to facilitate the globalisation of scientific networks and the development of international databases to support scientific and criminal investigations. This article considers what lessons can be learned from a series of inter-laboratory comparison exercises organised by the Forensic Isotope Ratio Mass Spectrometry (FIRMS) network in terms of reference materials (RMs), the management of data quality, and technical limitations. The results showed that within-laboratory precision (repeatability) was generally good but between-laboratory accuracy (reproducibility) called for improvements. This review considers how stable isotope laboratories can establish a system of quality control (QC) and quality assurance (QA), emphasising issues of repeatability and reproducibility. For results to be comparable between laboratories, measurements must be traceable to the international δ-scales and, because isotope ratio measurements are reported relative to standards, a key aspect is the correct selection, calibration, and use of international and in-house RMs. The authors identify four principles which promote good laboratory practice. The principle of identical treatment by which samples and RMs are processed in an identical manner and which incorporates three further principles; the principle of identical correction (by which necessary corrections are identified and evenly applied), the principle of identical scaling (by which data are shifted and stretched to the international δ-scales), and the principle of error detection by which QC and QA results are monitored and acted upon. To achieve both good repeatability and good reproducibility it is essential to obtain RMs with internationally agreed δ-values. These RMs will act as the basis for QC and can be used to calibrate further in-house QC RMs tailored to the activities of specific laboratories. In-house QA standards must also be developed to ensure that QC-based calibrations and corrections lead to accurate results for samples. The δ-values assigned to RMs must be recorded and reported with all data. Reference materials must be used to determine what corrections are necessary for measured data. Each analytical sequence of samples must include both QC and QA materials which are subject to identical treatment during measurement and data processing. Results for these materials must be plotted, monitored, and acted upon. Periodically international RMs should be analysed as an in-house proficiency test to demonstrate results are accurate.


Asunto(s)
Isótopos/análisis , Isótopos/normas , Espectrometría de Masas/métodos , Espectrometría de Masas/normas , Humanos , Control de Calidad , Estándares de Referencia , Reproducibilidad de los Resultados
5.
J Anim Sci ; 86(11): 3054-61, 2008 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-18567734

RESUMEN

Two experiments were conducted at the Kansas State University Beef Cattle Research Center to determine the effects of feeding ground flaxseed (flax) during the receiving period on the growth, health, and subsequent finishing performance of heifers. Crossbred heifers (Exp. 1: n = 363, 214 +/- 1 kg of initial BW; Exp. 2: n = 377, 222 +/- 1 kg of initial BW) were purchased during January and April of 2006. Heifers were fed receiving rations based on steam-flaked corn with 0, 2, 4, or 6% ground flax (DM basis) for 56 d. Following the receiving period, cattle in Exp. 1 and 2 were fed steam-flaked corn-based diets for 150 and 147 d, respectively, and then slaughtered. Heifers were implanted 91 and 109 d before slaughter for Exp. 1 and 2, respectively. In Exp. 1, DMI during the receiving period tended to increase linearly (P = 0.09) with increasing flax in the diet. Average daily gain was 1.46, 1.56, 1.58, and 1.61 kg for heifers fed 0, 2, 4, and 6% flax, respectively (linear, P = 0.03). Final BW in Exp. 1 after the finishing period was increased (linear, P = 0.04) with increasing inclusion of flax in the receiving diets. In Exp. 2, growth performance and mortality during the receiving period were not different among treatments (P > 0.12). During the receiving period in Exp. 2, incidence of the first respiratory treatment tended to be greatest (P = 0.09) for heifers fed 4% flax. During the finishing period, DMI were 8.4, 8.4, 8.0, and 8.1 kg/d for 0, 2, 4, and 6% flax, respectively (linear, P = 0.05). In Exp. 2, LM areas were greatest (quadratic, P = 0.04) for cattle fed 2% flax at receiving. In general, feeding flax during the receiving period may have the potential to improve growth performance; however, performance between experiments was variable, and many factors excluding flax feeding may have contributed to this response.


Asunto(s)
Composición Corporal/fisiología , Complejo Respiratorio Bovino/dietoterapia , Dieta/veterinaria , Lino/metabolismo , Estado de Salud , Aumento de Peso/fisiología , Crianza de Animales Domésticos , Animales , Complejo Respiratorio Bovino/mortalidad , Bovinos , Femenino
6.
Rapid Commun Mass Spectrom ; 16(8): 774-84, 2002.
Artículo en Inglés | MEDLINE | ID: mdl-11921262

RESUMEN

A low-temperature coal tar has been fractionated by column chromatography into acetonitrile, pyridine and 1-methyl-2-pyrrolidinone- (NMP) solubles. The tar and its fractions have been examined by pyrolysis-gas chromatography/mass spectrometry (GC/MS). Fractionation by planar chromatography was also carried out for purposes of comparison. Molecular masses of the fractions were estimated by size-exclusion chromatography (SEC), and bulk structural characterisation was carried out by (13)C-NMR and UV-fluorescence spectrometry. SEC showed that the fractions shifted to progressively shorter elution times (higher apparent masses) with diminishing solubility, i.e. from acetonitrile to NMP solubles. UV-fluorescence spectra showed parallel shifts to longer wavelengths and lower fluorescence quantum yields, indicating increasing sizes of aromatic ring systems and increasingly complex molecules. GC/MS analysis of the tar showed alkanes from C10 to C32 and extensive series of alkylated aromatics, phenols, indenes, naphthalenes, phenanthrenes and fluoranthenes. Pyrolysis-GC/MS results for the acetonitrile solubles closely resembled the data for the tar sample, with extensive series of alkylated benzenes, phenols and naphthalenes as well as alkanes from C16 to C28. The pyridine-soluble fraction showed no significant aromatic pyrolysis products and only relatively weak signals for alkanes between C16 and C27. The NMP-soluble fraction showed even less overall signal, with no significant aromatic components and weak signals for alkanes between C21 and C25, even though (13)C-NMR analyses showed that approximately half of the carbon detected was aromatic. The aliphatics are assumed to provide bridging structures between polycyclic aromatic (PCA) ring systems.

7.
J Chromatogr A ; 921(2): 175-85, 2001 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-11471801

RESUMEN

Direct detection of most intact biohopanoids is not possible using conventional GC-MS techniques due to their highly functionalised and amphiphilic nature. Here we report the application of a new reversed-phase high-performance liquid chromatography method for the direct analysis of acetylated, intact bacteriohopanepolyols in solvent extracts of methanotrophic bacteria. Atmospheric pressure chemical ionisation mass spectrometric detection provides structural information relating to the number and types of functional groups present in the four biohopanoids detected: bacteriohopanetetrol, aminobacteriohopanetriol, -tetrol and -pentol. The method should facilitate the assessment of hopanoid composition of both bacteria and environmental samples.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Euryarchaeota/química , Espectrometría de Masas/métodos , Triterpenos/análisis , Presión Atmosférica
8.
Rapid Commun Mass Spectrom ; 15(11): 845-56, 2001.
Artículo en Inglés | MEDLINE | ID: mdl-11382931

RESUMEN

A sample of Baltic amber ( approximately 40 million yrs old) has been extracted using pentane, toluene and 1-methyl-2-pyrrolidinone (NMP). The relationship between solubility characteristics of the extracts in relation to molecular mass and chemical makeup has been investigated. The extracts were first characterised by (13)C-NMR spectrometry, size exclusion chromatography (SEC) and UV-fluorescence spectroscopy. The fractions differed less in terms of chemical structural features than they did in terms of molecular mass. This contrasts markedly with data on fractions of coal-derived liquids, but parallels results from petroleum-derived vacuum residues. In SEC, the toluene soluble/pentane insoluble fraction gave a peak for high mass material at about 67 000 u. Material excluded from the column porosity in this fraction and in NMP solubles eluted between 8 and 11 min, corresponding to polystyrene masses between 200 000 and several million u. A column with a larger pore size distribution was calibrated using polystyrene and polymethylmethacrylate standards with detection by a light-scattering evaporative analyser. The largest polystyrene standard (15.4 million u) eluted at 13.4 min, similar to that of the earliest eluting amber-derived material in the NMP solubles fraction. Results from probe-MS and pyrolysis-GC/MS have been used to confirm the similarity of chemical structures of the three solubility fractions. Broadly, low mass ions appear to correspond to the various monomeric units of structures present in the amber, the higher mass ions to dimer units and the molecular ions to the different combinations of three or more monomeric units. The main monomer groups have been identified in detail, showing a situation very different from that of coal-derived materials, where the sizes of aromatic ring systems increase with molecular size.

9.
J Reprod Med ; 41(7): 497-503, 1996 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-8829062

RESUMEN

OBJECTIVE: To demonstrate, in a university hospital setting, that the introduction of laparoscopically assisted vaginal hysterectomy reduced the need for abdominal hysterectomy and increased resident experience in vaginal surgery. STUDY DESIGN: All hysterectomies performed for benign gynecologic disease during one year, 1993-1994, at the Medical University of South Carolina Hospital, Charleston, after introduction of laparoscopically assisted vaginal hysterectomy were compared to those performed in preceding years, 1990-1993. RESULTS: Prior to 1993, > 70% of hysterectomies at the Medical University of South Carolina Hospital were performed abdominally. With the introduction of laparoscopically assisted vaginal hysterectomy, from a total of 155 hysterectomies performed in 1993-1994, the percentage of hysterectomies performed abdominally decreased to 39 without affecting the overall percentage of traditional vaginal hysterectomies, 29. Since laparoscopic hysterectomies were completed with a significant vaginal component to the operation, the actual resident experience with vaginal hysterectomy increased to 61% of hysterectomies. Straightforward vaginal hysterectomies were performed on patients with higher parity and traditional indications, such as cervical intraepithelial neoplasia and prolapse. Patients who underwent laparoscopically assisted vaginal hysterectomy were not considered candidates for traditional vaginal hysterectomy and had significantly fewer complications and hospital days but did have significantly smaller uteri and greater hospital charges than did patients who underwent abdominal hysterectomy (P < .05). No significant difference was found for length of operating time or blood loss between each method of hysterectomy. CONCLUSION: Laparoscopically assisted vaginal hysterectomy, when used as an alternative to abdominal hysterectomy in patients not considered candidates for vaginal hysterectomy, decreased the need for abdominal hysterectomy, with fewer complications, and shorter hospital stay and increased resident experience with vaginal surgery.


Asunto(s)
Histerectomía Vaginal/estadística & datos numéricos , Histerectomía/estadística & datos numéricos , Laparoscopía/estadística & datos numéricos , Vagina/cirugía , Adulto , Educación Médica , Femenino , Enfermedades de los Genitales Femeninos/epidemiología , Enfermedades de los Genitales Femeninos/cirugía , Neoplasias de los Genitales Femeninos/epidemiología , Neoplasias de los Genitales Femeninos/cirugía , Hospitales Universitarios/estadística & datos numéricos , Humanos , Histerectomía/métodos , Histerectomía Vaginal/métodos , Laparoscopía/métodos , Persona de Mediana Edad , South Carolina/epidemiología
11.
Rapid Commun Mass Spectrom ; 10(14): 1747-57, 1996.
Artículo en Inglés | MEDLINE | ID: mdl-8953778

RESUMEN

Flash pyrolysis/gas chromatography (py/GC) and py/GC/mass spectrometry (MS) have been utilized to characterize the cuticles of invertebrates chemically. Pyrolysis products have been identified and assigned to specific cuticular components. Acetylpyridones, acetamidofuran, 3-acetamido-5-methylfuran and 3-acetamido-(2 and 4)-pyrones are proposed as characteristic pyrolysis markers for chitin. Pyrolysis products displaying ions of m/z 70, 154, 168, 194 are thought to derive from diketopiperazine structures and provide potential markers for proteins and peptides in which proline, alanine, valine, arginine and glycine are the dominant amino acids. These products, constituting specific pyrolysis markers for invertebrate cuticles, may reflect the amino acid composition of their constituent structural proteins. The source of the various pyrolysis products of proteins has been verified by pyrolysis of reference proteins, peptides and amino acid mixtures. The presence of additional pyrolysis products related directly to histidine and catechol moieties is consistent with the chemical structure and composition proposed for arthropod cuticles based on recent work utilizing solid state 13C and 15N nuclear magnetic resonance. This study constitutes the first comprehensive chemical characterization of the pyrolysis products of invertebrate cuticles and provides the basis for future investigations requiring qualitative screening for cross-linked chitin and proteins in modern and fossil cuticles and in materials, e.g. geopolymers, that may be derived from them.


Asunto(s)
Quitina/análisis , Invertebrados/química , Proteínas/análisis , Animales , Fósiles , Liofilización , Cromatografía de Gases y Espectrometría de Masas
12.
J Am Soc Mass Spectrom ; 7(9): 965-71, 1996 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-24203611

RESUMEN

A method is described for the high-performance liquid chromatography (HPLC) mass spectrometry analysis of porphyrin mixtures by using an atmospheric pressure interface, which can operate in two modes: pneumatically assisted elecrrospray and atmospheric pressure chemical ionization (APCI). Optimization of the conditions and evaluation of spectral information has been carried out by using direct injection of free-base and metallo porphyrin standards. The most effective results were obtained using APCI. HPLC-APCI mass spectrometry analysis of the demetallated vanadyl porphyrin fraction from the Triassic Serpiano oil shale has allowed rapid characterization of the distribution; more than 50 significant components are present. The presence of trace amounts of high molecular weight (>C33) cycloalkano porphyrins indicates the occurrence of photic zone anoxia in the ancient water column. This example illustrates the potential of the approach for studies of porphyrin mixtures of environmental or biological significance, which should be applicable to other types of metallo and free-base components that can be separated by HPLC under normal or reversed-phase conditions.

13.
J Prosthet Dent ; 35(2): 192-201, 1976 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-55482

RESUMEN

Removable prostheses were used to determine that esthetics and speech could be improved for patients with permanent unilateral facial paralysis. Esthetics had to be compromised somewhat to obtain the maximum benefit for intelligible speech. This procedure can be beneficial in helping patients who are high surgical risks or for whom surgery, for various reasons, is unacceptable.


Asunto(s)
Parálisis Facial/terapia , Prótesis Maxilofacial , Cara/anatomía & histología , Humanos , Masculino , Persona de Mediana Edad , Cuidados Paliativos , Diseño de Prótesis , Habla
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