A highly sensitive LC-tandem MS assay for the measurement in plasma and in urine of salbutamol administered by nebulization during mechanical ventilation in healthy volunteers.

The new-generation nebulizers are commonly used for the administration of salbutamol in mechanically ventilated patients. The different modes of administration and new devices have not been compared. We developed a liquid chromatography-tandem mass spectrometry method for the determination of concentrations as low as 0.05 ng/mL of salbutamol, corresponding to the desired plasma concentration after inhalation. Salbutamol quantification was performed by reverse-phase HPLC. Analyte quantification was performed by electrospray ionization-triple quadrupole mass spectrometry using selected reaction monitoring detection ESI in the positive mode. The method was validated over concentrations ranging from 0.05 to 100 ng/mL in plasma and from 0.18 to 135 ng/mL in urine. The method is precise, with mean inter-day coefficient of variation (CV%) within 3.1-8.3% in plasma and 1.3-3.9% in urine, as well as accurate. The proposed method was found to reach the required sensitivity for the evaluation of different nebulizers as well as nebulization modes. The present assay was applied to examine whether salbutamol urine levels, normalized with the creatinine levels, correlated with the plasma concentrations. A suitable, convenient and noninvasive method of monitoring patients receiving salbutamol by mechanical ventilation could be implemented. Copyright © 2011 John Wiley & Sons, Ltd.

The development of automated methods for the determination of trace concentrations of carbomate pesticides in water using solid sorbent pre-concentration methods and high performance liquid chromatography /

Several automated reversed-phase HPLC methods have been developed to determine trace concentrations of carbamate pesticides (which are of concern in Ontario environmental samples) in water by utilizing two solid sorbent extraction techniques. One of the methods is known as on-line pre-concentration'. This technique involves passing 100 milliliters of sample water through a 3 cm pre-column, packed with 5 micron ODS sorbent, at flow rates varying from 5-10 mUmin. By the use of a valve apparatus, the HPLC system is then switched to a gradient mobile phase program consisting of acetonitrile and water. The analytes, Propoxur, Carbofuran, Carbaryl, Propham, Captan, Chloropropham, Barban, and Butylate, which are pre-concentrated on the pre-column, are eluted and separated on a 25 cm C-8 analytical column and determined by UV absorption at 220 nm. The total analytical time is 60 minutes, and the pre-column can be used repeatedly for the analysis of as many as thirty samples. The method is highly sensitive as 100 percent of the analytes present in the sample can be injected into the HPLC. No breakthrough of any of the analytes was observed and the minimum detectable concentrations range from 10 to 480 ng/L. The developed method is totally automated for the analysis of one sample. When the above mobile phase is modified with a buffer solution, Aminocarb, Benomyl, and its degradation product, MBC, can also be detected along with the above pesticides with baseline resolution for all of the analytes. The method can also be easily modified to determine Benomyl and MBC both as solute and as particulate matter. By using a commercially available solid phase extraction cartridge, in lieu of a pre-column, for the extraction and concentration of analytes, a completely automated method has been developed with the aid of the Waters Millilab Workstation. Sample water is loaded at 10 mL/min through a cartridge and the concentrated analytes are eluted from the sorbent with acetonitrile. The resulting eluate is blown-down under nitrogen, made up to volume with water, and injected into the HPLC. The total analytical time is 90 minutes. Fifty percent of the analytes present in the sample can be injected into the HPLC, and recoveries for the above eight pesticides ranged from 84 to 93 percent. The minimum detectable concentrations range from 20 to 960 ng/L. The developed method is totally automated for the analysis of up to thirty consecutive samples. The method has proven to be applicable to both purer water samples as well as untreated lake water samples.

Arsenic and germanium determination by hydride generation in the D.C. plasma optical emission spectrometer

Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).

Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

Studies on the insecticide - nematicide-oxamyl and its quantitative determination by gas chromatographic method

Ox amyl , an insecticide/nematicide with the chemical name; methyl ~'. ~·-dimethyl-~-(methylcarbamoyl)oxy-l-thiooxamimidate, and its major degradation compound; oxime or oximino compound, methyl ~',~'-dimethyl-~-hydroxy-l-thiooxamimidate were studied in this work. NMR and mass spectrometry were utilized in the structural studies. An attempt was made to explain the fragmentation patterns of some major peaks in the mass spectra of oxamyl and oxime. A new gas chromatographic method for the detection and determination of submicrogram levels of intact oxamyl using a electron-capture detector was developed. The principle of this method is to produce a derivative which is highly sensitive to an electron-capture detector. The derivative described is dinitrophenyl methylamine( DNPMA ) • Experimental conditions such as pH , reaction temperature , reaction time, the amount of reagent ( Dinitrofluaro benzene) etc. were thoroughly investigated and optimized. This method was successfully applied to the determination of oxamyl residues in tobacco leaves and soil. Throughout this J9D:oject , thin layer chromatography was also used in the separation:and clean up of oxamyl and oxime samples.

The determination of the helium discharge detector response to fixed gases

The Beckman Helium Discharge Detector has been found to be sensitive to the fixed gases oxygen, nitrogen, and hydrogen at detection levels 10-100 times more sensitive than possible with a Bow-Mac Thermal Conductivity Detector. Detection levels o~ approximately 1.9 E-4 ~ v/v oxygen, 3.1 E-4 ~ v/v nitrogen, and 3.0 E-3 ~ v/v hydrogen are estimated. Response of the Helium Discharge Detector was not linear, but is useable for quantitation over limited ranges of concentration using suitably prepared working standards. Cleanliness of the detector discharge electrodes and purity of the helium carrier and discharge gas were found to be critical to the operation of the detector. Higher sensitivities of the Helium Discharge Detector may be possible by the design and installation of a sensitive, solid-state electrometer.

Further characterization and determination of the single amino acid change in the tsI138 reovirus thermosensitive mutant

Many temperature-sensitive mutants have been isolated in early studies of mammalian reovirus. However, the bio- logical properties and nature of the genetic alterations remain incompletely explored for most of these mutants. The mutation harbored by the tsI138 mutant was already assigned to the L3 gene encoding the l1 protein. In the present study, this mu- tant was further studied as a possible tool to establish the role of the putative l1 enzymatic activities in viral multiplication. It was observed that synthesis of viral proteins is only marginally reduced, while it was difficult to recover viral particles at the nonpermissive temperature. A single nucleotide substitution resulting in an amino acid change was found; the position of this amino acid is consistent with a probable defect in assembly of the inner capsid at the nonpermissive temperature.

Spectrophotometric Determination of Chromium(III) with 2-Hydroxybenzaldiminoglycine

A spectrophotometric method employing 2-hydroxybenzaldiminoglycine (HBIG) is proposed for the determination of chromium(III). The results of the determinations are compared with the standard diphenyl carbazide method. The presently developed method is direct, simple, rapid, selective, sensitive and precise.

New Spectrophotometric Methods for the Determination of Nimesulide

Two simple and sensitive spectrophotometric methods (A and B)in the visible region have been developed for the determination of nimesulide in bulk and in dosage forms.Method A is based on the reaction of reduced nimesulide with nitrous acid followed by its coupling with phloroglucinol to yield an yellow colored azo dye with an absorption maximum of 400 nm and method B is based on the reaction of reduced nimesulide with p-dimethylamino benzaldehyde(PDAB) to form an yellow colored chromogen wiht an absorption maximum of 415 nm.When pharmaceutical preparations (Tablets and suspension) were analysed, the results obtained by the proposed methods are in good agreement with the labelled amounts and are comparable with the results obtained by a reported method.recovery in both the method is 98-101 %.

Spectrophotometric Methods for the Determination of Cafotaxime Sodium In Dosage Forms

Two simple and sensitive spectrophotometric methods(A and B) in the visible region have been developed for the determination of cefotaxime sodium (DFTS) in bulk and in dosage forms. Method A is based on the reaction of CFTS with nitrous acid under alkaline conditions to form a stable violet colored chromogen with absorption maximum of 560 nm and method B is based on the reaction of CFTS with1,10-phenanthroline and ferric chloride to form a red colored chromogen with the absorption maximum of 520 mm.The color obeyed Beer’s law in the concentration range of 100-500 µg/ml for method A and 1.6-16 µg/ml for method B, respectively.When pharmaceutical preparations containing CFTS were analysed, the results obtained by the proposed methods are in good agreement with the labeled amounts and are comparable with the results obtained using a UV spectrophotometric method.

Study on the determination of molecular distance in organic dye mixtures using dual beam thermal lens technique

A sensitive method based on the principle of photothermal phenomena to study the energy transfer processes in organic dye mixtures is presented. A dual beam thermal lens method can be very effectively used as an alternate technique to determine the molecular distance between donor and acceptor in fluorescein–rhodamine B mixture using optical parametric oscillator.

Electron Density Determination of Laser Induced Plasma from Polymethyl Methacrylate Using Phaseshift Detection Technique

Irradiation of a Polymethyl methacrylate target using a pulsed Nd-YAG laser causes plasma formation in the vicinity of the target. The refractive index gradient due to the presence of the plasma is probed using phase-shift detection technique. The phase-shift technique is a simple but sensitive technique for the determination of laser ablation threshold of solids. The number density of laser generated plasma above the ablation threshold from Polymethyl methacrylate is calculated as a function of laser fluence. The number density varies from 2×1016 cm-3 to 2×1017 cm-3 in the fluence interval 2.8-13 J · cm-2.

Damage threshold determination of bulk polymer samples using pulsed photothermal deflection technique

Photothermal deflection technique was used for determining the laser damage threshold of polymer samples of teflon (PTFE) and nylon. The experiment was conducted using a Q-switched Nd-YAG laser operating at its fundamental wavelength (1-06μm, pulse width 10 nS FWHM) as irradiation source and a He-Ne laser as the probe beam, along with a position sensitive detector. The damage threshold values determined by photothermal deflection method were in good agreement with those determined by other methods.

Voltammetric Sensors for the Determination of Pharmaceuticals

Electrochemical sensors are increasingly being investigated to perform measurements for single or multiple analytes. Demanded by modern medical diagnosis, advances in microfabrication technology have led to the development of fast, sensitive and selective electrochemical sensors for drug analysis. Electrochemical sensors for the measurement of analytes of interest in clinical chemistry are ideally suited for these applications, due to their high sensitivity and selectivity, simple-to-operate, rapid response time and low-cost. As part of the present investigations eight voltammetric sensors have been fabricated for six drugs such as PAM Chloride, Tamsulosin Hydrochloride, Hesperidin Methyl Chalcone, Guaiphenesin, Cephalexin and Amoxicillin trihydrate. The modification techniques adopted as part of the present work include multiwalled carbon nanotube (MWNT) based modifications, electropolymerization, gold nanoparticle (AuNP) based modifications and platinum nanoparticle (PtNP) based modifications. The thesis is divided into nine chapters

Why language matters: insights and challenges in applying a social determination of health approach in a North-South collaborative research program

Focus on “social determinants of health” provides a welcome alternative to the bio-medical illness paradigm. However, the tendency to concentrate on the influence of “risk factors” related to living and working conditions of individuals, rather than to more broadly examine dynamics of the social processes that affect population health, has triggered critical reaction not only from the Global North but especially from voices the Global South where there is a long history of addressing questions of health equity. In this article, we elaborate on how focusing instead on the language of “social determination of health” has prompted us to attempt to apply a more equity-sensitive approaches to research and related policy and praxis.