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PubMedDate not supplied

Normalization of priming solution ionized calcium concentration improves hemodynamic stability of neonates receiving venovenous ECMO.

The authors' objectives in this investigation were: 1) to prospectively determine whether a normocalcemic priming solution would result in elimination of hypocalcemia after the initiation of extracorporeal membrane oxygenation (ECMO); 2) to investigate whether normocalcemia would result in improvements in the patient's hemodynamics during the initiation of ECMO; and 3) to further define the relationship between ionized calcium measurements and total calcium, serum total protein, serum albumin, and total magnesium. This was a prospective study done in our neonatal intensive care unit, and included nine neonatal patients placed on ECMO for cardiopulmonary support. The bypass circuit was primed in the standardized manner with 100 mg calcium chloride. Circuit ionized calcium measurements were performed, and additional calcium chloride was added to normalize the ionized calcium in the priming solution. Ionized calcium was measured from the circuit and the patient before the initiation of ECMO, and then again from the patient 5, 10, 15, 30, 60, 120, and 240 minutes after the initiation of ECMO. The patients' mean arterial pressure was measured simultaneously with each ionized calcium measurement. Ionized calcium, serum total calcium, total protein, serum albumin, and total magnesium were measured from blood samples simultaneously collected four times daily. There was no significant change in the ionized calcium measured in the patients after the initiation of ECMO. There was, however, a significant increase in blood pressure 5 min after the initiation of ECMO (62 +/- 7 mmHg vs 53 +/- 6 mmHg, p = 0.01). Thereafter, there was no difference in blood pressure measured when compared with pre ECMO values. A poor correlation was demonstrated between ionized calcium and total calcium (r2 = 0.35), serum total protein (r2 = 0.26), serum albumin (r2 = 0.27), and total magnesium (r2 = 0.05). On the basis of the authors' data, the initiation of ECMO with a normocalcemic prime results in a minimal change in patient ionized calcium and resolution of the hypotension previously observed. In addition, there was poor correction between ionized calcium, total calcium, and other indirect measures of ionized calcium. Ionized calcium measurements are critical for patient hemodynamic stability before bypass and should be normalized in both the patient and priming solution before the initiation of bypass.

Blood Pressure↗
PubMed1984

Drug permeation through human skin II: Permeability of ionizable compounds.

The aim of this study was to establish whether ionized as well as un-ionized forms of certain 4-oxo-4H-1-benzopyran-2-carboxylic acids (chromone-2-carboxylic acids) with pKa values less than 2 permeated through excised human skin and, if so, to determine the permeability coefficients of the permeating species. The permeation properties of four carboxylic acids were studied as a function of concentration over the pH range 5-7 at 37 degrees C with plexiglass diffusion cells. Plots of J/CA- (the total flux due to un-ionized and ionized species obtained under steady-state conditions per unit concentration of ionized drug in the donor compartment) against CH3O+ resulted in straight-line relationships. The intercepts of these plots were shown to equal PA-, whereas the slopes multiplied by the Ka values of the compounds equalled PHA, the permeability coefficients of the ionized and un-ionized species, respectively. With all four compounds, both species were found to permeate skin, although the permeability coefficients of the un-ionized species were approximately 10(4) greater than those for the ionized species. It was demonstrated that the relative contributions of the ionized and un-ionized species to the total flux, as well as the total flux, vary significantly, depending on the pH of the drug solution in the donor cell. This may provide a means of controlling the flux of these and similar compounds through human skin.

Chromatography, High Pressure Liquid↗
PubMed2001

The effects of heparin anticoagulants and fill volume in blood gas syringes on ionized calcium and magnesium measurements.

We studied the effects of several heparin anticoagulants on ionized calcium and ionized magnesium measurements. Venous blood from 24 healthy donors was drawn into 20-ml syringes without an anticoagulant, and immediately analyzed for control results. They were then transferred to completely fill and half-fill each of four brands of syringes, and an evacuated non-anticoagulated blood-collection tube. All were analyzed for ionized calcium and magnesium. In some cases, either saline or a Ca/Mg solution was added to increase the range of concentrations. The final concentrations ranged from 0.94 to 2.09 (ionized calcium) and from 0.41 to 1.06 mmol/l (ionized magnesium). In full syringes, mean changes in ionized calcium or magnesium were <0.01 mmol/l over a range of concentrations usually encountered. The only definite effect was noted in half-full Martell syringes, where ionized calcium was lower by 0.028 mmol/l. At very high ionized calcium concentrations (>1.95 mmol/l) and ionized magnesium concentrations (>0.95 mmol/l), a few changes were noted of little clinical significance. We conclude that all the syringes evaluated have no clinically significant effects on ionized calcium or ionized magnesium concentrations when filled to capacity. When half-full, a few changes of marginal clinical significance were noted. All these effects were less than observed in serum, which is apparently affected by sample processing and/or clotting.

Anticoagulants↗
PubMed2005

Probing the shape and stereochemistry of molecular orbitals in locally flexible aromatic chains: a penning ionization electron spectroscopy and Green's function study of the electronic structure of biphenyl.

We report on the results of an exhaustive study of the interplay between the valence electronic structure, the topology and reactivity of orbitals, and the molecular structure of biphenyl by means of Penning ionization electron spectroscopy in the gas phase upon collision with metastable He*(2(3)S) atoms. The measurements are compared with one-particle Green's function calculations of one-electron and shake-up valence ionization spectra employing the third-order algebraic diagrammatic construction scheme [ADC(3)]. Penning ionization intensities are also analyzed by means of the exterior electron-density model and comparison with photoelectron spectra: in contrast with the lines originating from sigma orbitals, ionization lines belonging to the pi-band system have large Penning ionization cross sections due to their greater extent outside the molecular van der Waals surface. The involved chemi-ionization processes are further experimentally investigated using collision-energy-resolved Penning ionization electron spectroscopy. The cross sections of pi-ionization bands exhibit a markedly negative collision-energy dependence and indicate that the interaction potential that prevails between the molecule and the He*(2(3)S) atom is strongly attractive in the pi-orbital region. On the other hand, the partial ionization cross sections pertaining to sigma-ionization channels are characterized by more limited collision-energy dependencies, as a consequence of rather repulsive interactions within the sigma-orbital region. A comparison of ADC(3) simulations with the Penning ionization electron spectra and UV photoelectron spectra measured by Kubota et al. [Chem. Phys. Lett. 1980, 74, 409] on thin films of biphenyl deposited at 170 and 109 K on copper demonstrates that biphenyl molecules lying at the surface of polycrystalline layers adopt predominantly a planar configuration, whereas within an amorphous sample most molecules have twisted structures similar to those prevailing in the gas phase.

Journal Article↗
PubMed1998

Conduction-band-edge ionization thresholds of DNA components in aqueous solution.

Numerous investigations have focused on DNA damage induced by ionizing radiation; however, photoionization threshold energies of nucleic acid components in aqueous solution are not known. Herein, data from gas-phase photoelectron experiments have been combined with results from self-consistent field and post-self-consistent field molecular orbital calculations and with theoretical Gibbs free energies of hydration to describe aqueous ionization energies of 2'-deoxythymidine 5'-phosphate (5'-dTMP-) and 2'-deoxycytidine 5'-phosphate (5'-dCMP-). For the test molecules, indole and tryptophan, this approach yields aqueous ionization energies (4.46 and 4.58 eV, respectively) in agreement with experimental values (4. 35 and 4.45 eV). When uridine and 2'-deoxythymidine ionization energies are evaluated, the results agree with recent data from 193-nm laser measurements indicating that uridine ionization occurs via a one-photon event. For 5'-dCMP- and 5'-dTMP-, a comparison of aqueous ionization energies with gas-phase ionization potentials (IPs) indicates that hydration alters the relative energies of ionization events. In the gas phase, phosphate vertical IPs are approximately 1.3 eV smaller than base IPs. In aqueous solution, the base and phosphate ionization energies are more similar, and only differ by approximately 0.5 eV. For 5'-dCMP- and 5'-dTMP-, the increased favorableness of base ionization, which accompanies hydration, is consistent with experimental data indicating that, at 77 K in aqueous perchlorate glasses, the primary photoionization pathway involves base ionization followed by deprotonation.

Chemical Phenomena↗
PubMed1998

Serum ionized versus total magnesium in patients with intestinal or liver disease.

In serum, magnesium exists in three fractions: protein-bound, complex-bound and free ionized form. Only the free ionized fraction is biologically active. Until recently, only the measurement of serum total magnesium has been in clinical use. Now, commercially available instruments using new ion-selective electrodes for Mg++ have made possible the reliable measurement of serum ionized magnesium in clinical practice. For the measurement of serum ionized magnesium we used a magnesium-selective electrode installed in a six-channel electrolyte analyzer. We compared the use of ionized versus total magnesium measurement in 52 patients with intestinal disease, 54 with liver disease, and in 75 healthy control subjects. In the patients with alcoholic liver disease both serum ionized and total magnesium were lower, and in those with inflammatory bowel disease slightly higher than in control subjects. The correlation coefficient between serum ionized and total magnesium was r=0.87 (p<0.001) in the patients, and r=0.75 (p<0.001) in the controls. In the patient group the fraction of ionized magnesium in the total was negatively related to the serum albumin level (r=-0.41, p<0.001). Serum total magnesium was below the reference range in 30 out of 150 measurements, serum ionized magnesium in only 9 out of 150 measurements, respectively. Thus, 21 cases with low total but normal ionized magnesium (two thirds of hypomagnesemia according to serum total magnesium) were false positive. Total magnesium measurement may overestimate the incidence of hypomagnesemia when significant hypoalbuminemia is present. Measurement of serum ionized magnesium instead of total magnesium may therefore be of advantage in evaluating patients with hypoalbuminemia and when hypomagnesemia is expected.

Adolescent↗
PubMed1992

[The ionized calcium in the blood of domestic chickens: dependence on age and sex].

In the present study concentration of ionized calcium and the correlation between total and ionized calcium in blood of domestic fowl and its dependence on age and sex were investigated. Furthermore a possible influence of blood sampling procedure on the measured values was assessed. Leghorn chickens of either sex, aged 3, 9, 25, and 80 weeks, respectively, were used. Blood sampling was performed by vein-puncture and indwelling catheters, respectively, of both ulnaris vein and artery of animals which had been fasting for 12 hours. Determinations of ionized calcium concentration was carried out by use of an ion-selective electrode (ICA1), and of total calcium concentration in plasma using atomic absorption, respectively. After attainment of sexual maturity total calcium in roosters rose from 2.73 to 2.85 mmol/l, whereas ionized calcium fell from 1.45 to 1.40 mmol/l and per cent fraction of ionized/total calcium (extent of ionization) from 53.1 to 49.1%, respectively. After attainment of sexual maturity in hens, the content of total calcium in venous blood rose from 2.78 to 5.78 mmol/l, and of ionized calcium from 1.45 to 1.59 mmol/l, respectively, whereas the extent of ionization was significantly reduced from 52.2 to 27.1%. On comparison of the vein-puncture and indwelling catheter technique a marked influence of the blood sampling procedure on calcium concentrations measured in blood of chicken became evident. On attainment of sexual maturity both the arterial and the venous blood (sampled from indwelling catheters) of hens showed levels of ionized calcium about 8% higher as compared to roosters. The extent of ionization amounted to 39% in sexually mature females as opposed to 51% in males. Concentrations of calcium ions in venous blood averaged 0.07 to 0.08 mmol/l higher compared to arterial blood in either sex. Concentration of ionized calcium did not exhibit any correlation to total calcium in adult animals. However, the concentration of ionized calcium was inversely correlated to blood pH.

Age Factors↗
PubMed1990

Failure of pH to predict ionized calcium percentage in healthy horses.

Blood, serum, and plasma total calcium concentrations and plasma and serum ionized calcium concentrations were anaerobically determined by use of a calcium-specific electrode for samples obtained from 39 healthy horses. Mean (+/- SD) serum ionized calcium concentration was 6.6 +/- 0.3 mg/dl (1.6 +/- 0.1 mmol/L) and the mean serum ionized calcium percentage was 58.2 +/- 3.4%. Serum ionized calcium percentage was not significantly correlated with serum pH. Plasma ionized calcium percentage was weakly correlated with plasma pH (r = -0.480; P less than or equal to 0.05). Ionized calcium concentration was determined in serum samples manipulated in vitro by additions of 1 to 80 microliters of 0.1N hydrochloric acid or sodium hydroxide to yield 6 to 10 pH values between 6.8 and 8.2. In all horses, the relationship between serum ionized calcium percentage and serum pH at these pH values was then examined by use of a repeated-measures multiple regression analysis. Correlations between serum ionized calcium percentage and adjusted serum pH value for each horse were highly significant (P less than or equal to 0.05); however, analysis of pooled data from all horses indicated that a statistically significant relationship between serum pH and ionized calcium percentage did not exist. Lack of a significant relationship between these variables was most likely attributable to heterogeneity of variance of ionized calcium percentage among horses, reflecting variation in undefined biochemical constituents of serum that affect the equilibrium of calcium binding. When it is essential to evaluate the calcium status of a horse, direct measurement of serum ionized calcium concentration is recommended.

Analysis of Variance↗
PubMed1998

Ionized and total magnesium concentrations in blood from dogs with naturally acquired parvoviral enteritis.

OBJECTIVE: To determine whether pretreatment total and ionized blood magnesium concentrations were associated with outcome for dogs with parvoviral enteritis and whether ionized magnesium concentration was related to total magnesium concentration or other laboratory values. DESIGN: Prospective cohort study. ANIMALS: 61 healthy dogs and 72 dogs with parvoviral enteritis. PROCEDURE: Total, ionized, and pH-normalized ionized magnesium concentrations, ionized and pH-normalized ionized calcium concentrations, pH, sodium and potassium concentrations, and Hct were measured prior to treatment. chi 2 Analyses were used to test for associations between outcome and age and between outcome and treatment with antiendotoxin antibody. Pearson's correlation coefficients were calculated to determine whether ionized magnesium concentration was linearly associated with other laboratory values. RESULTS: Total and ionized magnesium concentrations were not significantly different between healthy dogs and dogs with parvoviral enteritis or between dogs surviving and those not surviving parvoviral enteritis. The only laboratory value strongly correlated with ionized magnesium concentration was pH-normalized ionized magnesium concentration. Of the factors tested, none were significantly associated with outcome, except that dogs 16 weeks old or less treated with antiendotoxin antibody were significantly more likely to die than were dogs 16 weeks old or less that were not treated with antiendotoxin antibody. CLINICAL IMPLICATIONS: Total and ionized blood magnesium concentrations cannot be used to consistently predict outcome for dogs with parvoviral enteritis. Antiendotoxin antibody should be used with caution in dogs 16 weeks old or less.

Age Factors↗
PubMed2006

Factors influencing the electrospray intrasource separation and selective ionization of glycerophospholipids.

The external electric field induces a separation of cations from negative electrolyte ions in the infusate while differential ionization of molecular species that possess differential electrical propensities can be induced in either the positive- or negative-ion mode during the electrospray ionization process. These physical and electrical processes that occur in the electrospray ion source have been used to selectively ionize lipid classes possessing different electrical propensities that are now known as "intrasource separation and selective ionization". However, the chemical principles underlying charge-dependent alterations in ionization efficiencies responsible for the selective ionization of lipid classes are not known with certainty. Herein, we examined the multiple factors that contribute to intrasource separation and selective ionization of lipid classes under optimal instrumental conditions. We demonstrated that many different lipid classes could be selectively ionized in the ion source and that intrasource resolution of distinct molecular constituents was independent of lipid concentration, flow rate, and residual ions under most experimental conditions. Moreover, the presence of alkaline conditions facilitates the selective ionization of many lipid classes through a mechanism independent of the design of the ESI ion source. Collectively, this study provides an empirical foundation for understanding the chemical mechanisms underlying intrasource separation and selective ionization of lipid classes that can potentially be used for global analysis of cellular lipidomes without the need for chromatographic separation.

Algorithms↗
PubMed2006

Enhancing electrospray ionization efficiency of peptides by derivatization.

With the advent of electrospray ionization mass spectrometry, the world was given a new way to look at complex peptide mixtures. Identification of proteins via their signature peptides requires ionization of a representative portion of the peptides derived from proteins by proteolysis. Unfortunately, matrix effects prohibited electrospray ionization of many peptides. This paper describes the development of a new labeling reagent that simultaneously adds a permanent positive charge to peptides and increases their hydrophobicity to enhance their ionization efficiency. The labeling agent is preactivated with N-hydroxysuccinimide to react with primary amines to form a peptide bond. In the most dramatic case, ionization efficiency of the peptide ADRDQYELLCLDNTRKPVDEYK increased 500-fold after derivatization as opposed to other peptides where ionization efficiency was impacted little. Ionization efficiency of peptides was enhanced roughly 10-fold in general by derivatization. Peptides of less than 500 Da experienced the greatest increase in ionization efficiency by derivatization. Poor ionization efficiency of native peptides was found to be due more to their inherent structural properties than the matrix in which ionization occurs.

Amino Acid Sequence↗
PubMed2001

[The design and evaluation of horizontal pipe mini-flame atomization and ionization synchronous detector in GC/AAS].

Gas chromatography/atomic absorption spectroscopy(GC/AAS) is a good method for the species analysis of organometallic compounds. But the traditional atomizers are not very suitable for this technology and all of them response only to one kind of signal--the concentration of the metallic atoms of the ground state. They can not give any information about the organic group of organometallic compounds and organic compounds which coexist with the former. For GC/AAS we want to design and manufacture a new kind of detector which is much more sensitive and has a much smaller dead volume and will sensitively and synchronously response to the atomization signal of organometallic compound and ionization signal of organic compound. The authors have noticed that the atomization of organometallic compound and ionization of organic compound have been existing in the same hydrogen flame. The question is how to gain and exchange and output the two signals which are completely different in characters. For this purpose we designed and manufactured a new type of horizontal pipe mini-flame atomization and ionization synchronous detector. The key part is a T type glass tube (80 mm x 13 mm x 10 mm i.d.) which covers horizontally on the jet of the mini-flame atomizer and a long pipe stainless steel collector (70 mm x 9.5 mm o.d. x 9 mm i.d.) is tightly inserted in the tube. The light beam of the hollow cathode lamp passes through the hydrogen flame along the axial center of the glass tube and the ground state metallic atoms in the flame diffuses to both ends of the tube along the axial center of the glass tube too. This process enriches the depth of the light absorption and then increases the sensitivity of atomization. At the same time the long pipe collector can enrich the collection efficiency of the ionization and increases the sensitivity and widens the linear range. So the detector can synchronously and sensitively detect the organometallic and organic compounds. The detection limit for atomization of the organometallic compound(diethylmercury) is 2.5 x 10(-11) g.s-1 and for ionization of the organic compound (benzene) is 1.0 x 10(-11) g.s-1. The linear range is 7.0 x 10(2) for atomization of diethylmercury (r = 0.9989) and 2.5 x 10(5) for ionization of benzene (r = 0.9992). The selectivity of the detector to the organic solvent under the optimum operating condition of atomization is 10(4)-10(7). The relative standard deviation (RSD, n = 11) of the peak area in the optimum operating conditions of atomization for the organometallic compound (diethylmercury) and of ionization for the organic compound (benzene) is 1.8% and 1.5% respectively. Under the same operating condition, the atomization and the ionization can not reach the optimum performance at the same time. If the atomization is in the optimum performance state, the performance for ionization is like a chromatographic thermal conductivity detector (TCD). The optimum performance of the atomization and ionization can be quickly adjusted by changing the flow rates of the corresponding gases such as H2, N2 and air.

Benzene↗
PubMed1997

Pressure-dependent ionization of Tyr 9 in glutathione S-transferase A1-1: contribution of the C-terminal helix to a "soft" active site.

The glutathione S-transferase (GST) isozyme A1-1 contains at its active site a catalytic tyrosine, Tyr9, which hydrogen bonds to, and stabilizes, the thiolate form of glutathione, GS-. In the substrate-free GST A1-1, the Tyr 9 has an unusually low pKa, approximately 8.2, for which the ionization to tyrosinate is monitored conveniently by UV and fluorescence spectroscopy in the tryptophan-free mutant, W21F. In addition, a short alpha-helix, residues 208-222, provides part of the GSH and hydrophobic ligand binding sites, and the helix becomes "disordered" in the absence of ligands. Here, hydrostatic pressure has been used to probe the conformational dynamics of the C-terminal helix, which are apparently linked to Tyr 9 ionization. The extent of ionization of Tyr 9 at pH 7.6 is increased dramatically at low pressures (p1/2 = 0.52 kbar), based on fluorescence titration of Tyr 9. The mutant protein W21F:Y9F exhibits no changes in tyrosine fluorescence up to 1.2 kbar; pressure specifically ionizes Tyr 9. The volume change, delta V, for the pressure-dependent ionization of Tyr 9 at pH 7.6, 19 degrees C, was -33 +/- 3 mL/mol. In contrast, N-acetyl tyrosine exhibits a delta V for deprotonation of -11 +/- 1 mL/mol, beginning from the same extent of initial ionization, pH 9.5. The pressure-dependent ionization is completely reversible for both Tyr 9 and N-acetyl tyrosine. Addition of S-methyl GSH converted the "soft" active site to a noncompressible site that exhibited negligible pressure-dependent ionization of Tyr 9 below 0.8 kbar. In addition, Phe 220 forms part of an "aromatic cluster" with Tyr 9 and Phe 10, and interactions among these residues were hypothesized to control the order of the C-terminal helix. The amino acid substitutions F220Y, F2201, and F220L afford proteins that undergo pressure-dependent ionization of Tyr 9 with delta V values of 31 +/- 2 mL/mol, 43 +/- 3 mL/mol, and 29 +/- 2 mL/mol, respectively. The p1/2 values for Tyr 9 ionization were 0.61 kbar, 0.41 kbar, and 0.46 kbar for F220Y, F220I, and F220L, respectively. Together, the results suggest that the C-terminal helix is conformationally heterogeneous in the absence of ligands. The conformations differ little in free energy, but they are significantly different in volume, and mutations at Phe 220 control the conformational distribution.

Binding Sites↗
PubMed1996

Fetal ionized magnesium levels parallel maternal levels during magnesium sulfate therapy for preeclampsia.

OBJECTIVE: Little is known about ion regulation in fetuses. Our aim was to determine the effects of magnesium sulfate therapy on ionized (bioactive) magnesium in the cord blood of pregnancies complicated by preeclampsia. STUDY DESIGN: Seventy-four pregnant women were studied (37 preeclamptic and 37 controls matched for maternal age, gravidity, and gestational age). The preeclamptic women received intravenous magnesium sulfate 6 gm load followed by 2 gm/hour for > or = 4 hours; controls were not preeclamptic and received no magnesium. Maternal venous and fetal cord blood samples were obtained from study and control patients and were analyzed for sodium, potassium, total magnesium, ionized magnesium, total calcium, and ionized calcium. Comparisons between the groups were made and analyzed by the Mann-Whitney U test. RESULTS: There were no significant differences between the treatment and control group cord samples with respect to sodium or potassium. However, total magnesium and ionized magnesium were significantly elevated (p < 0.001) in cord samples of the treated group. At the same time ionized calcium and total calcium were reduced. Interestingly, ionized calcium levels were lower in preeclamptic women before magnesium sulfate therapy was begun, whereas total calcium levels were not different. Importantly, there was no difference between maternal and fetal ionized magnesium levels in either treatment or control groups. CONCLUSIONS: In preeclamptic women undergoing magnesium sulfate therapy, ionized magnesium levels in cord blood parallel maternal levels. Before magnesium therapy ionized calcium levels were lower in preeclamptic women than in matched controls. In the presence of elevated magnesium levels ionized calcium appears to be tightly regulated.

Adolescent↗
PubMed2003

Secondary ionization of chemical warfare agent simulants: atmospheric pressure ion mobility time-of-flight mass spectrometry.

For the first time, the use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative ionization sources (electrospray ionization (ESI), secondary electrospray ionization (SESI), and electrical discharge (corona) ionization (CI)) were employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- and gas-phase samples. For liquid-phase samples, ESI was used as the sample introduction and ionization method. For the secondary ionization (SESI, CI, and traditional (63)Ni ionization) of vapor-phase samples, two modes of sample volatilization (heated capillary and thermal desorption chamber) were investigated. Simulant reference materials, which closely mimic the characteristic chemical structures of CWA as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, were used in this study. A mixture of four G/V-type nerve simulants (dimethyl methylphosphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, and 2-(butylamino)ethanethiol) and one S-type vesicant simulant (2-chloroethyl ethyl sulfide) were found in each case (sample ionization and introduction methods) to be clearly resolved using the IM(tof)MS method. In many cases, reduced mobility constants (K(o)) were determined for the first time. Ion mobility drift times, flight times, relative signal intensities, and fragmentation product signatures for each of the CWA simulants are reported for each of the methods investigated.

Journal Article↗
PubMed1999

Differentiation of microorganisms based on pyrolysis-ion trap mass spectrometry using chemical ionization.

The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles.

Fatty Acids↗
PubMed2001

Experimental p(wall) and p(cel) correction factors for ionization chambers in low-energy clinical proton beams.

Current dosimetry protocols for clinical protons using ionization chambers do not take into account ionization chamber-dependent perturbation correction factors. In the present investigation, the relative response of 17 cylindrical ionization chambers was evaluated at three proton beam qualities: at two points in a modulated beam and one point in a non-modulated beam, all with an incident energy of 75 MeV. Thirteen of the ionization chambers had a Farmer-type geometry but consisted of different combinations of wall and central electrode materials. All ionization chambers were calibrated in terms of air kerma as well as in terms of absorbed dose to water in a 60Co beam. The relative response of the ionization chambers was compared with results of Monte Carlo simulations of proton and secondary electron transport in the phantom and the ionization chamber geometry. The results of the measurements for cylindrical ionization chambers show relative perturbation effects that are limited to 0.5-1%, resulting in perturbation correction factors that are larger than unity compared with an NE2571 ionization chamber. The experimental relative wall and total perturbation correction factors agree with Monte Carlo calculated values, indicating that the differences between the responses of different ionization chambers are due to secondary electron effects. This conclusion is supported by the comparison of our results with those from other investigators after re-analysis of their data. The central electrode perturbation correction factor for an aluminium electrode in a Farmer-type geometry was found to be unity within the experimental uncertainties.

Electrons↗
PubMed2003

Development of ionized hypomagnesemia is associated with higher mortality rates.

OBJECTIVE: Previous studies have shown a wide variation in the prevalence of total serum hypomagnesemia in intensive are unit (ICU) patients and in associated mortality rates. As the ionized part of magnesium is the active portion, we sought to define the prevalence of ionized hypomagnesemia in critically ill patients and to evaluate its relationship with organ dysfunction, length of stay, and mortality. DESIGN: Prospective observational study. SETTING: A 31-bed, medical-surgical, university hospital ICU. PATIENTS: A total of 446 consecutive patients admitted to the ICU over a 3-month period. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: The ionized magnesium level (normal value, 0.42-0.59 mmol/L) was measured at admission and then every day until discharge from the ICU. At admission, 18% of patients had ionized hypomagnesemia, 68% had normal ionized magnesium levels, and 14% had ionized hypermagnesemia. There was no significant difference in the length of stay or in the mortality rate between these three groups of patients. Hypomagnesemic patients more frequently had total and ionized hypocalcemia, hypokalemia, and hypoproteinemia. A total of 23 patients developed ionized hypomagnesemia during their ICU stay; these patients had higher Acute Physiology And Chronic Health Evaluation II (14.9 +/- 5.4 vs. 11.0 +/- 6.2) and Sequential Organ Failure Assessment (SOFA; 7.1 +/- 5.4 vs. 3.9 +/- 2.8) scores at admission (p <.01 for both), a higher maximum SOFA score during their ICU stay (10.0 +/- 5.6 vs. 4.4 +/- 3.2, p <.01), a higher prevalence of severe sepsis and septic shock (57 vs. 11%, p <.01), a longer ICU stay (15.4 +/- 15.5 vs. 2.8 +/- 4.7 days, p <.01), and a higher mortality rate (35% vs. 12%, p <.01) than the other patients. The major risk factors for developing hypomagnesemia during the ICU stay were a prolonged ICU stay, treatment with diuretics, and sepsis. CONCLUSION: Development of ionized hypomagnesemia during an ICU stay is associated with a worse prognosis. It is often associated with the use of diuretics and the development of sepsis. Monitoring of ionized magnesium levels may have prognostic, and perhaps therapeutic, implications.

APACHE↗