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PubMed1996

Plasma ionized magnesium during acute hyperventilation in humans.

1. Respiratory alkalosis accompanies the clinical syndrome of tetany, precipitates cardiac arrhythmias and predisposes to coronary vasoconstriction. Magnesium plays a critical role in the maintenance of membrane function, and magnesium depletion is often associated with cardiac arrhythmias or vasoconstriction. 2. As technology for detecting circulating ionized magnesium (the most interesting form with respect to physiological and biological properties) is now available in the form of new magnesium-selective electrodes, the effect of respiratory alkalosis induced by voluntary overbreathing for 30 min on circulating ionized magnesium was studied in eight healthy subjects. 3. The total plasma magnesium concentration was not modified by hyperventilation. On the contrary, hyperventilation was associated with a significant reduction in the ionized magnesium concentration of 0.05 (0.02-0.15) mmol/l (median and range) and in the free magnesium fraction of 0.06 (0.01-0.19). During hyperventilation the relative intravascular magnesium mass, calculated from changes in total plasma magnesium concentration and haematocrit, decreased significantly. 4. It is concluded that acute overbreathing reduces the circulating ionized magnesium concentration and the intravascular magnesium mass. It is therefore conceivable that extracellular magnesium deficiency is at least a subsidiary cause of the syndrome of tetany and the cardiac complications that are precipitated by hyperventilation.

Acute Disease↗
PubMed1999

Comparison of blood ionized calcium and acid-base variables in samples obtained from different sampling sites in dairy cows.

Ionized calcium (Ca2+) concentrations, pH, blood gas tensions (pCO2 and pO2), base excess (BE), and bicarbonate (HCO3-) concentrations were determined and standard ionized calcium (stCa2+) concentrations were calculated (Ca2+ corrected to pH 7.4) for the blood withdrawn from the jugular vein, the coccygeal vein or coccygeal artery and the milk vein in 29 clinically healthy post-partum dairy cows. The blood withdrawal site had no significant effect on the blood ionized calcium and standard ionized calcium (mean differences among the blood samples varied between 0.01 and 0.05 mmol/l), or on bicarbonate concentrations or base excess. pH, pCO2 and pO2 were significantly lower or higher in samples taken from the coccygeal vein compared to other venous blood samples.

Acid-Base Equilibrium↗
PubMed1996

Signal Transduction and Cellular Responses to Ionizing Radiation.

The current understanding of cellular responses to ionizing radiation fuses traditional radiobiological concepts with recent insight into underlying molecular mechanisms. Cell cycle arrest, induction of specific cascades of genes, and activation of DNA repair mechanisms have been reported after radiation exposure. Of particular importance is the mitogen-activated protein (MAP) kinase signaling pathway, in which the ras and raf oncogenes participate. Both of these genes have been implicated in the cellular resistance to killing by ionizing radiation. Furthermore, regulated NF-gammaB transcriptional activation may be important for the pleiotrophic responses of cells to ionizing radiation. Disruption of this signaling cascade may contribute to the radiation sensitivity syndrome seen in ataxia telangiectasia. In this review, these pathways are consolidated into ionizing radiation signal transduction pathways that lead from the cell membrane/cytosol to the nuclear DNA.

Journal Article↗
PubMed1993

Ionized serum magnesium levels in umbilical cord blood of normal pregnant women at delivery: relationship to calcium, demographics, and birthweight.

Using a novel ion-selective electrode for ionized Mg (IMg2+), we sought to: (1) determine levels and fractions of IMg2+ in umbilical vessels of normal pregnant women: (2) determine their relationships with ionized calcium (ICa2+) levels: (3) determine whether any demographic or clinical parameters affect these levels of divalent cations: and (4) compare levels of IMg2+, total Mg, percent IMg2+, and ICa2+ with sera of normal pregnant and nonpregnant women. We obtained umbilical arterial and venous serum from 38 normal subjects and venous samples from 26 normal pregnant women and 42 nonpregnant women. The mean umbilical venous IMg2+ level (0.51 +/- 0.01 mmol/liter) was significantly greater than the umbilical arterial level (0.48 +/- 0.01 mmol/liter, p < 0.05), and the latter was similar to maternal venous levels (0.48 +/- 0.01 mmol/liter). The maternal venous mean value is 20% less than that found (0.60 +/- 0.005 mmol/liter) in peripheral serum of nonpregnant women. The ionized fractions were significantly (p < 0.01) higher in the umbilical veins than umbilical arteries, and the percent IMg2+ fractions were similar in umbilical arteries and maternal venous blood. IMg2+ levels were lower in multiparous patients and those who received epidural analgesia and higher in patients who had operative vaginal delivery and in Asians. Ionized fractions of Mg in umbilical veins were higher in large for gestational age infants. Our findings provide evidence of a Mg deficiency in pregnancy and suggest that measurement of IMg2+ may have clinical value for diagnosis and therapy of such deficiency.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗
PubMed2004

On the copper oxide neutral cluster distribution in the gas phase: detection through 355 nm and 193 nm multiphoton and 118 nm single photon ionization.

The distribution of neutral copper oxide clusters in the gas phase created by laser ablation is detected and characterized through time-of-flight mass spectroscopy (TOFMS). The neutral copper oxide clusters are ionized by two different approaches: Multiphoton absorption of 355 and 193 nm radiation; and single photon absorption of 118 nm radiation. Based on the observed cluster patterns as a function of experimental conditions (e.g., copper oxide or metal sample, ablation laser power, expansion gas, etc.) and on the width of the TOFMS features, one can uncover the true neutral cluster distribution of CumOn species following laser ablation of the sample. Ablation of a metal sample generates only small neutral CumOn clusters for m less, similar 4 and n approximately 1, 2. Ablation of copper oxide samples generates neutral clusters of the form CumOm (m < or = 4) and CumO(m-1) (m > 4). These clusters are directly detected without fragmentation using single photon, photoionization with 118 nm laser radiation. Using 355 and 193 nm multiphoton ionization, the observed cluster ions are mostly of the form Cu2mOm+ for 4 < or = m < or = 10 (193 nm ionization) and CumO1,2 (355 nm ionization) for copper oxide samples. Neutral cluster fragmentation due to multiphoton processes seems mainly to be of the form CumO(m,m-1) --> CumO(m/2,m/2+1). Neutral cluster growth mechanisms are discussed based on the cluster yield from different samples (e.g., Cu metal, CuO powder, and Cu2O powder).

Journal Article↗
PubMed2004

Mass analyzed threshold ionization spectroscopy of p-fluorostyrene.

Adiabatic ionization energy (AIE) and two-color threshold ion vibrational spectra of p-fluorostyrene have been measured by mass analyzed threshold ionization (MATI) method via three different intermediate levels in the first excited state, vibrationless S1 origin, 42(1)41(1), and 23(1) vibronic levels. Features of the ion vibrational spectra indicates that the geometry of the molecular ion including the conformation of the vinyl chain in the ionic ground state (D0) is almost identical to that of its neutral ground state (S0), and ionization has very little effect on the vibrational potentials of the aromatic ring modes. Comparison of the AIE with the reported value of styrene shows that fluorination at the para position of the aromatic ring has little effect on energy of the electron ejected in ionization process from the styrene chromophore.

Journal Article↗
PubMed2004

Photodissociation and multiphoton dissociative ionization processes in CH(3)S(2)CH(3) at 193 nm studied using velocity-map imaging.

Dissociation and ionization processes in dimethyl disulfide, CH(3)S(2)CH(3), induced by one- or two-photon absorption of 193 nm light, have been studied using velocity-map ion imaging. The analysis of the ion images of the CH(3)S(2) (+), CH(3)S(+), S(2) (+), and S(+) fragments has allowed the characterization of the scattering dynamics of some of the main photolysis and dissociative-ionization processes. In particular, the experiments corroborate the formation of electronically excited SCH(3)((2)A(1)) products in the 193 nm photodissociation of dimethyl disulfide seen in earlier studies, and show that laser ionization provides a very sensitive method for their detection. The data have also allowed determination of the recoil energy and angular distributions of the CH(3)S(2) (+) and CH(3)S(+) products of the two-photon dissociative-ionization of the CH(3)S(2)CH(3) molecule. The measured distributions for these products are consistent with the formation of a transient parent ion which dissociates after a substantial intramolecular rearrangement, possibly yielding the most stable isomeric forms of the fragments, namely CH(2)S(2)H(+) and CH(2)SH(+).

Journal Article↗
PubMed2005

A theoretical study of the gas-phase chemi-ionization reaction between uranium and oxygen atoms.

The U+O chemi-ionization reaction has been investigated by quantum chemical methods. Potential-energy curves have been calculated for several electronic states of UO and UO(+). Comparison with the available spectroscopic and thermodynamic values for these species is reported and a mechanism for the chemi-ionization reaction U+O-->UO(+)+e(-) is proposed. The U+O and Sm+O chemi-ionization reactions are the first two metal-plus-oxidant chemi-ionization reactions to be studied theoretically in this way.

Journal Article↗
PubMed2005

Accurate ab initio predictions of ionization energies of hydrocarbon radicals: CH2, CH3, C2H, C2H3, C2H5, C3H3, and C3H5.

The ionization energies for methylene (CH2), methyl (CH3), ethynyl (C2H), vinyl (C2H3), ethyl (C2H5), propargyl (C3H3), and allyl (C3H5) radicals have been calculated by the wave-function-based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled-cluster level with single and double excitations plus a quasiperturbative triple excitation [CCSD(T)]. When it is appropriate, the zero-point vibrational energy correction, the core-valence electronic correction, the scalar relativistic effect correction, the diagonal Born-Oppenheimer correction, and the high-order correlation correction have also been made in these calculations. The comparison between the computed ionization energy (IE) values and the highly precise experimental IE values determined in previous pulsed field ionization-photoelectron (PFI-PE) studies indicates that the CCSD(T)/CBS method is capable of providing accurate IE predictions for these hydrocarbon radicals achieving error limits well within +/-10 meV. The benchmarking of the CCSD(T)/CBS IE predictions by the PFI-PE experimental results also lends strong support for the conclusion that the CCSD(T)/CBS approach with high-level energy corrections can serve as a valuable alternative for reliable IE determination of radicals, particularly for those radicals with very unfavorable Franck-Condon factors for photoionization transitions near their ionization thresholds.

Journal Article↗
PubMed2005

One-photon mass-analyzed threshold ionization spectroscopy of CH2BrI: extensive bending progression, reduced steric effect, and spin-orbit effect in the cation.

One-photon mass-analyzed threshold ionization (MATI) spectrum of CH2BrI was obtained using coherent vacuum-ultraviolet radiation generated by four-wave difference-frequency mixing in Kr. Unlike CH2ClI investigated previously, a very extensive bending (Br-C-I) progression was observed. Vibrational frequencies of CH2BrI+ were measured from the spectra and the vibrational assignments were made by utilizing frequencies calculated by the density-functional-theory (DFT) method using relativistic effective core potentials with and without the spin-orbit terms. A noticeable spin-orbit effect on the vibrational frequencies was observed from the DFT calculations, even though its influence was not so dramatic as in CH2ClI+. A simple explanation based on the bonding characteristics of the molecular orbitals involved in the ionization is presented to account for the above differences between the MATI spectra of CH2BrI and CH2ClI. The 0-0 band of the CH2BrI spectrum could be identified through the use of combined data from calculations and experiments. The adiabatic ionization energy determined from the position of this band was 9.5944+/-0.0006 eV, which was significantly smaller than the vertical ionization energy reported previously.

Journal Article↗
PubMed2005

A vacuum ultraviolet pulsed field ionization-photoelectron study of cyanogen cation in the energy range of 13.2-15.9 eV.

The vacuum ultraviolet pulsed field ionization-photoelectron and photoionization efficiency spectra of NCCN have been measured in the energy region of 13.25-17.75 eV. The analyses of these spectra have provided accurate ionization energy (IE) values of 13.371+/-0.001, 14.529+/-0.001, 14.770+/-0.001, and 15.516+/-0.001 eV for the formation of NCCN(+) in the X(2)Pi(g), A(2)Sigma(g) (+), B(2)Sigma(u) (+), and C(2)Pi(u) states, respectively. The ionization energy [NCCN(+)(B(2)Sigma(u) (+))] value determined here indicates that the origin of the NCCN(+)(B(2)Sigma(u) (+)) state lies lower in energy by 25 meV than previously reported. A set of spectroscopic parameters for NCCN(+)(X(2)Pi(g)) has been calculated using high level ab initio calculations. The experimental spectra are found to consist of ionizing transitions populating the vibronic levels of NCCN(+), which consist of pure vibronic progressions, combination modes involving the symmetric CN stretch, the CC stretch, and even quanta of the antisymmetric CN stretch, and bending vibrations. These bands are identified with the guidance of the present ab initio calculations.

Journal Article↗
PubMed2006

IR+vacuum ultraviolet (118 nm) nonresonant ionization spectroscopy of methanol monomers and clusters: neutral cluster distribution and size-specific detection of the OH stretch vibrations.

Small methanol clusters are formed by expanding a mixture of methanol vapor seeded in helium and are detected using vacuum UV (vuv) (118 nm) single-photon ionization/linear time-of-flight mass spectrometer (TOFMS). Protonated cluster ions, (CH3OH)(n-1)H+ (n=2-8), formed through intracluster ion-molecule reactions following ionization, essentially correlate to the neutral clusters, (CH3OH)n, in the present study using 118 nm light as the ionization source. Both experimental and Born-Haber calculational results clarify that not enough excess energy is released into protonated cluster ions to initiate further fragmentation in the time scale appropriate for linear TOFMS. Size-specific spectra for (CH3OH)n (n=4 to 8) clusters in the OH stretch fundamental region are recorded by IR+vuv (118 nm) nonresonant ion-dip spectroscopy through the detection chain of IR multiphoton predissociation and subsequent vuv single-photon ionization. The general structures and gross features of these cluster spectra are consistent with previous theoretical calculations. The lowest-energy peak contributed to each cluster spectrum is redshifted with increasing cluster size from n=4 to 8, and limits near approximately 3220 cm(-1) in the heptamer and octamer. Moreover, IR+vuv nonresonant ionization detected spectroscopy is employed to study the OH stretch first overtone of the methanol monomer. The rotational temperature of the clusters is estimated to be at least 50 K based on the simulation of the monomer rotational envelope under clustering conditions.

Journal Article↗
PubMed2006

Electron-impact ionization of helium clusters close to the threshold: appearance energies.

We have investigated the ionization threshold behavior of small helium cluster ions (cluster size n=2-10) formed via electron-impact ionization of neutral helium droplets and derive appearance energies for mass-selected cluster ions using a nonlinear least-square-fitting procedure. Moreover, we report magic numbers in the mass spectrum observed at the electron energy of 70 eV. The apparatus used for the present measurements is a hemispherical electron monochromator combined with a quadrupole mass spectrometer. Our experiment demonstrates that helium clusters are not only exclusively formed via direct ionization above the atomic ionization potential but also indirectly via autoionizing Rydberg states. The present results are compared with previous electron-impact and photoionization results.

Journal Article↗
PubMed2006

Resonantly enhanced multiphoton ionization and zero kinetic energy photoelectron spectroscopy of 2-indanol conformers.

We report studies of a supersonically cooled 2-indanol using two-color resonantly enhanced multiphoton ionization (REMPI) and two-color zero kinetic energy (ZEKE) photoelectron spectroscopy. In the REMPI experiment, we have identified three conformers of 2-indanol and assigned the vibrational structures of the first electronically excited state for the two major conformers. Conformer Ia contains an intramolecular hydrogen bond between the -OH group and the phenyl ring, while conformer IIb has the -OH group in the equatorial position. We have further investigated the vibrational spectroscopy of the cation for the two major conformers using the ZEKE spectroscopy. The two conformers display dramatically different vibrational distributions. The ZEKE spectrum of conformer Ia shows an extensive progression in the puckering mode of the five member ring, indicating a significant geometry change upon ionization. The ZEKE spectra of conformer IIb are dominated by single vibronic transitions, and the intensity of the ZEKE signal is much stronger than that of conformer Ia. These results indicate an invariance of the molecular frame during ionization for conformer IIb. We have performed ab initio and density functional theory calculations to obtain potential energy surfaces along the dihedral angle involving the -OH group for all three electronic states. In addition, we have also calculated the vibrational distribution of the ZEKE spectrum for the puckering mode of the five member ring. Not only the vibrational frequencies but also the intensity distributions for both conformers have been reproduced satisfactorily. The adiabatic ionization energies have been determined to be 68 593+/-5 cm(-1) for conformer Ia and 68 981+/-5 cm(-1) for conformer IIb.

Cations↗
PubMed2002

Incidence of complications for subtotal ionized field ablation of the tonsils.

OBJECTIVE: Ionized field ablation, or coblation-assisted subtotal tonsillectomy, has been described as a new alternative technique for the management of tonsillar disease. This study was designed to review the incidence of complications in patients undergoing this procedure. STUDY DESIGN: A 10-surgeon retrospective chart review of the intraoperative and postoperative complications of patients undergoing ionized field ablation subtotal removal of tonsils was performed. Postoperative pain, dietary restrictions, and activity level were not reviewed. RESULTS: Of the 528 patients who underwent ionized field ablation of their tonsils, the incidence of intraoperative and postoperative complications compared favorably with those reported in retrospective studies in the literature for traditional subcapsular tonsillectomy. Significant postoperative bleeding occurred in less than 1%, and only 1 patient required surgical control of bleeding in the operating room. No patients required transfusions of any blood products. CONCLUSIONS: Ionized field ablation subtotal tonsillectomy may offer an alternative to traditional subcapsular tonsillar surgery with a decreased incidence of postoperative complications. Further study is necessary to establish the complication rate of this technique.

Adolescent↗
PubMed2001

Serum ionized magnesium in post-traumatic headaches.

The objective of this study was to determine the values of serum ionized magnesium, total magnesium, and ionized calcium/ionized magnesium ratios in children with headaches. One hundred thirty-five children with primary complaints of headaches were classified according to the criteria of the International Headache Society. Blood samples were obtained and tested for ionized magnesium (IMg(2+)), total magnesium, ionized calcium (ICa(2+)), and pH. The ICa(2+)/IMg(2+) ratio was calculated. Nine children were given a diagnosis of post-traumatic headache. Six of them had statistically significant (P <.05) lowered IMg(2+) levels and high ICa(2+)/IMg(2+) ratios. Abnormalities in serum IMg(2+) concentrations and ICa(2+)/IMg(2+) ratios were found in children with post-traumatic headaches, but total magnesium levels were normal.

Adolescent↗
PubMed2006

The galactic cosmic ray ionization rate.

The chemistry that occurs in the interstellar medium in response to cosmic ray ionization is summarized, and a review of the ionization rates that have been derived from measurements of molecular abundances is presented. The successful detection of large abundances of H(3)(+) in diffuse clouds and the recognition that dissociative recombination of H(3)(+) is fast has led to an upward revision of the derived ionization rates. In dense clouds the molecular abundances are sensitive to the depletion of carbon monoxide, atomic oxygen, nitrogen, water, and metals and the presence of large molecules and grains. Measurements of the relative abundances of deuterated species provide information about the ion removal mechanisms, but uncertainties remain. The models, both of dense and diffuse clouds, that are used to interpret the observations may be seriously inadequate. Nevertheless, it appears that the ionization rates differ in dense and diffuse clouds and in the intercloud medium.

Astronomical Phenomena↗
PubMed1974

The activity-related ionization in carbonic anhydrase.

The catalytic activity of carbonic anhydrase (EC 4.2.1.1) is linked to the ionization of a group in close proximity to the essential zinc ion. Studies have been undertaken to delineate the ionizations germane to the active-site chelate system. Several imidazole ligand systems were studied in order to approach a representative chelate. The simplest involved the complexation of Zn(II) by imidazole and by N-methylimidazole. As well, two bidentate systems, Zn(II)-4,4'-bis-imidazoylmethane and Co(II)-cyclic-L-histidyl-L-histidine were investigated. It was found that in a species containing metal-bound water and imidazole coordinated by means of the pyridinium nitrogen, the most acidic group was the pyrrole N-H in the imidazole ring. By the use of N-methylimidazole, the pK(a) of a metal-bound water molecule in a tri-imidazole ligand field was found to be 9.1. Noting the preference for labilization of the pyrrole hydrogen, the catalytic features of carbonic anhydrase are reexamined assuming that the pK(enz) is associated with the N-H ionization, and not with the ionization of metal-bound water.

Binding Sites↗