Rapid quantification of free cholesterol in tears using direct insertion/electron ionization-Mass spectrometry

Purpose. To establish a simple and rapid analytical method, based on direct insertion/electron ionization-mass spectrometry (DI/EI-MS), for measuring free cholesterol in tears from humans and rabbits. Methods. A stable-isotope dilution protocol employing DI/EI-MS in selected ion monitoring mode was developed and validated. It was used to quantify the free cholesterol content in human and rabbit tear extracts. Tears were collected from adult humans (n = 15) and rabbits (n = 10) and lipids extracted. Results. Screening, full-scan (m/z 40-600) DI/EI-MS analysis of crude tear extracts showed that diagnostic ions located in the mass range m/z 350 to 400 were those derived from free cholesterol, with no contribution from cholesterol esters. DI/EI-MS data acquired using selected ion monitoring (SIM) were analyzed for the abundance ratios of diagnostic ions with their stable isotope-labeled analogues arising from the D6-cholesterol internal standard. Standard curves of good linearity were produced and an on-probe limit of detection of 3 ng (at 3:1 signal to noise) and limit of quantification of 8 ng (at 10:1 signal to noise). The concentration of free cholesterol in human tears was 15 ± 6 μg/g, which was higher than in rabbit tears (10 ± 5 μg/g). Conclusions. A stable-isotope dilution DI/EI-SIM method for free cholesterol quantification without prior chromatographic separation was established. Using this method demonstrated that humans have higher free cholesterol levels in their tears than rabbits. This is in agreement with previous reports. This paper provides a rapid and reliable method to measure free cholesterol in small-volume clinical samples. © 2013 The Association for Research in Vision and Ophthalmology, Inc.

Ion-molecule reactions reveal facile radical migration in peptides

Ion-molecule reactions between molecular oxygen and peptide radicals in the gas phase demonstrate that radical migration occurs easily within large biomolecules without addition of collisional activation energy.

Heat of formation of the hydroperoxyl radical HOO via negative ion studies

We present a determination of Delta(f)H(298)(HOO) based upon a negative. ion thermodynamic cycle. The photoelectron spectra of HOO- and DOO- were used to measure the molecular electron affinities (EAs). In a separate experiment, a tandem flowing afterglow-selected ion flow tube (FA-SIFT) was used to measure the forward and reverse rate constants for HOO- + HCdropCH reversible arrow HOOH + HCdropC(-) at 298 K, which gave a value for Delta(acid)H(298)(HOO-H). The experiments yield the following values: EA(HOO) = 1.078 +/- 0.006 eV; T-0((X) over tilde HOO - (A) over tilde HOO) = 0.872 +/- 0.007 eV; EA(DOO) = 1.077 +/- 0.005 eV; T-0((X) over tilde DOO - (A) over tilde DOO) = 0.874 +/- 0.007 eV; Delta(acid)G(298)(HOO-H) = 369.5 +/- 0.4 kcal mol(-1); and Delta(acid)H(298)(HOO-H) = 376.5 +/- 0.4 kcal mol(-1). The acidity/EA thermochemical cycle yields values for the bond enthalpies of DH298(HOO-H) = 87.8 +/- 0.5 kcal mol(-1) and Do(HOO-H) = 86.6 +/- 0.5 kcal mol(-1). We recommend the following values for the heats of formation of the hydroperoxyl radical: Delta(f)H(298)(HOO) = 3.2 +/- 0.5 kcal mol(-1) and Delta(f)H(0)(HOO) = 3.9 +/- 0.5 kcal mol(-1); we recommend that these values supersede those listed in the current NIST-JANAF thermochemical tables.

Negative-ion photoelectron spectroscopy, gas-phase acidity, and thermochemistry of the peroxyl radicals CH3OO and CH3CH2OO

Methyl, methyl-d(3), and ethyl hydroperoxide anions (CH3OO-, CD3OO-, and CH3CH2OO-) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer, gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities: EA[CH3OO, (X) over tilde (2)A"] = 1.161 +/- 0.005 eV, EA[CD3OO, (X) over tilde (2)A"] = 1.154 +/- 0.004 eV, and EA[CH3CH2OO, (X) over tilde (2)A"] = 1.186 +/- 0.004 eV. The photoelectron spectra yield values for the term energies: DeltaE((X) over tilde 2A"-(A) over tilde 2A')[CH3OO] = 0.914 +/- 0.005 eV, DeltaE((X) over tilde (2)A"-(A) over tilde 2A') [CD3OO] = 0.913 +/- 0.004 eV, and DeltaE((X) over tilde (2)A"-(A) over tilde (2)A')[CH3CH2OO] = 0.938 +/- 0.004 eV. A localized RO-O stretching mode was observed near 1100 cm(-1) for the ground state of all three radicals, and low-frequency R-O-O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow-selected ion flow tube k(FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Delta (acid)G(298)(CH3OOH) = 367.6 +/- 0.7 kcal mol(-1), Delta (acid)G(298)(CD3OOH) = 367.9 +/- 0.9 kcal mol(-1), and Delta (acid)G(298)(CH3CH2OOH) = 363.9 +/- 2.0 kcal mol(-1). From these acidities we have derived the enthalpies of deprotonation: Delta H-acid(298)(CH3OOH) = 374.6 +/- 1.0 kcal mol(-1), Delta H-acid(298)(CD3OOH) = 374.9 +/- 1.1 kcal mol(-1), and Delta H-acid(298)(CH2CH3OOH) = 371.0 +/- 2.2 kcal mol(-1). Use of the negative-ion acidity/EA cycle provides the ROO-H bond enthalpies: DH298(CH3OO-H) 87.8 +/- 1.0 kcal mol(-1), DH298(CD3OO-H) = 87.9 +/- 1.1 kcal mol(-1), and DH298(CH3CH2OO-H) = 84.8 +/- 2.2 kcal mol(-1). We review the thermochemistry of the peroxyl radicals, CH3OO and CH3CH2OO. Using experimental bond enthalpies, DH298(ROO-H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The "electron affinity/acidity/CBS" cycle yields Delta H-f(298)[CH3OO] = 4.8 +/- 1.2 kcal mol(-1) and Delta H-f(298)[CH3CH2OO] = -6.8 +/- 2.3 kcal mol(-1).

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

From short pulses to short breaks : exotic plasma bullets via residual electron control

Plasma plumes with exotically segmented channel structure and plasma bullet propagation are produced in atmospheric plasma jets. This is achieved by tailoring interruptions of a continuous DC power supply over the time scales of lifetimes of residual electrons produced by the preceding discharge phase. These phenomena are explained by studying the plasma dynamics using nanosecond-precision imaging. One of the plumes is produced using 2-10μs interruptions in the 8kV DC voltage and features a still bright channel from which a propagating bullet detaches. A shorter interruption of 900ns produces a plume with the additional long conducting dark channel between the jet nozzle and the bright area. The bullet size, formation dynamics, and propagation speed and distance can be effectively controlled. This may lead to micrometer-and nanosecond-precision delivery of quantized plasma bits, warranted for next-generation health, materials, and device technologies.

Mechanisms of sulfide ion oxidation during cyanidation. Part II : Surface catalysis by pyrite

The mechanisms and the reaction products for the oxidation of sulfide ions in the presence of pyrite have been established. When the leach solution contains free sulfide ions, oxidation occurs via electron transfer from the sulfide ion to dissolved oxygen on the pyrite mineral surface, with polysulfides being formed as an intermediate oxidation product. In the absence of cyanide, the polysulfides are further oxidised to thiosulfate, whilst with cyanide present, thiocyanate and sulfite are also formed from the reaction of polysulfides with cyanide and dissolved oxygen. Polysulfide chain length has been shown to affect the final reaction products of polysulfide oxidation by dissolved oxygen. The rate of pyrite catalysed sulfide ion oxidation was found to be slower in cyanide solutions compared to cyanide free solutions. Mixed potential measurements indicated that the reduction of oxygen at the pyrite surface is hindered in the presence of cyanide. The presence of sulfide ions was also found to activate the pyrite surface, increasing its rate of oxidation by oxygen. This effect was particularly evident in the presence of cyanide; in the presence of sulfide the increase in total sulfur from pyrite oxidation was 2.3 mM in 7 h, compared to an increase of <1 mM in the absence of sulfide over 24 h.

Investigation on bioactivity of titanium dioxide thin films fabricated by electron cyclotron resonance plasma aided pulsed laser deposition

Titanium dioxide thin films with a rutile crystallinite size around 20 nm were fabricated by pulsed laser deposition (PLD) aided with an electron cyclotron resonance (ECR) plasma. With annealing treatment, the crystal size of the rutile crystallinite increased to 100 nm. The apatite-forming ability of the films as deposited and after annealing was investigated in a kind of simulated body fluid with ion concentrations nearly equal to those of human blood plasma. The results indicate that ECR aided PLD is an effective way both to fabricate bioactive titanium dioxide thin films and to optimize the bioactivity of titanium dioxide, with both crystal size and defects of the film taken into account.

Microscopic ion fluxes in plasma-aided nanofabrication of ordered carbon nanotip structures

Three-dimensional topography of microscopic ion fluxes in the reactive hydrocarbon-based plasma-aided nanofabrication of ordered arrays of vertically aligned single-crystalline carbon nanotip microemitter structures is simulated by using a Monte Carlo technique. The individual ion trajectories are computed by integrating the ion equations of motion in the electrostatic field created by a biased nanostructured substrate. It is shown that the ion flux focusing onto carbon nanotips is more efficient under the conditions of low potential drop Us across the near-substrate plasma sheath. Under low- Us conditions, the ion current density onto the surface of individual nanotips is higher for higher-aspect-ratio nanotips and can exceed the mean ion current density onto the entire nanopattern in up to approximately five times. This effect becomes less pronounced with increasing the substrate bias, with the mean relative enhancement of the ion current density ξi not exceeding ∼1.7. The value of ξi is higher in denser plasmas and behaves differently with the electron temperature Te depending on the substrate bias. When the substrate bias is low, ξi decreases with Te, with the opposite tendency under higher- Us conditions. The results are relevant to the plasma-enhanced chemical-vapor deposition of ordered large-area nanopatterns of vertically aligned carbon nanotips, nanofibers, and nanopyramidal microemitter structures for flat-panel display applications. © 2005 American Institute of Physics.

Dust charge and ion drag forces in a high-voltage, capacitive radio frequency sheath

The charge of an isolated dust grain and ion drag forces on the grain in a collisionless, high-voltage, capacitive rf sheath are studied theoretically. The studies are carried out assuming that the positive ions are monoenergetic, as well as in more realistic approximation, assuming that the time-averaged energy distribution of ions impinging on the dust grain has a double-peaked hollow profile. For the nonmonoenergetic case, an analytical expression for the ion flux to the dust grain is obtained. It is studied how the dust charge and ion drag forces depend on the rf frequency, electron density at plasma-sheath boundary, electron temperature and ratio of the effective oscillation amplitude of rf current to the electron Debye length. It is shown that the dust charge and ion drag forces obtained in the monoenergetic ion approximation may differ from those calculated assuming that the ions are nonmonoenergetic. The difference increases with increasing the width of the ion energy spread in the ion distribution. © 2009 American Institute of Physics.

Monoclinic β-MoO3 nanosheets produced by atmospheric microplasma : application to lithium-ion batteries

Porous high surface area thin films of nanosheet-shaped monoclinic MoO 3 were deposited onto platinized Si substrates using patch antenna-based atmospheric microplasma processing. The films were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and electrochemical analysis. The electrochemical analysis shows original redox peaks and high charge capacity, and also indicates a reversible electrochemical behaviour particularly beneficial for applications in Li-ion batteries. SEM shows that the films are highly porous and consist of nanosheets 50-100 nm thick with surface dimensions in the micrometre range. HRTEM reveals that the MoO3 nanosheets consist of the monoclinic beta phase of MoO3. These intricate nanoarchitectures made of monoclinic MoO3 nanosheets have not been studied previously in the context of applications in Li-ion batteries and show superior structural and morphological features that enable effective insertion of Li ions.

Ion-acoustic waves in a dust-contaminated plasma

A self-consistent theory of ion-acoustic waves in dusty gas discharge plasmas is presented. The plasma is contaminated by fine dust particles with variable charge. The stationary state of the plasma and the dispersion and damping characteristics of the waves are investigated accounting for ionization, recombination, dust charge relaxation, and dissipation due to electron and ion elastic collisions with neutrals and dusts, as well as charging collisions with the dusts.

Spatially averaged model of complex-plasma discharge with self-consistent electron energy distribution

A global, or averaged, model for complex low-pressure argon discharge plasmas containing dust grains is presented. The model consists of particle and power balance equations taking into account power loss on the dust grains and the discharge wall. The electron energy distribution is determined by a Boltzmann equation. The effects of the dust and the external conditions, such as the input power and neutral gas pressure, on the electron energy distribution, the electron temperature, the electron and ion number densities, and the dust charge are investigated. It is found that the dust subsystem can strongly affect the stationary state of the discharge by dynamically modifying the electron energy distribution, the electron temperature, the creation and loss of the plasma particles, as well as the power deposition. In particular, the power loss to the dust grains can take up a significant portion of the input power, often even exceeding the loss to the wall.

Ion-acoustic waves in a complex plasma with negative ions

A wave propagation in a complex dusty plasma with negative ions was considered. The relevant processes such as ionization, electron attachment, diffusion, positive-negative ion recombination, plasma particle collisions, as well as elastic Coulomb and inelastic dust-charging collisions were taken self-consistently. It was found that the equilibrium of the plasma as well as the propagation of ion waves were modified to various degrees by these effects.

Ion-assisted functional monolayer coating of nanorod arrays in hydrogen plasmas

Uniformity of postprocessing of large-area, dense nanostructure arrays is currently one of the greatest challenges in nanoscience and nanofabrication. One of the major issues is to achieve a high level of control in specie fluxes to specific surface areas of the nanostructures. As suggested by the numerical experiments in this work, this goal can be achieved by manipulating microscopic ion fluxes by varying the plasma sheath and nanorod array parameters. The dynamics of ion-assisted deposition of functional monolayer coatings onto two-dimensional carbon nanorod arrays in a hydrogen plasma is simulated by using a multiscale hybrid numerical simulation. The numerical results show evidence of a strong correlation between the aspect ratios and nanopattern positioning of the nanorods, plasma sheath width, and densities and distributions of microscopic ion fluxes. When the spacing between the nanorods and/or their aspect ratios are larger, and/or the plasma sheath is wider, the density of microscopic ion current flowing to each of the individual nanorods increases, thus reducing the time required to apply a functional monolayer coating down to 11 s for a 7-μm-wide sheath, and to 5 s for a 50-μm-wide sheath. The computed monolayer coating development time is consistent with previous experimental reports on plasma-assisted functionalization of related carbon nanostructures [B. N. Khare et al., Appl. Phys. Lett. 81, 5237 (2002)]. The results are generic in that they can be applied to a broader range of plasma-based processes and nanostructures, and contribute to the development of deterministic strategies of postprocessing and functionalization of various nanoarrays for nanoelectronic, biomedical, and other emerging applications.