Complexation of hydrogen by lithium: structures,energies and vibrational spectra of Li+ (H2) n (n = 1–4), Li-H(H2) m and Li-H + (H2) m (m = 1–3)

The interaction of metals with hydrogen is of importance in several areas of technology. Lithium-hydrogen complexes are particularly amenable to theoretical study. Although no stable compound of the Li atom and H₂ has been found, a weak dative interaction forms between the σ bond of H₂ and the positively charged Li atom for Li⁺, Li-H⁺, and Li-H. At least four H₂ molecules can be complexed by Li⁺, and three by Li-H⁺ and Li-H. The presence of the Li ion does not substantially weaken the H₂ bond, nor is the energy of dissociation affected; however, the Li ion does form stable complexes with the dissociated H atoms.     

On the discrimination of bound and free sodium ions in solutions of biomolecules by means of the T1 relaxation.

The interactions of charged macromolecules with counterions have been extensively examined previously by ²³Na NMR, leading to the model that the counterions can be classified as beeing both “free” and “bound” in solution. We will demonstrate that the two dimensional time evolution approach for resolving a composite “free-induction-decay” opens the possibilities to measure both the T₁ of the free sodium ion and the T₁ of the sodium ion bound to a macromolecule simultaneously. A lot of various compounds as DNA and Heparin serve as models to demonstrate the usefulness of this new method.     

Synthesis and electrocatalytic activities of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocubes

In this article, a hydrothermal method was developed to synthesize Co₃O₄ nanocubes using hydrogen peroxide (H₂O₂) as oxidant, Co(NO₃)₂·6H₂O as a cobalt source. The products are characterized in detail by multiform techniques including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are Co₃O₄ nanocubes with size ranging between 20 and 40 nm. The effects of the hydrogen peroxide concentration on the size of the products have been studied. The electrocatalytic activities of H₂O₂ reduction on Co₃O₄ nanocubes in phosphate buffer were also evaluated.     

Single-molecule Detection of Reactive Oxygen Species: Application to Photocatalytic Reactions

In this review, we have focused on the oxidation reactions of single dye molecules by reactive oxygen species (ROS). The methodologies for the single-molecule detection of ROS, such as hydroxyl radical (HO^•), singlet oxygen (O₂(a¹Δ_g)), and hydrogen peroxide (H₂O₂), have been introduced together with examples. In particular, a successful application using the single-molecule fluorescence technique for the investigation of the TiO₂ photocatalytic oxidation reactions is demonstrated in detail.     

NO Fluorescence Sensing by Europium Tetracyclines Complexes in the Presence of H2O2

The effect on the fluorescence of the europium:tetracycline (Eu:Tc), europium:oxytetracycline (Eu:OxyTc) and europium:chlortetracycline (Eu:ClTc) complexes in approximately 2:1 ratio of nitric oxide (NO), peroxynitrite (ONOO^?), hydrogen peroxide (H₂O₂) and superoxide (O₂ ^·?) was assessed at three ROS/RNS concentrations levels, 30 °C and pH 6.00, 7.00 and 8.00. Except for the NO, an enhancement of fluorescence intensity was observed at pH 7.00 for all the europium tetracyclines complexes—the high enhancement was observed for H₂O₂. The quenching of the fluorescence of the Tc complexes, without and with the presence of other ROS/RNS species, provoked by NO constituted the bases for an analytical strategy for NO detection. The quantification capability was evaluated in a NO donor and in a standard solution. Good quantification results were obtained with the Eu:Tc (3:1) and Eu:OxyTc (4:1) complexes in the presence of H₂O₂ 200 μM with a detection limit of about 3 μM (Eu:OxyTc).     

Localisation of hydrogen peroxide accumulation during Solanum tuberosum cv. Rywal hypersensitive response to Potato virus Y

The reactive oxygen species hydrogen peroxide (H₂O₂) was detected cytochemically in Solanum tuberosum cv. Rywal tissues as a hypersensitive response (HR) 24 and 48 h after a Potato virus Y (PVY) infection.Hydrogen peroxide was detected in vivo by its reaction with 3.3-diaminobenzidine, producing a reddish-brown staining in contact with H₂O₂. Hydrogen peroxide was detected in the necrotic area of the epidermal and mesophyll cells 24 and 48 h after the PVY infection. Highly localised accumulations of H₂O₂ were found within xylem tracheary elements, and this was much more intensive than in non-infected leaves. Hydrogen peroxide was detected cytochemically in HR also by its reaction with cerium chloride, producing electron-dense deposits of cerium perhydroxides.Inoculation with PVY^NTN and also PVY^N Wi induced a rapid hypersensitive response during which highly localised accumulations of H₂O₂ was detected in plant cell walls. The most intensive accumulation was present in the bordering cell walls of necrotic mesophyll cells and the adjacent non-necrotic mesophyll cells. Intensive electron-dense deposits of cerium perhydroxide were found along ER cistrenae and chloroplast envelopes connected with PVY particles. The precipitates of hydrogen peroxide were detected in the nuclear envelope and along tracheary elements, especially when virus particles were present inside. The intensive accumulation of H₂O₂ at the early stages of potato–PVY interaction is consistent with its role as an antimicrobial agent and for this reason it has been regarded as a signalling molecule.     

H2O2–Ng dynamics predictions using an accurate potential energy surface

ABSTRACT

Based on ab initio calculations, our research group has built an analytical ground-state potential energy surface (PES) for hydrogen peroxide– noble gas (Ng) interactions, such as H₂O₂–He, H₂O₂–Ne, H₂O₂–Ar, H₂O₂–Kr, and H₂O₂–Xe complexes. From this PES, it was verified that the Ng presence does not affect the equilibrium values of the H₂O₂ dihedral angles. This happens because the H₂O₂ intramolecular barriers have much higher energies than the atom–bond interaction within these complexes. From this point of view, it is indeed reasonable to consider the H₂O₂ system as a rigid rotor, frozen at its equilibrium configuration. We present in this work the torsional motion for the H₂O₂ isolated system, the vibration–rotation energy levels and spectroscopic constants for hydrogen peroxide–noble gas by using the aforementioned PES. The predicted H₂O₂ torsional motions are in good agreement with both theoretical and experimental results available in the literature. Regarding H₂O₂–Ng ro-vibrational energies and spectroscopic constants, it is the first time that these calculations are presented in the literature. The current theoretical predictions are expected to be useful in the future experimental investigations.     

Complex formation and phosphate-H2O interactions in a concentrated aqueous Mg(H2PO4)2 solution.

X-ray diffraction data from a solution of Mg(H₂PO₄)₂ were examined. The experimental distribution curve shows peaks at about 2.10, 2.7–2.9, 3.6, 3.9 and 4.25 Å. The 3.6 Å peak reveals the formation of inner sphere magnesium-phosphate complexes Mg(H₂O)_6-z(H₂PO₄)^+2-z_z, in which oxygens from phosphate groups substitute z water molecules of the hydrated Mg(H₂O)²⁺₆ ions. Least squares refinements of the i(s) curve are consistent with a structural unit in which the phosphate tetrahedron shares a corner with one magnesium octahedron with MgOP angle of 147 deg. Each phosphate ion interacts with about eight water molecules.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

闭壳层金掺杂钛氧团簇阴离子解离氢分子研究

Dissociation of molecular hydrogen (H₂) is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H₂ dissociation by Au₁-doped closed-shell titanium oxide cluster anions AuTi₃O₇^- and AuTi₃O₈^- has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and massselected to react with H₂ in an ion trap reactor. In the reaction of AuTi₃O₈^- with H₂, the ion pair Au⁺-O₂^2- rather than Au⁺-O^2- is the active site to promote H₂ dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H₂ dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H₂ activation and dissociation.     

Water enrichment by hydroxyl and hydrogen peroxide due to cavitation treatment: GHz four-wave mixing spectroscopy

Four-waves mixing spectroscopy has been applied to detection of H₂O₂ and OH molecules in water after different treatments in a cavitation jet. The considerable growth of the ortho-H₂O, OH, and H₂O₂ rotational lines amplitude in cavitation water relatively to distilled water and 1% hydrogen peroxide aqueous solution have been found. This fact was interpreted as the exhibition of H₂O molecules dissociation onto atoms and recombination into OH and H₂O₂. Four-waves mixing spectra fitting gives the evaluation of H₂O₂ rotational line’s amplitude increasing in cavitation water by factor of ～3 in comparison to 1% H₂O₂ aqueous solution.     

The role of hydrogen peroxide in the deposition of cerium-based conversion coatings

Cerium-based conversion coatings are progressing as an effective alternative to hazardous chromate-based systems used in the treatment of metal surfaces. However, there is still considerable debate over the mechanism by which these coatings are formed. Here, titrations of cerium-based conversion coating solutions were carried out in order to model the reactions that occur at the metal-solution interface during coating, with a particular emphasis on investigating the role of hydrogen peroxide (H₂O₂). The titration curves obtained support the proposed formation of Ce(III) peroxo complexes such as Ce(H₂O₂)³⁺ as an initial step, followed by deprotonation, oxidation and precipitation to form peroxo-containing Ce(IV) species such as Ce^(IV)(O₂)(OH)₂. The precipitates resulting from titrations were characterised by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis, confirming the presence of peroxo bonds, and nano-sized CeO₂ crystallites that decreased in size with increasing H₂O₂ concentration. Characterisation of cerium conversion coatings on aluminium alloy surfaces confirmed the presence of peroxo species in the coatings, thereby supporting the titration model.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

Spectrofluorometric Determination of Hydrogen Peroxide

A Spectrofluorometric method for microdetermination of H₂O₂ has been developed. The method is based on the oxidation of hydrogen peroxide with ceric ion in acid solution and measurement of the fluorescence during titration of the Ce(III) ions produced. The fluorescent species have excitation and emission maxima at 260 and 360 nm, respectively. The detection limit of measurement by this method was 0.1 ppm hydrogen peroxide.     

SIMS,EID and flash-filament investigation of O2, H2, (O2 + H2) and H2O interaction with vanadium

Comparative investigations of secondary ion emission, electron induced ion emission and flash filament signals from polycrystalline vanadium surfaces exposed to well-defined O₂, H₂, H₂O and (O₂ + H₂) doses (<500 L) have been carried out. The vanadium target could be heated and bombarded by either electrons (300 eV) or ions (3 keV) under ultra high vacuum conditions (<10^?10 Torr). The investigations were carried out with a computer controlled ultra high vacuum mass spectrometer. The experimental results establish exact reproducible spectra of well defined surface layers. They give detailed insight into the reactions between H₂, O₂ H₂O and vanadium, and some interactions between these species. They further indicate the importance of bulk and surface diffusion as well as the influence of the probing ion and electron bombardment. A clear distinction between bulk oxygen, surface oxides, and adsorbed oxygen for the vanadium-oxygen interaction at room temperature could be established. For the interaction of hydrogen with clean and oxygen covered vanadium surfaces the formation of adsorbed hydrogen, bulk solution of hydrogen, and the formation of OH groups and H₂O could be demonstrated. A detection limit below 10^?5 of one single monolayer for metal bonded hydrogen could be established.     

A hydrogen peroxide electrochemical sensor based on Ag nanoparticles grown on ITO substrate

In this article, the Ag nanoparticles were synthesized on indium tin oxide conducting glass (ITO) substrate using the electrochemical deposition method. The morphology analysis of the deposits using scanning electron microscope (SEM) reveals that the sizes and densities of the Ag nanoparticles were tuned by varying the time of electrodeposition. The structure of the deposits was characterized by X-ray diffraction (XRD). The prepared Ag nanoparticles electrode was then applied to detect hydrogen peroxide (H₂O₂) in 0.01 M pH 7.0 phosphate buffer medium. The present electrochemical sensing platform exhibited good electrocatalytic activity towards the reduction of H₂O₂. The detection sensitivity of the sensor was 0.237 mA mM⁻¹. This method is very simple, inexpensive, and undemanding, thus it should be extensively applied in many fields for the detection of H₂O₂.     

Effects of concentrated NaCl and KCl solutions on the behaviour of aqueous peptide bond environment: single-particle dynamics and H-bond structural relaxation

The effects of salt concentrations on the structure, dynamics and hydrogen bond structural relaxation properties of ～1.10 M aqueous N-methylacetamide (NMA) solution at 308 K are studied by classical molecular dynamics simulations. We have considered the concentration range of salts solution from 0.222 to 3.756 M to investigate the behaviour of aqueous environment of peptide bonds in the presence of concentrated NaCl and KCl solution. It is found that the addition of salt solution facilitates the structural breaking of aqueous NMA hydrogen bonds, as a result the number of hydrogen bonds per NMA molecule and their stability decreases. The water and NMA molecule shows slower translational and rotational dynamics with increasing salt concentrations due to additional ion atmospheric friction. Our result shows that the cation–O_NMA radial distribution function decreases whereas the Cl^?─H_NMA radial distribution function increases with ion concentration. On the other hand, the cation–O_water and Cl^?─H_water radial distribution function shows very negligible change with respect to ion concentration. We have also calculated NMA–water and water–water hydrogen bond structural relaxation times. It is observed that the hydrogen bond structural relaxation of O_NMA─H_water is comparatively slower than the H_NMA─O_water hydrogen bond, which can be attributed to higher number and greater stability of the former hydrogen bond than the latter. The change of the dynamical quantities observed here is more prominent in addition of NaCl rather than the KCl solution.     

Rotational statistics and thermodynamic functions of hydrogen peroxide

Partition functions for both the rotational modes (hindered internal rotation and overall rotation) of the hydrogen peroxide (H₂O₂) molecule in the ground electronic state are studied using quantum and classical Gibbsian statistical mechanics. The partition functions are used to calculate rotational thermodynamic functions (internal energy, enthalpy, Helmholtz free energy, Gibbs free energy and entropy) of a hydrogen peroxide gas of weakly interacting molecules at temperatures above 300 K.     

Hydration-induced conformational changes in protonated 2,4-pentanedione in the gas phase

Starting with H⁺[CH₃C(O)CH₂C(O)CH₃] (denoted H⁺PD), the protonated diketone-water clusters H⁺PD(H₂O) _n (n = 1–3) have been characterized by density functional theory calculations in combination with vibrational predissociation spectroscopy to explore the conformational changes of a protonated bifunctional ion solvated by water in the gas phase. Theoretical calculations for H⁺PD revealed that the ion contains an intramolecular hydrogen bond (IHB), with two oxygen atoms bridged by the extra proton in an O—H⁺ … O form. Attachment of one water molecule to it readily ruptures this IHB, replacing the H⁺ by the H₃O⁺ moiety. Further replacement of the IHB by two water molecules occurs at n = 2 and the ?C(O)CH₂C(O)- chain is fully opened (or unfolded) after transfer of the extra proton to the water trimer at n = 3. To verify the computational findings, infrared spectroscopic measurements were performed using a vibrational predissociation ion trap spectrometer to identify cluster isomers from the signatures of hydrogen bonded and non-hydrogen bonded OH stretching spectra of H⁺PD(H₂O)_2,3 produced in a corona discharge supersonic expansion. Besides open form isomers, evidence for the formation of water-bridged structures has been found for H⁺PD(H₂O)₃ at an estimated temperature of 200 K. A detailed illustration of the unfolding steps as well as the energy profiles for the evolution of a two-water bridge isomer from the protonated H⁺PD monomer are analysed pictorially (including both stable intermediates and transition states) in the present investigation.     

Growth of SiO2 on InP substrate by liquid phase deposition

We have grown silicon dioxide (SiO₂) on indium phosphorous (InP) substrate by liquid phase deposition (LPD) method. With inserting InP wafer in the treatment solution composed of SiO₂ saturated hydrofluorosilicic acid (H₂SiF₆), 0.1 M boric acid (H₃BO₃) and 1.74 M diluted hydrochloric acid (HCl), the maximum deposition rate and refractive index for the as-grown LPD-SiO₂ film were about 187.5 Å/h and 1.495 under the constant growth temperature of 40 °C. The secondary ion mass spectroscope (SIMS) and energy dispersive X-ray (EDX) confirmed that the elements of silicon, oxygen, and chloride were found in the as-grown LPD-SiO₂ film. On the other hand, the effects of treatment solution incorporated with the hydrogen peroxide (H₂O₂) that can regulate the concentration of OH⁻ ion were also shown in this article. The experimental results represented that the deposition rate decreases with increasing the concentration of hydrogen peroxide due to the reduced concentration of SiO₂ saturated H₂SiF₆ in treatment solution.