NMR-spectroscopic mapping of an engineered cavity in the I14A mutant of HPr from Staphylococcus carnosus using xenon

The interaction between the histidine-containing phosphocarrier protein HPr and xenon atoms in solution is studied in the present paper. Wild-type HPr as well as the exchange mutant I14A have been studied. Specific binding of xenon into an engineered cavity created via the exchange of amino acid residue I14 by alanine could be shown using 1H-15N heteronuclear single-quantum coherence (HSQC) spectroscopy. Xenon binding results in pronounced changes of the 1H and 15N chemical shifts of amide groups close to the cavity. In addition to this observation which allows the NMR-spectroscopic mapping of such cavities, we have shown that the entire molecule is slightly rearranged as a result of xenon binding. In contrast, wild-type HPr only exhibits minor chemical shift changes due to the nonspecific interactions with the xenon atoms in solution.     

Molecular simulation of the high-pressure phase equilibria of binary atomic fluid mixtures using the exponential-6 intermolecular potential

Molecular simulation results using the exponential-6 intermolecular potential are reported for the phase behaviour of the atomic binary mixtures of neon+xenon, helium+neon, helium+argon and helium+xenon. These binary mixtures exhibit both vapour–liquid and liquid–liquid phase equilibria up to very high pressures. Comparison with experiment indicates good overall agreement. The results indicate that the exponential-6 intermolecular potential is a useful generic potential for molecular simulation.     

Probing the hydrophobic cavity of lipid transfer protein from Nicotiana tabacum through xenon-based NMR spectroscopy

The hydrophobic cavity of Lipid Transfer Protein 1 from Nicotiana tabacum is investigated in detail by NMR using xenon as a spy. The analysis of the (129)Xe chemical shifts and self-relaxation times gives evidence of protein-xenon interaction. Thermodynamics of the binding is characterized through the study of aliphatic (1)H and (13)C chemical shift variation as a function of xenon pressure. The binding constant is evaluated to 75.5 +/- 1.0 M(-1) at 293 K. The location of xenon inside the cavity is deduced from SPINOE experiments. The noble gas appears to occupy four sites, and xenon self-relaxation experiments indicate that it quickly jumps between different sites. The chemical shifts of amide protons and nitrogens also depend on the xenon concentration, either specifically or nonspecifically for atoms at the external surface of the protein. Yet, contrary to aliphatic atoms, they do not correspond to short-range interactions as confirmed by magnetization transfer experiments between laser-polarized xenon and protons in H(2)O. These (15)N chemical shift variations, used in combination with (15)N transverse self-relaxation rates to determine the lower limit of the binding rate, consequently reveal subtle changes in the structure of the protein upon binding.     

On the position of helium and neon in the Periodic Table of Elements

Helium and neon, the two lightest noble gases, have been traditionally positioned by IUPAC in the Group 18 of the Periodic Table of Elements, together with argon, and other unreactive or moderately reactive gaseous elements (krypton, xenon, radon), and oganesson. In this account we revive the old discussion on the possible placement of helium in the Group 2, while preserving the position of neon in Group 18. We provide quantum-chemical arguments for such scenario—as well as other qualitative and quantitative arguments—and we describe previous suggestions in the literature which support it or put it into question. To this author’s own taste, He should be placed in Group 2.     

Ab initio molecular orbital studies of the vibrational spectra of the van der Waals complexes of boron trifluoride with the noble gases

The molecular structures, interaction energies, charge transfer properties and vibrational spectra of the van der Waals complexes formed between boron trifluoride and the noble gases neon, argon, krypton and xenon have been computed using second and fourth order M?ller-Plesset perturbation theory and the Los Alamos National Laboratory LANL2DZ basis set. The complexes are all symmetric tops, with the noble gas atom acting as a sigma electron donor along the C3 axis of the BF3 molecule. The interaction energies are all vanishingly small, and the amount of charge transferred in each case is of the order of 0.01e. The directions of the wavenumber shifts of the symmetric bending (nu2) and antisymmetric stretching (nu3) modes of the BF3 fragment confirm those determined experimentally, and the shifts are shown to correlate well with the polarizability of the noble gas atom and the inverse sixth power of the intermonomer separation. The nu2 mode is substantially more sensitive to complexation than the nu3 vibration.     

Velocity dependence of the total cross section for helium-argon,neon-krypton and neon-xenon scattering

Velocity dependences of the total collision cross sections for scattering of helium by argon, neon by krypton and neon by xenon were measured using a time of flight method of velocity selection. For neon scattering glory oscillations were observed from which values of ?r_m (the product of the well depth and the internuclear separation at the minimum) were determined for various Lennard-Jones potentials. Comparison is made with the results from diffusion experiments and differential scattering measurements.     

Dynamics of xenon binding inside the hydrophobic cavity of pseudo-wild-type bacteriophage T4 lysozyme explored through xenon-based NMR spectroscopy

Wild-type bacteriophage T4 lysozyme contains a hydrophobic cavity with binding properties that have been extensively studied by X-ray crystallography and NMR. In the present study, the monitoring of 1H chemical shift variations under xenon pressure enables the determination of the noble gas binding constant (K = 60.2 M(-1)). Although the interaction site is highly localized, dipolar cross-relaxation effects between laser-polarized xenon and nearby protons (SPINOE) are rather poor. This is explained by the high value of the xenon-proton dipolar correlation time (0.8 ns), much longer than the previously reported values for xenon in medium-size proteins. This indicates that xenon is highly localized within the protein cavity, as confirmed by the large chemical shift difference between free and bound xenon. The exploitation of the xenon line width variation vs xenon pressure and protein concentration allows the extraction of the exchange correlation time between free and bound xenon. Comparison to the exchange experienced by protein protons indicates that the exchange between the open and closed conformations of T4 lysozyme is not required for xenon binding.     

Spin‐orbit ZORA and four‐component Dirac–Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble gas dimers

Hartree–Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange‐correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin‐orbit zeroth‐order regular approximation Hamiltonian in combination with the large Slater‐type basis set QZ4P as well as with the four‐component Dirac–Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles with noniterative triple excitations [CCSD(T)] calculations using the very large polarization‐consistent basis sets aug‐pcSseg‐4 for He, Ne and Ar, aug‐pcSseg‐3 for Kr, and the AQZP basis set for Xe. For the dimers also, zero‐point vibrational (ZPV) corrections are obtained at the CCSD(T) level with the same basis sets were added. Best estimates of the dimer chemical shifts are generated from these nuclear magnetic shieldings and the relative importance of electron correlation, ZPV, and relativistic corrections for the shieldings and chemical shifts is analyzed. © 2015 Wiley Periodicals, Inc.     

Noble gas-actinide complexes of the CUO molecule with multiple Ar,Kr, and Xe atoms in noble-gas matrices

Laser-ablated U atoms react with CO in excess argon to produce CUO, which is trapped in a triplet state in solid argon at 7 K, based on agreement between observed and relativistic density functional theory (DFT) calculated isotopic frequencies ((12)C(16)O, (13)C(16)O, (12)C(18)O). This observation contrasts a recent neon matrix investigation, which trapped CUO in a linear singlet state calculated to be about 1 kcal/mol lower in energy. Experiments with krypton and xenon give results analogous to those with argon. Similar work with dilute Kr and Xe in argon finds small frequency shifts in new four-band progressions for CUO in the same triplet states trapped in solid argon and provides evidence for four distinct CUO(Ar)(4-n)(Ng)(n) (Ng = Kr, Xe, n = 1, 2, 3, 4) complexes for each Ng. DFT calculations show that successively higher Ng complexes are responsible for the observed frequency progressions. This work provides the first evidence for noble gas-actinide complexes, and the first example of neutral complexes with four noble gas atoms bonded to one metal center.     

Spectroscopic characterization of a neon surface-wave sustained (2.45 GHz) discharge at atmospheric pressure

In this paper a spectroscopic study of a microwave (2.45 GHz) neon surface-wave sustained discharge (SWD) at atmospheric pressure in a quartz tube has been carried out in order to determine the plasma characteristic parameters (e.g. electron temperature and density, gas temperature, absorbed power per electron) and also to identify possible deviations from the thermodynamic equilibrium for this kind of microwave discharge. The results have been compared to experiments in the literature for other noble gas (helium and argon) SWDs generated under similar experimental conditions. Intermediate values between those of argon and helium plasmas were obtained for characteristic neon plasma parameters (temperatures and electron density). An important departure from the Saha equilibrium was exhibited by neon SWDs.     

Gas‐Hydrate Packing and Stability at High Pressures

The decomposition temperatures of double gas hydrates of tetrahydrofuran with noble gases from krypton to helium at pressures up to 15 kbar were found by differential thermal analysis. The stability of hydrates was shown to rise as their packing coefficient increases. Krypton and argon hydrates retain the original cubic structure II in the whole pressure range. In neon and helium systems, polyhedral double hydrates have upper stability limits at 7.4 and 6.0 kbar, respectively.     

Double clathrate hydrates of tetrabutylammonium fluoride + helium, neon, hydrogen and argon at high pressures

Decomposition curves of double ionic clathrate hydrates of tetrabutylammonium fluoride with helium, neon, hydrogen and argon were studied at pressures up to 800 MPa. Formation of double hydrates with helium, neon and hydrogen does not lead to any significant increase of the temperatures of decomposition of these hydrates; at high temperatures the hydrates may decompose even at lower temperatures than the hydrate of pure tetraalkylammonium salt does. Decomposition temperatures of double hydrates with argon in all cases were 4–8 °C higher in comparison with the decomposition temperature of ionic clathrate hydrates of tetrabutylammonium fluoride. We suppose that this behavior is caused by simultaneous effect of three factors on hydrate decomposition temperature: (1) partial filling of the small cavities in the framework of the hydrate with water molecules, (2) weakness of the van der Waals interactions between the gas molecules and the host water molecules, and (3) dissolution of helium, hydrogen and neon in the solution of tetrabutylammonium salt causing a decrease of melting temperatures of the hydrates formed from these solutions.     

Enthalpies of aqueous solution of noble gases at 25°C

The standard enthalpies of solution of rare gases (helium, neon, argon, krypton, and xenon) in water at 25°C have been measured by a high precision steady-state calorimetric method. The aqueous solvation process is energetically favorable at 25°C for the gases studied. Values of the standard free energy, enthalpy, and entropy changes are found to be well correlated with cavity surface areas and the number of water molecules in the first solvation shell. Also, the values of the standard enthalpy and entropy of solution for the rare gases are found to have the same dependence on the number of solvation shell water molecules as inorganic and hydrocarbon gases. These results imply that the dominant source of enthalpy and entropy change resides in the first solvation shell.     

Cryptophane-xenon complexes in organic solvents observed through NMR spectroscopy

The interaction of xenon with cryptophane derivatives is analyzed by NMR by using either thermal or hyperpolarized noble gas. Twelve hosts differing by their stereochemistry, cavity size, and the nature and the number of the substituents on the aromatic rings have been included in the study, in the aim of extracting some clues for the optimization of (129)Xe-NMR based biosensors derived from these cage molecules. Four important properties have been examined: xenon-host binding constant, in-out exchange rate of the noble gas, chemical shift, and relaxation of caged xenon. This work aims at understanding the main characteristics of the host-guest interaction in order to choose the best candidate for the biosensing approach. Moreover, rationalizing xenon chemical shift as a function of structural parameters would also help for setting up multiplexing applications. Xenon exhibits the highest affinity for the smallest cryptophane, namely cryptophane-111, and a long relaxation time inside it, convenient for conservation of its hyperpolarization. However, very slow in-out xenon exchange could represent a limitation for its future applicability for the biosensing approach, because the replenishment of the cage in laser-polarized xenon, enabling a further gain in sensitivity, cannot be fully exploited.     

A comparative study of two cavities for generating a microwave induced plasma in helium or argon as a detector in gas chromatography

In the microwave induced plasma (MIP) detector both $\text{1}\text{4}$λ-Evenson and Beenakker cavities are used. The last one also operates at atmospheric pressure. Both cavities are investigated with some simple alkanes. In the gas chromatographical system helium and argon are used as carrier gas. Measuring the C emission line, the Beenakker cavity with argon shows the greatest sensitivity, the best detection limit (0.2 ng C/s) and a good linear dynamic range (> 800). The best detection limit for H emission is found at use of the Beenakker cavity with helium (0.13 ng $\text{H}\text{s}$). The results of measuring the H emission line using the Beenakker cavity with argon are poor. It was further shown that, although it is in principle possible to determine a ratio formula or molecular formula with the aid of a reference compound, the results are inadequate for ‘unknown’ compounds.     

Effect of pH and counterions on the encapsulation properties of xenon in water-soluble cryptophanes

In the ¹²⁹Xe NMR‐based biosensing approach in which the hyperpolarized noble gas is transported to biological receptors for a sensitive molecular imaging, cryptophanes are excellent xenon host systems. However to avoid formation of self‐organized systems, these hydrophobic cage molecules can be rendered water soluble by introduction of ionic groups. We show that the sensitivity of xenon to its local environment and the presence of these ionic functions can lead to interesting properties. For a first water‐soluble cryptophane derivative, we show that a precise monitoring of the local pH can be performed. For a second cryptophane, the presence of ionic groups close to the cryptophane cavity modifies the xenon binding constant and in–out exchange rate. The latter allows the tuning of physical properties of xenon–cryptophane interactions without resorting to a change of the cavity size. These results open new perspectives on the influence of chemical modifications of cryptophanes for optimizing the biosensor properties.     

Simulations of the absorption band of the D-state of Hg2 in rare gas matrices

We present molecular dynamics simulations of the absorption spectra of the Hg₂ molecule in solid neon, argon, and xenon. The simulations were performed using classical molecular dynamics (MD) and a diatomic-in-molecules (DIM) treatment of the mixing of the different states of Hg₂ induced by the environment. The experimental relative shifts of the X0_g⁺–D1_u transition band are qualitatively well reproduced. The origin of these shifts is identified as the result of two combined factors: the effect of the host onto the Hg–Hg equilibrium distances and the different interaction of each matrix with the Hg₂ electronic states.     

Bond dissociation energy and Lewis acidity of the xenon fluoride cation

This study focuses upon the Lewis acid reactivity of XeF(+) with various bases in the gas phase and the determination of the bond dissociation energy of XeF(+). The bond dissociation energy of XeF(+) has been measured by using energy-resolved collision-induced dissociation with neon, argon, and xenon target gases. Experiments with neon target yield a 298 K bond dissociation enthalpy of 2.81 +/- 0.09 eV, and those with argon target give a similar value at 2.83 +/- 0.12 eV. When using a xenon target, a significantly lower value of 1.95 +/- 0.16 eV was observed, which corresponds closely with previous measurements and theoretical predictions. It is proposed that the lighter target gases give inefficient excitation of the XeF(+) vibration leading to dissociation at energies higher than the BDE. Novel xenon-base adducts have been prepared in a flowing afterglow mass spectrometer by termolecular addition to XeF(+) and by reaction of base with XeF(+)(H(2)O). New species have been characterized qualitatively by CID, and it is found that the products formed reflect the relative ionization energies of the fragments. Among the new xenon-containing species that have been prepared are the first examples of xenon carbonyls.     

The determination of neon and argon in helium by atomic absorption spectrophotometry

An atomic absorption spectrophotometric technique is described for the determination of neon and argon, respectively, in helium. The accuracies obtained for nanomoles of neon and argon, respectively, were +2.1 and -1.5%. Two Geissler-type discharge tubes containing neon and argon, respectively, were used as emission sources; the absorption source was a quartz cell which contained the sample and related standards that were excited by a high-frequency oscillator. The spectral lines that were employed were neon 6402 Å and argon 8115 Å. Because the spectral lines used had transitions to metastable energy levels, instead of ground levels, a conventional monochromator was suitable.     

Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.