Search Results (28)

To investigate the effect of Botrytis cinerea infection severity on the flavor characteristics of Petit Manseng noble rot wine, this study analyzed wines produced from Petit Manseng grapes grown in the eastern foothills of Helan Mountain, Ningxia, China. The grapes were categorized into three groups based on infection status: uninfected, mildly infected, and severely infected with Botrytis cinerea. Headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) and an electronic nose were employed to detect and analyze the aroma components of wines under the three infection conditions. Additionally, trained sensory panelists conducted sensory evaluations of the wine aromas. The results revealed that wines made from severely infected grapes exhibited the richest and most complex aroma profiles. A total of 70 volatile compounds were identified, comprising 32 esters, 17 alcohols, 5 acids, 8 aldehydes and ketones, 4 terpenes, and 4 other compounds. Among these, esters and alcohols accounted for the highest contents. Key aroma-active compounds included isoamyl acetate, ethyl decanoate, phenethyl acetate, ethyl laurate, hexanoic acid, linalool, decanoic acid, citronellol, ethyl hexanoate, and methyl octanoate. Sensory evaluation indicated that the “floral aroma”, “pineapple/banana aroma”, “honey aroma”, and “overall aroma intensity” were most pronounced in the severely infected group. These findings provide theoretical support for the harvesting of severely Botrytis cinerea-infected Petit Manseng grapes and the production of high-quality noble rot wine in this region. Full article

Interpretation of ⁴⁰Ar/³⁹Ar dates of alkali feldspar and U-Pb dates of apatite depends on the dominant mechanism of isotopic transport in these minerals, which can be either diffusion or fluid-assisted dissolution-reprecipitation. To clarify the contributions of these processes, we have conducted a holistic study of alkali feldspar, apatite and other minerals from the Mt. Isa Inlier in NE Australia. Mineral characterisation by electron microscopy, optical cathodoluminescence imaging and element mapping reveal a complex interplay of textures resulting from magmatic crystallisation, deuteric recrystallisation, local deformation with subsequent higher-temperature alteration, and finally ubiquitous low-temperature alteration. U-Pb and Pb isotopic data for zircon, apatite, fluorite and alkali feldspar suggest that the latter event occurred at ~300 Ma and was associated with fluid-assisted exchange of Pb isotopes between minerals in the same rock, causing some apatite grains to have ²⁰⁷Pb-corrected U-Pb dates that exceed their crystallisation age. However, this event had no unequivocal effect on the ⁴⁰Ar/³⁹Ar or Rb-Sr systematics of the alkali feldspar, which were disturbed by higher-temperature alteration at ~1450 Ma. The age of the latter event is derived from Rb-Sr data. ⁴⁰Ar/³⁹Ar dates are very scattered and suggest that ⁴⁰Ar redistribution proceeded by diffusion in the presence of traps in some places and by dissolution-reprecipitation with variable amounts of recycling in other places. Our results demonstrate the complex effects that interaction with limited amounts of fluids can have on ⁴⁰Ar/³⁹Ar dates of alkali feldspar and U-Pb dates of apatite and thereby reinforce previous critique of their suitability for thermochronological reconstructions. We further identify and discuss potential implications for noble gas geochronology of groundwaters and fission track dating of apatite. Full article

Recent progress in studies of Rydberg double-well electronic energy states of MeNg (Me = 12-group atom, Ng = noble gas atom) van der Waals (vdW) molecules is presented and analysed. The presentation covers approaches in experimental studies as well as ab initio-calculations of potential energy curves (PECs). The analysis is shown in a broader context of Rydberg states of hetero- and homo-diatomic molecules with PECs possessing complex ‘exotic’ structure. Laser induced fluorescence (LIF) excitation spectra and dispersed emission spectra employed in the spectroscopical characterization of Rydberg states are presented on the background of the diverse spectroscopic methods for their investigations such as laser vaporization–optical resonance (LV-OR), pump-and-probe methods, and polarization labelling spectroscopy. Important and current state-of-the-art applications of Rydberg states with irregular potentials in photoassociation (PA), vibrational and rotational cooling, molecular clocks, frequency standards, and molecular wave-packet interferometry are highlighted. Full article

The interactions between plasma and liquids cause complex physical and chemical reactions at the gas–liquid contact surface, producing numerous chemically active particles that can rapidly reduce noble metal ions. This study uses atmospheric-pressure surface dielectric barrier discharge (DBD) plasma to treat ethanol aqueous solutions containing noble metal precursors, and stable gold, platinum, and palladium colloids are obtained within a few minutes. To evaluate the mechanism of the reduction of noble metal precursors by atmospheric-pressure surface DBD plasma, the corresponding metal colloids are prepared first by activating an ethanol aqueous solution with plasma and then adding noble metal precursors. It is found that the long-lived active species hydrogen peroxide (H₂O₂) plays a dominant role in the synthesis process, which has distinct effects on different metal ions. When HAuCl₄ and H₂PdCl₄ are used as precursors, H₂O₂ acts as a reducing agent, and AuCl₄⁻ and PdCl₄²⁻ ions can be reduced to metallic Au and Pd. However, when AgNO₃ is the precursor, H₂O₂ acts as an oxidising agent, and Ag⁺ ions cannot be reduced to obtain metal colloids because metallic Ag can be dissolved in H₂O₂ under acidic conditions. A similar phenomenon was also observed for the preparation of Pd colloid-PA with a plasma-activated ethanol aqueous solution using Pd(NO₃)₂ as a Pd precursor. Full article

According to Bader’s quantum theory of atoms in molecules (QTAIM), the simultaneous presence of a bond path and the corresponding bond critical point between any two atoms is both a necessary and sufficient condition for the atoms to be bonded to one another. In principle, this means that this pair of atoms should make a stabilizing contribution to the molecular system. However, the multitude of so-called counterintuitive bond paths strongly suggests that this statement is not necessarily true. Particularly ‘troublesome’ are endohedral complexes, in which encapsulation-enforced proximity between the trapped guest (e.g., an atom) and the host’s cage system usually ‘produces’ many counterintuitive bond paths. In the author’s opinion, the best evidence to demonstrate the repulsive nature of the intra-cage guest⋯host interaction is the use of some trapping systems containing small escape channels and then showing that the initially trapped entity spontaneously escapes outside the host’s cage during geometry optimization of the initially built guest@host endohedral complex. For this purpose, a group of 24 Ng@[3${}_n$]cyclophane (3$\le n\le$6) endohedral complexes is used. As a result, arguments are presented showing that Bader’s topological bond path does not necessarily indicate a stabilizing interaction. Full article

A comprehensive analysis of the intermolecular interaction energy and anharmonic vibrations of 41 structures of the HXeY⋯HX (X, Y = F, Cl, Br, I) family of noble-gas-compound complexes for all possible combinations of Y and X was conducted. New structures were identified, and their interaction energies were studied by means of symmetry-adapted perturbation theory, up to second-order corrections: this provided insight into the physical nature of the interaction in the complexes. The energy components were discussed, in connection to anharmonic frequency analysis. The results show that the induction and dispersion corrections were the main driving forces of the interaction, and that their relative contributions correlated with the complexation effects seen in the vibrational stretching modes of Xe–H and H–X. Reasonably clear patterns of interaction were found for different structures. Our findings corroborate previous findings with better methods, and provide new data. These results suggest that the entire group of the studied complexes can be labelled as “naturally blueshifting”, except for the complexes with HI. Full article

This article provides a discussion on the nature of bonding between noble gases (Ng) and noble metals (M) from a quantum chemical perspective by investigating compounds such as NgMY (Y=CN, O, NO₃, SO₄, CO₃), [NgM−(bipy)]+, NgMCCH, and MCCNgH complexes, where M=Cu, Ag, Au and Ng=Kr−Rn, with some complexes containing the lighter noble gas atoms as well. Despite having very low chemical reactivity, noble gases have been observed to form weak bonds with noble metals such as copper, gold, and silver. In this study, we explore the factors that contribute to this unusual bonding behavior, including the electronic structure of the atoms involved and the geometric configuration of the concerned fragments. We also investigate the metastable nature of the resulting complexes by studying the energetics of their possible dissociation and internal isomerization channels. The noble gas-binding ability of the bare metal cyanides are higher than most of their bromide counterparts, with CuCN and AgCN showing higher affinity than their chloride analogues as well. In contrast, the oxides seem to have lower binding power than their corresponding halides. In the oxide and the bipyridyl complexes, the Ng-binding ability follows the order Au > Cu > Ag. The dissociation energies calculated, considering the zero-point energy correction for possible dissociation channels, increase as we move down the noble gas group. The bond between the noble gases and the noble metals in the complexes are found to have comparable weightage of orbital and electrostatic interactions, suggestive of a partial covalent nature. The same is validated from the topological analysis of electron density. Full article

The generation of ozone and nitrogen oxides by laser-induced dielectric breakdown (LIDB) in mixtures of air with noble gases Ar, He, Kr, and Xe is investigated using OES and IR spectroscopy, mass spectrometry, and absorption spectrophotometry. It is shown that the formation of NO and NO₂ noticeably depends on the type of inert gas; the more complex electronic configuration and the lower ionization potential of the inert gas led to increased production of NO and NO₂. The formation of ozone occurs mainly due to the photolytic reaction outside the gas discharge zone. Equilibrium thermodynamic analysis showed that the formation of NO in mixtures of air with inert gases does not depend on the choice of an inert gas, while the equilibrium concentration of the NO+ ion decreases with increasing complexity of the electronic configuration of an inert gas. Full article

In this work, the binding features of adducts formed by a noble gas (Ng = He, Ne, Ar, Kr, Xe, and Rn) atom and the oxygen molecule (O₂) in its ground $\Sigma _g^{-}{}_3{}^{}$, in the past target of several experimental studies, have been characterized under different theoretical points of view to clarify fundamental aspects of the intermolecular bond. For the most stable configuration of all Ng–O₂ systems, binding energy has been calculated at the theory’s CCSD(T)/aug-cc-pVTZ level and compared with the experimental findings. Rovibrational energies, spectroscopic constants, and lifetime as a function of temperature were also evaluated by adopting properly formulated potential energy curves. The nature of the interaction involved was deeply investigated using charge displacement analysis, symmetry-adapted perturbation theory (SAPT), and natural bond orbital (NBO) methods. In all adducts, it was found that the charge transfer plays a minor role, although O₂ is an open shell species exhibiting a positive electron affinity. Obtained results also indicate that the dispersion attraction contribution is the main responsible for the complex stability. Full article

The structure, stability, and bonding situation of some exemplary noble gas-silicon cations were investigated at the MP2/aVTZ level of theory. The explored species include the mono-coordinated NgSiX₃⁺ (Ng = He-Rn; X = H, F, Cl) and NgSiF₂²⁺ (Ng = He-Rn), the di-coordinated Ar₂SiX₃⁺ (X = H, F, Cl), and the “inserted” FNgSiF₂⁺ (Ng = Kr, Xe, Rn). The bonding analysis was accomplished by the method that we recently proposed to assay the bonding situation of noblegas compounds. The Ng-Si bonds are generally tight and feature a partial contribution of covalency. In the NgSiX₃⁺, the degree of the Ng-Si interaction mirrors the trends of two factors, namely the polarizability of Ng that increases when going from Ng = He to Ng = Rn, and the Lewis acidity of SiX₃⁺ that decreases in the order SiF₃⁺ > SiH₃⁺ > SiCl₃⁺. For the HeSiX₃⁺, it was also possible to catch peculiar effects referable to the small size of He. When going from the NgSiF₃⁺ to the NgSiF₂²⁺, the increased charge on Si promotes an appreciable increase inthe Ng-Si interaction, which becomes truly covalent for the heaviest Ng. The strength of the bond also increases when going from the NgSiF₃⁺ to the “inserted” FNgSiF₂⁺, likely due to the cooperative effect of the adjacent F atom. On the other hand, the ligation of a second Ar atom to ArSiX₃⁺ (X = H, F, Cl), as to form Ar₂(SiX₃⁺), produces a weakening of the bond. Our obtained data were compared with previous findings already available in the literature. Full article

Superphane, i.e., [2.2.2.2.2.2](1,2,3,4,5,6)cyclophane, is a very convenient molecule in studying the nature of guest⋯host interactions in endohedral complexes. Nevertheless, the presence of as many as six ethylene bridges in the superphane molecule makes it practically impossible for the trapped entity to escape out of the superphane cage. Thus, in this article, I have implemented the idea of using the superphane derivatives with a reduced number of ethylene linkers, which leads to the [2${}_n$] cyclophanes where $n<6$. Seven such cyclophanes are then allowed to form endohedral complexes with noble gas (Ng) atoms (He, Ne, Ar, Kr). It is shown that in the vast majority of cases, the initially trapped Ng atom spontaneously escapes from the cyclophane cage, creating an exohedral complex. This is the best proof that the Ng⋯cyclophane interaction in endohedral complexes is indeed highly repulsive, i.e., destabilizing. Apart from the ‘sealed’ superphane molecule, endohedral complexes are only formed in the case of the smallest He atom. However, it has been shown that in these cases, the Ng⋯cyclophane interaction inside the cyclophane cage is nonbonding, i.e., repulsive. This highly energetically unfavorable effect causes the cyclophane molecule to ‘swell’. Full article

The structures and spectral features of protonated noble gas clusters are examined using a first principles approach. Protonated noble gas monomers (NgH⁺) and dimers (NgH⁺Ng) have a linear structure, while the protonated noble gas trimers (Ng₃H⁺) can have a T-shaped or linear structure. Successive binding energies for these complexes are calculated at the CCSD(T)/CBS level of theory. Anharmonic simulations for the dimers and trimers unveil interesting spectral features. The symmetric NgH⁺Ng are charactized by a set of progression bands, which involves one quantum of the asymmetric Ng-H⁺ stretch with multiple quanta of the symmetric Ng-H⁺ stretch. Such a spectral signature is very robust and is predicted to be observed in both T-shaped and linear isomers of Ng₃H⁺. Meanwhile, for selected asymmetric NgH⁺Ng’, a Fermi resonance interaction involving the first overtone of the proton bend with the proton stretch is predicted to occur in ArH⁺Kr and XeH⁺Kr. Full article

Herein, we report the mechanistic investigation of the formation of nickel (Ni) nanocrystallites during the formation of amorphous silicon nitride at a temperature as low as 400 °C, using perhydropolysilazane (PHPS) as a preformed precursor and further coordinated by nickel chloride (NiCl₂); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl₂ catalyzed dehydrocoupling reactions between Si-H and N-H bonds in PHPS to afford ternary silylamino groups, which resulted in the formation of a nanocomposite precursor via complex formation: Ni(II) cation of NiCl₂ coordinated the ternary silylamino ligands formed in situ. By monitoring intrinsic chemical reactions during the precursor pyrolysis under inert gas atmosphere, it was revealed that the Ni-N bond formed by a nucleophilic attack of the N atom on the Ni(II) cation center, followed by Ni nucleation below 300 °C, which was promoted by the decomposition of Ni nitride species. The latter was facilitated under the hydrogen-containing atmosphere generated by the NiCl₂-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si₃N₄ matrix surrounding Ni nanocrystallites. Full article

Multidimensional potential energy surfaces for heavy noble gas–propylene oxide systems are obtained by applying the phenomenological method successfully used to describe homologous systems involving He and Ne atoms. Such potential energy surfaces, where the interaction exclusively arises from the anisotropic van der Waals interaction components, are given in an analytical form. Therefore, they can be easily used as force fields to carry out molecular simulations to evaluate spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide (a prototype chiral species) with a noble gas atom (a prototype isotropic partner) by two-body collisions under a variety of conditions. Several potential energy minima are identified on the surfaces, which are confirmed and characterized by high level ab initio calculations. The next step to further generalize this methodology is its extension to systems involving propylene oxide-diatomic molecules (as H₂, O₂ and N₂), as well as to propylene oxide dimers. Full article

We undertake a van der Waals inquiry at very low temperatures so as to find signs of a classical–quantum frontier. We investigate the relation of such signs with the celebrated van der Waals gas–liquid transition. We specialize the discussion with respect to the noble gases. For such purpose, we use rather novel thermal statistical quantifiers such as the disequilibrium, the statistical complexity, and the thermal efficiency. Fruitful insights are thereby gained. Full article