Exploring the mechanism of graphene-oxide reduction by hydrazine in a multi-epoxide environment with DFT calculations.

Reduction mechanisms between hydrazine and a multi-epoxide arrangement were investigated on a finite-sized graphene-oxide model with density functional theory. Three multistep reaction pathways were explored to examine different graphene-oxide (GO) deoxygenation scenarios. Epoxides sharing the same hexagonal ring show the typical one-by-one elimination of the oxygen functional groups through two protonation steps and the formation of cis-diazine and water. Nevertheless, the migration of one of the epoxy groups to an out-of-ring position has to precede the reduction. When a hexagonal ring separates two epoxy groups, forming a partially reduced surface with two hydroxyl groups is energetically favoured. This reduction product is so stable that it may remain on the surface after the termination of the reduction process. If further deoxygenation occurs, it can lead to surface fragmentation due to the ring opening of the remaining epoxides. The formation of nitrogen-containing functional groups at the edge of the graphene-oxide flake is also considered, and their surface presence is evaluated based on their thermodynamic stabilities.

Computational modelling of ammonia addition on partially reduced graphene oxide flakes.

Density functional theory is employed to model the chemisorption of ammonia on epoxy-containing polycyclic aromatic hydrocarbons (PAHs) and understand the reaction mechanism of ammonia addition on partially reduced graphene oxide flakes. Coronene (C24H12) and ovalene (C32H14) based four-epoxy group containing molecules are used to mimic the RGO surface properties. The reaction mechanism changing effect of a second ammonia molecule as well as explicit water molecules is considered. The proposed reaction mechanism consists of two steps: the migration of one epoxy group out of the modelled four-epoxy group formation to a thermodynamically less stable one and the nucleophilic addition of the ammonia molecule. The second step involves forming an amine group and reducing an epoxy group to a hydroxyl one. Interestingly, the forming amine group bonds to the carbon atom with the smallest bond order among the available ones and not necessarily to the carbon atom of the opening epoxy ring. Incorporating a second ammonia molecule has a negligible effect on the overall reaction mechanism, while in the presence of one water molecule, the reaction goes through a different pathway involving a trimolecular state during the nucleophilic addition. Including more than one water molecule or applying an implicit solvent model does not cause further changes in the reaction.

Triazaphospholenium Tetrafluoroborate: A Phosphorus Analogue of a 1,2,3-Triazole-Derived Carbene.

3H-1,2,3,4-Triazaphosphole derivatives can be selectively alkylated with Meerwein's reagent at the most nucleophilic nitrogen atom. According to the principle of valence isoelectronicity, the corresponding phosphorus heterocycle represents the first formal phosphorus analogue of the well-known 1,2,3-triazolylidenes (mesoionic carbenes). Theoretical calculations revealed that the cation in triazaphospholenium tetrafluoroborate is an aromatic system with a high degree of π-conjugation. First investigations showed that the cationic phosphorus heterocycle can stabilize a [Cu2 Br4 ]2- dianion by formation of a neutral coordination compound with an unusual bonding situation between phosphorus and copper(I).

Pyridyl-functionalised 3H-1,2,3,4-triazaphospholes: synthesis, coordination chemistry and photophysical properties of low-coordinate phosphorus compounds.

Novel conjugated, pyridyl-functionalised triazaphospholes with either tBu or SiMe3 substituents at the 5-position of the N3 PC heterocycle have been prepared by a [3+2] cycloaddition reaction and compared with structurally related, triazole-based systems. Photoexcitation of the 2-pyridyl-substituted triazaphosphole gives rise to a significant fluorescence emission with a quantum yield of up to 12 %. In contrast, the all-nitrogen triazole analogue shows no emission at all. DFT calculations indicate that the 2-pyridyl substituted systems have a more rigid and planar structure than their 3- and 4-pyridyl isomers. Time-dependent (TD) DFT calculations show that only the 2-pyridyl-substituted triazaphosphole exhibits similar planar geometry, with matching conformational arrangements in the lowest energy excited state and the ground state; this helps to explain the enhanced emission intensity. The chelating P,N-hybrid ligand forms a Re(I) complex of the type [(N^N)Re(CO)3 Br] through the coordination of nitrogen atom N(2) to the metal centre rather than through the phosphorus donor. Both structural and spectroscopic data indicate substantial π-accepting character of the triazaphosphole, which is again in contrast to that of the all-nitrogen-containing triazoles. The synthesis and photophysical properties of a new class of phosphorus-containing extended π systems are described.

Significant cation effects in carbon dioxide-ionic liquid systems.

Carbon dioxide-ionic liquid systems are of great current interest, and significant efforts have been made lately to understand the intermolecular interactions in these systems. In general, all the experimental and theoretical studies have concluded so far that the main solute-solvent interaction takes effect through the anion, and the cation has no, or only a secondary role in solvation. In this theoretical approach it is shown that this view is unfounded, and evidence is provided that, similarly to the benzene-CO(2) system, dispersion interactions are present between the solute and the cation. Therefore, this defines a novel site for tailoring solvents to tune CO(2) solubility.

Structure and other molecular properties of actinide trichlorides AnCl3 (An = Th-Cm).

The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl3 and CmCl3 with their well-defined 6dσ/7s hybrid and 5f(7) configurations, respectively. In contrast, the intermediate actinides (PaCl3-AmCl3) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl3 the ground-state molecular geometries proved to be pyramidal with C(3v) symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.

Dibenzophosphapentaphenes: exploiting P chemistry for gap fine-tuning and coordination-driven assembly of planar polycyclic aromatic hydrocarbons.

A synthetic route to planar P-modified polycylic aromatic hydrocarbons (PAHs) is described. The presence of a reactive σ(3),λ(3)-P moiety within the sp(2)-carbon scaffold allows the preparation of a new family of PAHs displaying tunable optical and redox properties. Their frontier molecular orbitals (MOs) are derived from the corresponding phosphole MOs and show extended conjugation with the entire π framework. The coordination ability of the P center allows the coordination-driven assembly of two molecular PAHs onto a Au(I) ion.

Updating the Methodology of Identifying Maize Hybrids Resistant to Ear Rot Pathogens and Their Toxins-Artificial Inoculation Tests for Kernel Resistance to Fusarium graminearum, F. verticillioides, and Aspergillus flavus.

Resistance to toxigenic fungi and their toxins in maize is a highly important research topic, as mean global losses are estimated at about 10% of the yield. Resistance and toxin data of the hybrids are mostly not given, so farmers are not informed about the food safety risks of their grown hybrids. According to the findings aflatoxin regularly occurs at preharvest in Hungary and possibly other countries in the region can be jeopardized. We tested, with an improved methodology (two isolates, three pathogens, and a toxin control), 18 commercial hybrids (2017-2020) for kernel resistance (%), and for toxin contamination separately by two-two isolates of F. graminearum, F. verticillioides (mg/kg), and A. flavus (µg/kg). The preharvest toxin contamination was measured in the controls. Highly significant kernel resistance and toxin content differences were identified between hybrids to the different fungi. Extreme high toxin production was found for each toxic species. Only about 10-15% of the hybrids showed higher resistance to the fungal species tested and lower contamination level of their toxins. The lacking correlations between resistance to different fungi and toxins suggest that resistance to different fungi and response to toxin contamination inherits independently, so a toxin analysis is necessary. For safety risk estimation, separated artificial and natural kernel infection and toxin data are needed against all pathogens. Higher resistance to A. flavus and F. verticillioides stabilizes or improves feed safety in hot and dry summers, balancing the harmful effect of climate changes. Resistance and toxin tests during variety registration is an utmost necessity. The exclusion of susceptible or highly susceptible hybrids from commercial production results in reduced toxin contamination.

The Role of Preharvest Natural Infection and Toxin Contamination in Food and Feed Safety in Maize, South-East Hungary, 2014-2021.

Mycotoxins originating in the preharvest period represent a less studied research problem, even though they are of the utmost practical significance in maize production, determining marketability (within EU limits), and storage ability, competitiveness, and profit rate. In this study, 18-23 commercial hybrids were tested between 2014 and 2021. Natural infection from Fusarium spp. was higher than 1.5%, and for Aspergillus spp. this was normally 0.01% or 0, much lower than would be considered as severe infection. In spite of this, many hybrids provided far higher toxin contamination than regulations allow. The maximum preharvest aflatoxin B1 was in 2020 (at 2286 µg/kg), and, in several cases, the value was higher than 1000 µg/kg. The hybrid differences were large. In Hungary, the presence of field-originated aflatoxin B1 was continuous, with three AFB1 epidemics in the 8 years. The highest DON contamination was in 2014 (at 27 mg/kg), and a detectable DON level was found in every hybrid. FUMB1+B2 were the highest in 2014 (at 45.78 mg/kg). At these low infection levels, correlations between visual symptoms and toxin contaminations were mostly non-significant, so it is not feasible to draw a conclusion about toxin contamination from ear rot coverage alone. The toxin contamination of hybrids for a percentage of visual infection is highly variable, and only toxin data can decide about food safety. Hybrids with no visual symptoms and high AFB1 contamination were also identified. Preharvest control, including breeding and variety registration, is therefore of the utmost importance to all three pathogens. Even natural ear rot and toxin data do not prove differences in resistance, so a high ear rot or toxin contamination level should be considered as a risk factor for hybrids. The toxin control of freshly harvested grain is vital for separating healthy and contaminated lots. In addition, proper growing and storage conditions must be ensured to protect the feed safety of the grain.

Hydrolysis of imidazole-2-ylidenes.

The direct reaction of an imidazole-2-ylidene in a predominantly aqueous environment [about 0.1 M solution in a H(2)O (>60%)/THF solvent system] was investigated for the first time. The reaction yielded a stable solution of the corresponding imidazolium-hydroxide of pH 13, which is in agreement with results from an ab initio molecular dynamics simulation. In contrast, hydrolysis of the carbene in a mainly aprotic environment (>80% THF) gives a hydrogen-bridged carbene-water complex which could be detected by NMR and IR spectroscopies for the first time. This complex converts slowly to two isomeric ring opened products and is at higher water concentration in dynamic equilibrium with the imidazolium hydroxide. A computational mechanistic study of the carbene hydrolysis with a gradually increasing number of water molecules revealed that the imidazolium-hydroxide structure can only be optimized with three or more water molecules as reactants, and with the increasing number of water molecules its stability is increasing with respect to the carbene-water complex. In agreement with the experimental results, these findings point out that solvent stabilization and basicity of the hydroxide ion plays a crucial role in the reaction. With increasing number of water molecules the barriers connecting the reaction intermediates are getting smaller, and the ring opened hydrolysis products can be derived from imidazolium-hydroxide type intermediates. Computational studies on the hydrolysis of a nonaromatic imidazolidine-2-ylidene analogue clearly indicated the analogous ring-opened product to be by 10-12 kcal/mol more stable than the appropriate ion pair and the carbene-water complex, in agreement with the known aromatic stabilization of imidazol-2-ylidenes. Accordingly, these molecules hydrolyze with exclusive formation of the ring-opened product.

Bonding in negative ions: the role of d orbitals in the heavy analogues of pyridine and furan radical anions.

We have used a potential wall method to investigate the role of d orbitals in the a(2) singly-occupied molecular orbitals of (2)A(2) negative ion states of two molecular series: pyridine, phosphabenzene, arsabenzene, stibabenzene (C(5)H(5)X, X = {N, P, As, Sb}), and furan, thiophene, selenophene, tellurophene (C(4)H(4)X, X = {O, S, Se, Te}). Unlike for the lower lying doubly occupied orbitals, heteroatom d-carbon p in-phase (bonding) interactions in these a(2) orbitals are clearly identified and explain the 0.5 eV stabilization of the (2)A(2) radical anion state in those compounds where the heteroatoms have d orbitals in the valence shell, compared to compounds where d orbitals are missing in the valence shell of the heteroatoms. The performance of both the potential wall approach and the approximate expression of Tozer and De Proft for calculating negative electron affinities has been also investigated, through a comparison with results obtained using electron-transmission spectroscopy experiments.

Adsorption of glycine on the anatase (101) surface: an ab initio study.

The adsorption of glycine on a clean anatase (101) surface was studied by first principles calculations. Glycine was found to bind to the surface in an undissociated form, utilizing both the carboxyl and the amino groups for the binding. The adsorption energy was found to be -23.0 kcal mol(-1). Two other configurations were found to be only slightly (by 0.6 and 1.1 kcal mol(-1)) less stable, one binding only through the lone pair of the amino group, the other adopting a dissociated binding mode. The conformational strain of glycine was found to have a significant effect on the adsorption energy. The adsorption properties of the amino and carboxyl functional groups of glycine were compared to those of ammonia and formic acid. While the amino group shows a similar binding energy to that of ammonia, the carboxyl group of glycine is able to create stronger binding to the anatase surface than formic acid.

Lepidocrocite-like structure of the TiO(2) monolayer grown on Ag(100).

Titanium oxide ultrathin films were grown on Ag(100) by evaporation of titanium in an O(2) atmosphere. The growth of the oxide films was monitored by means of XPS. The Ti2p XPS spectra indicate the formation of films with a TiO(2) stoichiometry in the whole range of coverages studied here. The STM results show that titania films appear to grow as islands of uniform thickness up to the completion of the first layer. Up to the formation of one complete monolayer, a (5 × 1) LEED pattern is observed. This pattern can be interpreted as a coincidence mesh and the lattice parameters of the oxide layer are very close to those of TiO(2) films with a lepidocrocite-like structure. However, the STM images show a long-range coincidence between the periodicity of the oxide film and that of the substrate along the short side of the oxide unit cell revealing that this lattice parameter is not exactly equal to that of the substrate. Above the monolayer coverage, additional spots become visible in the LEED pattern which can be interpreted in terms of the unit cell of rutile (110). The structural determination was carried out for the monolayer of titania by means of XPD and LEED intensity analysis. The results of these investigations demonstrate that the titania monolayer has a lepidocrocite-like structure. The DFT calculations carried out for the titania monolayer show the higher stability of the lepidocrocite structure with respect to other structures derived from crystallographic planes of bulk TiO(2) phases. Moreover, these calculations allow us to determine the oxide-substrate interface energy as well as to clarify the effect of the strain on the stability of the oxide layer.

Synthesis, electronic properties, and reactivity of phospholes and 1,1'-biphospholes bearing 2- or 3-thienyl C-substituents.

Two series of phospholes and 1,1'-biphospholes bearing either 2- or 3-thienyl substituents at the C atoms are prepared by using the Fagan-Nugent route. Their optical (UV/Vis absorption, fluorescence spectra) and electrochemical properties are systematically evaluated. Of particular interest, the first ever reported 3-thienyl-substituted phospholes exhibit higher LUMO levels than their 2-thienyl analogues, and show accordingly different physical properties. This study also reveals that the 1,1'-biphospholes exhibit sigma-pi conjugation. The phosphole and 1,1'-biphosphole derivatives bearing 3-thienyl substituents are characterized by X-ray diffraction study. The structure-property relationship established following the experimental data are fully supported by theoretical studies including time-dependent(TD)-DFT spectra. A photocyclization reaction performed on the thioxo- and oxophospholes having 3-thienyl substituents affords a novel ring-fused phosphole-thiophene derivative, which was characterized by an X-ray diffraction study. The structure and electronic properties of this novel dithienophosphole are discussed based on experimental and theoretical data.

Natural radioactivity of thermal springs and related precipitates in Gellért Hill area, Buda Thermal Karst, Hungary.

The elevated radioactivity of the thermal waters of Buda Thermal Karst (BTK), Hungary is known and studied since the beginning of the 20th century. In the recent studies, the anomalous 222Rn/226Ra ratios have drawn the attention to the existence of local 222Rn source. Biogeochemical precipitates (i.e. biofilms) in spring caves were found to have high adsorption capacity, accumulating e.g. 226Ra. Biogeochemical precipitates are ubiquitous in the thermal springs of BTK, occurring in different amount and colours (dark grey, brown, red, white), and have different microbial communities and elemental composition. The detailed investigation of the radioactivity of spring waters highlighted the different 226Ra and 222Rn activity concentrations. The present study aimed to survey the radioactivity of the thermal springs of Gellért Hill area, together with the biogeochemical precipitates and air above the water level, and to assess the evolution of the radioactivity of known-aged precipitates, formed during in situ experiments. We found that the basic physicochemical parameters of the spring waters (field parameters, major ions) do not affect the adsorption capacity of biogeochemical precipitates. It was revealed by the conducted in situ experiments, that the flow conditions influence the evolution rate of precipitates, so their adsorption capacity. The 222Rn activity concentrations of spring waters are dependent on the area of the water surface, volume of air space above the water level, ventilation of the caves/channels and presence of calcite layer on the water surface. The latter has a blocking effect on degassing.

Radon as a natural tracer for underwater cave exploration.

The Molnár János cave is one of the largest hypogenic caves of the Buda Thermal Karst (Budapest, Hungary) and mainly characterized by water-filled passages. The major outflow point of the waters of the cave system is the Boltív spring, which feeds the artificial Malom Lake. Previous radon measurements in the cave system and in the spring established the highest radon concentration (71 BqL-1) in the springwater. According to previous studies, the origin of radon was identified as iron-hydroxide containing biofilms, which form where there is mixing of cold and thermal waters, and these biofilms efficiently adsorb radium from the thermal water component. Since mixing of waters is responsible for the formation of the cave as well, these iron-hydroxide containing biofilms and the consequent high radon concentrations mark the active cave forming zones. Based on previous radon measurements, it is supposed that the active mixing and cave forming zone has to be close to the spring, since the highest radon concentration was measured there. Therefore radon mapping was carried out with the help of divers in order to get a spatial distribution of radon in the cave passages closest to the spring. Based on our measurements, the highest radon activity concentration (84 BqL-1) was found in the springwater. Based on the distribution of radon activity concentrations, direct connection was established between the spring and the István-room of the cave, which was verified by an artificial tracer. However, the distribution of radon in the cave passages shows lower concentrations (18-46 BqL-1) compared to the spring, therefore an additional deep inflow from hitherto unknown cave passages is assumed, from which waters with high radon content arrive to the spring. These passages are assumed to be in the active cave formation zone. This study proved that radon activity concentration distribution is a useful tool in underwater cave exploration.

The stability of η2-H2 borane complexes - a theoretical investigation.

Non-metallic η(2)-H2 complexes are extremely rare; moreover in the case of boranes (with the exception of the BH5 molecule) the existence of such structures was only indicated by computational studies. In a recent paper we have demonstrated that external electron donor groups can stabilize the η(2)-H2 complexes, similar to the backdonation in the case of transition metals. In this paper we present evidence of a new stabilizing effect: electron donation from the B-R bonds to the H2 σ* orbital. The stability and electronic structure of several mono-, di-, and trisubstituted borane-H2 complexes were investigated by ab initio calculations. SiR3 groups were found to facilitate the σ(B-R)→σ*(H-H) interaction, increasing the stability of the η(2) complexes. Furthermore in the case of tris(trimethyl)silylborane, the exceptional stability of a novel neutral pentavalent borane structure is shown.

Ab initio modeling of trititanate nanotubes.

Nanotubes with H2Ti3O7 stoichiometry have been studied by ab initio methods in the diameter range of ∼20-60 Å. The distribution of the protons on the unit cell surface and its effect on the structure and electronic properties of the titanium dioxide backbone has been investigated. The preferred protonation pattern was found to be the function of the diameter of the nanotube and the convexity of the surface. Trititanate tubes have been found to be more stable than lepidocrocite nanotubes at all diameters. At diameters<50 Å the dissociation of water from the internal surface and the emergence of a new tube wall structure was observed. Band gaps were found to change only slightly with the curvature, the maximum difference from the flat slab values was ±0.5 eV.

Ab initio modeling of TiO2 nanotubes.

TiO(2) nanotubes constructed from a lepidocrocite-like TiO(2) layer were investigated with ab initio methods employing the periodic CRYSTAL code. The dependence of strain energies, structural and electronic properties on the tube diameter was investigated in the 18-57 A range. Nanotubes constructed by a (0,n) rollup proved to be the most stable at all diameters. All three types of rollup undergo significant reconstruction at diameters <25 A. All investigated structures possess a high ( approximately 5.4 eV) band gap compared to bulk TiO(2) phases (3.96 and 4.63 eV for rutile and anatase calculated with the same functional and basis set).