Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study

The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X₃/X atom(s) of the NC-C₆H₂-X₃ and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F₃ and F-C-X₃ (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (E_int) were observed for the F-C-F₃∙∙∙NC-C₆H₂-X₃ complexes compared with the F-C-F₃∙∙∙NCX analogs. Moreover, significant E_int was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X₃/X atom(s). Among Set I complexes, the highest negative E_int was ascribed to the F-C-F₃∙∙∙NC-C₆H₂-I₃ complex with a value of −1.23 kcal/mol. For Set II complexes, E_int values of F-C-X₃ bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mol for the W-C-F₃ analogs. However, V_s,max quantities exhibited higher values in the case of W-C-F₃ molecules compared with F-C-X₃; preferable negative E_int were ascribed to the F-C-X₃ bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X₃ substituents. Dispersion forces (E_disp) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes.     

Electronic Structure of Unsaturated V2O5(001) and (100) Surfaces: Ab Initio Density Functional Theory Studies

Vanadium oxides based materials are well known to play an active role as catalysts in many chemical processes of technological importance like for example hydrocarbon oxidation reactions or selective catalytic reduction of NO _x in the presence of ammonia. Usually the (010) surface is pointed out as the most important, however one has to underline that other low-indices surfaces are by far less studied. In the present study the electronic structure of V₂O₅(001) and (100) surfaces are determined by ab initio DFT methods using gradient-corrected RPBE exchange-correlation functional. As models of surface sections different embedded V₁₄O₄₅H₂₀, V₁₄O₄₄H₁₈, and V₂₁O₆₅H₂₅ clusters are considered for the (001) surface and V₁₂O₄₀H₂₀, V₁₄O₄₆H₂₂, V₁₆O₅₂H₂₄ for the (100) surface. Detailed analyses of the electronic structure of each cluster are performed using charge density distributions, Mayer bond orders, electrostatic potential maps, character of frontier orbitals, and density of states (total as well as partial, atom projected). Results of the calculations show that overall negative charge of the surface oxygen sites scales with their coordination independent of the surface orientation. Terminal oxygen O(1) is charged the least negatively while doubly coordinated atoms –O(2) and O^e(2) have charge twice as large. This indicates that bridging (for (001) and (100) netplanes) and edging (only for (001) netplane) oxygen sites are more nucleophilic than terminal vanadyl sites, which becomes important in view of the reactivity of the different sites for surface chemical reactions. Vanadium atoms present at these surfaces are positively charged (electrophilic) and may play a role of electron acceptors. The unsaturated surfaces show a strong tendency to surface relaxation that manifest by large relaxation energies.     

高氯酸提取土壤中形态铁及其直接测定的研究

利用1 mol/L高氯酸提取果园土壤中的Fe(Ⅱ),建立了在1 mol/L高氯酸体系下,Fe(Ⅱ)与邻菲啉显色反应(5ε10=1.1×104L/(mol.cm)的分光光度法。具有快速、灵敏、提取与测定体系一致的优点。吸光度与浓度在0.063~8.0μg/mL范围内具有良好的线性,检出限为29 ng/mL,相对标准偏差≤2.11%,平均回收率为97.5%。该法用于测定土壤中形态铁的提取与测定,均获得满意结果。     

Effect of Hindered Phenol AO‐80 on the Damping Properties for Nitrile‐Butadiene Rubber/Phenolic Resin: Molecular Simulation and Experimental Study

A combined study of molecular dynamics (MD) simulation, experimental, and linear regression analysis method is presented for hindered phenol of 3,9‐bis[1,1‐dimethyl‐2‐{b‐(3‐tertbutyl‐4‐hydroxy‐5‐methylphenyl)propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro‐[5,5]‐undecane (AO‐80)/nitrile‐butadiene rubber/linear phenolic resin (AO‐80/NBR/PR) composites with different AO‐80 contents to quantitatively establish the relations between microstructure and damping performance. The number of hydrogen bonds (N_HBs), the fractional free volume (FFV), and the binding energy (E_binding) of AO‐80/NBR/PR composites with different AO‐80 content are calculated by MD simulation from the microscopic scale. Damping parameters, including the loss factor peak (tan δ_max) and the loss peak area (TA) (tan δ > 0.3), are obtained by dynamic mechanical analysis from macroscopic scale. The quantitative relationships between microstructure parameters (N_HBs, E_binding, and FFV) and macroscopic damping properties (tan δ_max and TA) are obtained by linear regression analysis. This research is expected to provide a theoretical guidance for improving the damping performance of rubber‐based organic hybrid composites.     

The Reactions of Bromide with Ozone Towards Bromate and the Hypobromite Puzzle: A Density Functional Theory Study

Taking the solvent water into account, the energetics of the reactions of O₃ with Br^? leading to BrO₃ ^? have been calculated by Density Functional Theory at the B3LYP/6–311+G(d)/SCRF =COSMO level. Br^? reversibly forms an adduct, BrOOO^?, (ΔG?=?+6 kJ mol^?1) that decays spin allowed into BrO^? and O₂(¹Δ_g) (ΔG?=?+13 kJ mol^?1). BrO^? undergoes an oxidation to BrO₂ ^? and a reduction to Br^?. This may be accounted for if two different adducts, OBrOOO^? and BrOOOO^?, decay into BrO^? plus O₂ and Br^? plus 2 O₂. After cyclization, OBrOOO^? may also lead to Br^? plus 2 O₂.     

Fluorine Scan of Inhibitors of the Cysteine Protease Human Cathepsin L: Dipolar and Quadrupolar Effects in the π‐Stacking of Fluorinated Phenyl Rings on Peptide Amide Bonds

The π‐stacking of fluorinated benzene rings on protein backbone amide groups was investigated, using a dual approach comprising enzyme–ligand binding studies complemented by high‐level quantum chemical calculations. In the experimental study, the phenyl substituent of triazine nitrile inhibitors of human cathepsin L (hCatL), which stacks onto the peptide amide bond Gly67?Gly68 at the entrance of the S3 pocket, was systematically fluorinated, and differences in inhibitory potency were measured in a fluorimetric assay. Binding affinity is influenced by lipophilicity (clog P), the dipole and quadrupole moments of the fluorinated rings, but also by additional interactions of the introduced fluorine atoms with the local environment of the pocket. Generally, the higher the degree of fluorination, the better the binding affinities. Gas phase calculations strongly support the contributions of the molecular quadrupole moments of the fluorinated phenyl rings to the π‐stacking interaction with the peptide bond. These findings provide useful guidelines for enhancing π‐stacking on protein amide fragments.     

A Case Study of the Morphological and Molecular Variation within a Ciliate Genus: Taxonomic Descriptions of Three Dysteria Species (Ciliophora,Cyrtophoria), with the Establishment of a New Species

Three Dysteria species, D. crassipes Claparède & Lachmann, 1859; D. brasiliensis Faria et al., 1922; and D. paracrassipes n. sp., were collected from subtropical coastal waters of the East China Sea, near Ningbo, China. The three species were studied based on their living morphology, infraciliature, and molecular data. The new species D. paracrassipes n. sp. is very similar to D. crassipes in most morphological features except the preoral kinety, which is double-rowed in the new species (vs. single-rowed in D. crassipes). The difference in the small ribosomal subunit sequences (SSU rDNA) between these two species is 56 bases, supporting the establishment of the new species. The Ningbo population of D. crassipes is highly similar in morphology to other known populations. Nevertheless, the SSU rDNA sequences of these populations are very different, indicating high genetic diversity and potentially cryptic species. Dysteria brasiliensis is cosmopolitan with many described populations worldwide and four deposited SSU rDNA sequences. The present work supplies morphological and molecular information from five subtropical populations of D. brasiliensis that bear identical molecular sequences but show significant morphological differences. The findings of this study provide an opportunity to improve understanding of the morphological and genetic diversity of ciliates.     

Study on the induction period of methane aromatization over Mo/HZSM-5: partial reduction of Mo species and formation of carbonaceous deposit

The induction period of dehydrogenation and aromatization of methane over Mo/HZSM-5 was studied by combining a pulse reaction method with TPSR, UV laser Raman, and ¹³C CPMAS NMR techniques. BET and XRD results showed that Mo species were well dispersed on/in the zeolite. TPSR in CH₄ stream revealed that Mo species were reduced in at least two different stages before the formation of benzene. TPR results were in agreement with TPSR results. The two stages might be attributed to the reduction of two kinds of Mo⁶⁺ species to low valence Mo species. One was polymolybdate MoO₃, and the other was crystalline MoO₃. UV Raman spectra showed the existence of octahedrally coordinated polymolybdate species. XRD, however, did not detect any crystalline MoO₃, possibly because they were too small to be detected with this technique. Pulse reaction results indicated that pre-reduction of the catalyst and formation of carbonaceous deposit could shorten the induction period. It is concluded that the formation of active sites during the induction period via partial reduction of Mo⁶⁺ species and formation of carbonaceous deposit on partially reduced Mo species is of significance for methane aromatization over Mo/HZSM-5. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of Reactive Sulfur Species in Cultured Vascular Endothelial Cells after Exposure to TGF-β1: Induction of Cystathionine γ-Lyase and Cystathionine β-Synthase Expression Mediated by the ALK5-Smad2/3/4 and ALK5-Smad2/3-ATF4 Pathways

Transforming growth factor-β₁ (TGF-β₁) occurs at high levels at damage sites of vascular endothelial cell layers and regulates the functions of vascular endothelial cells. Reactive sulfur species (RSS), such as cysteine persulfide, glutathione persulfide, and hydrogen persulfide, are cytoprotective factors against electrophiles such as reactive oxygen species and heavy metals. Previously, we reported that sodium trisulfide, a sulfane sulfur donor, promotes vascular endothelial cell proliferation. The objective of the present study was to clarify the regulation and significance of RSS synthesis in vascular endothelial cells after exposure to TGF-β₁. Bovine aortic endothelial cells in a culture system were treated with TGF-β₁ to assess the expression of intracellular RSS, the effect of RSS on cell proliferation in the presence of TGF-β₁, induction of RSS-producing enzymes by TGF-β₁, and intracellular signal pathways that mediate this induction. The results suggest that TGF-β₁ increased intracellular RSS levels to modulate its inhibitory effect on proliferation. The increased production of RSS, probably high-molecular-mass RSS, was due to the induction of cystathionine γ-lyase and cystathionine β-synthase, which are RSS-producing enzymes, and the induction was mediated by the ALK5-Smad2/3/4 and ALK5-Smad2/3-ATF4 pathways in vascular endothelial cells. TGF-β₁ regulates vascular endothelial cell functions such as proliferation and fibrinolytic activity; intracellular high-molecular-mass RSS, which are increased by TGF-β₁, may modulate the regulation activity in vascular endothelial cells.