Investigating the mechanism of the selective hydrogenation reaction of cinnamaldehyde catalyzed by Pt<Subscript>n</Subscript> clusters

Cinnamaldehyde (CAL) belongs to the group of aromatic α,β-unsaturated aldehydes; the selective hydrogenation of CAL plays an important role in the fine chemical and pharmaceutical industries. Using Pt_n clusters as catalytic models, we studied the selective hydrogenation reaction mechanism for CAL catalyzed by Pt_n (n?=?6, 10, 14, 18) clusters by means of B3LYP in density functional theory at the 6-31+?G(d) level (the LanL2DZ extra basis set was used for the Pt atom). The rationality of the transition state was proved by vibration frequency analysis and intrinsic reaction coordinate computation. Moreover, atoms in molecules theory and nature bond orbital theory were applied to discuss the interaction among orbitals and the bonding characteristics. The results indicate that three kinds of products, namely 3-phenylpropyl aldehyde, 3-phenyl allyl alcohol and cinnamyl alcohol, are produced in the selective hydrogenation reaction catalyzed by Pt_n clusters; each pathway possesses two reaction channels. Pt_n clusters are more likely to catalyze the activation and hydrogenation of the C?=?O bond in CAL molecules, eventually producing cinnamic alcohol, which proves that Pt_n clusters have a strong reaction selectivity to catalyze CAL. The reaction selectivity of the catalyzer cluster is closely related to the size of the Pt_n cluster, with Pt₁₄ clusters having the greatest reaction selectivity.

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Graphical Abstract The reaction mechanism for the selective hydrogenation reaction ofcinnamaldehyde catalyzed by Pt_n clusters was studied by densityfunctional theory. The reactionselectivity of cluster catalyzer was concluded to be closely related to the size of Pt_n clusters, with Pt₁₄ clusters having the greatest reaction selectivity

     

Noble gas supported boron-pentagonal clusters B<Subscript>5</Subscript>Ng<Subscript>n</Subscript><Superscript>3+</Superscript>: exploring the structures and bonding

A novel type of trivalent BNg five-membered cational species B₅Ng_n³⁺(Ng = He~Rn, n = 1~5) has been found and investigated theoretically using the B3LYP and MP2 methods with the def2-QZVPPD and def2-TZVPPD basis sets. The geometry, harmonic vibrational frequencies, bond energies, charge distribution, bond nature, aromaticity, and energy decomposition analysis of these structures were reported. The calculated B?Ng bond energy is quite large (the averaged bond energy is in the range of 209.2~585.76 kJ mol^-1) for heavy rare gases and increases with the Ng atomic number. The analyses of the molecular wavefunction show that in the BNg compounds of heavy Ng atoms Ar~Rn, the B?Ng bonds are of typical covalent character. Nuclear independent chemical shifts display that both B₅³⁺ and B₅Ng_n³⁺(n=1~5) have obvious aromaticity. Energy decomposition analysis shows that these BNg compounds are mainly stabilized by the σ-donation from the Ng valence p orbital to the B₅³⁺ LUMO. These findings offer valuable clues toward the design and synthesis of new stable Ng-containing compounds.     

Architectures,electronic structures,and stabilities of Cu-doped Ge<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> clusters: density functional modeling

The present study reports the geometries, electronic structures, growth behavior, and stabilities of neutral and ionized copper-doped germanium clusters containing 1–20 Ge atoms within the framework of linear combination of atomic orbitals density functional theory (DFT) under the spin-polarized generalized gradient approximation. It was found that Cu-capped Ge _n (or Cu-substituted Ge _n+1) and Cu-encapsulated Ge _n clusters mostly occur in the ground state at a particular cluster size (n). In order to explain the relative stabilities of the ground-state clusters, parameters such as the average binding energy per atom (BE), the embedding energy (EE), and the fragmentation energy (FE) of the clusters were calculated, and the resulting values are discussed. To explain the chemical stabilities of the clusters, parameters such as the energy gap between the highest occupied and the lowest unoccupied molecular orbitals (the HOMO–LUMO gap), the ionization energy (IP), the electron affinity (EA), the chemical potential (μ), the chemical hardness (η), and the polarizability were calculated, and the resulting values are also discussed. Natural atomic orbital (NAO) and natural bond orbital (NBO) analyses were also used to determine the electron-counting rule that should be applied to the most stable Ge₁₀Cu cluster. Finally, the relevance of the calculated results to the design of Ge-based superatoms is discussed.

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Figure Contributions of the valance orbitals of the Ge and Cu atom(s) to the HOMO of the ground-state icosahedral Ge₁₀Cu cluster obtained from NBO analysis. The numbers below the clusters represent the occupancies of the HOMO orbitals

     

Adsorption and phase transitions in adsorbed systems: structural properties of CCl<Subscript>4</Subscript> layers adsorbed on a graphite surface

We present the results of simulations of a CCl₄ monolayer adsorbed on a graphite surface. The CCl₄ molecule was represented either by a shapeless superatom or by its atomic sites. The simulations were carried out over a large range of temperatures, from 20 K up to 340 K. We address the following problems: (1) the influence of molecular shape on the structure and stability of phases (particularly at low temperatures), and (2) the influence of the graphite corrugation on layer stability and mechanism of phase transitions. In particular, we discuss the possibility and conditions of the appearance of hexatic phase in the system. Figure Temperature dependence of Φ6 order parameter for CCl₄ monolayer adsorbed onsmooth and corrugated surfaces, in the spherical Lennard Jones (LJ) approximation.For comparison, the order parameter calculated for MacDonald’s five-site potential is also presented     

Distribution of telomeric (TTAGGG)<Subscript>n</Subscript> sequences in avian chromosomes

The physical ends of mammalian and other vertebrate chromosomes consist of tandemly repeated (TTAGGG)(n) hexamers, nucleating a specialized telomeric structure. However, (TTAGGG)(n) sequences can also occur at non-telomeric sites, providing important insights into karyotypic evolution. By fluorescence in situ hybridization (FISH) we studied the chromosomal distribution of (TTAGGG)(n) sequences in 16 bird species, representing seven different orders. Many species, in particular the ratites, display (TTAGGG)(n) hybridization signals in interstitial and centromeric regions of their macrochromosomes in addition to the typical telomeric signals. In some but not all species these non-telomeric sites coincide with C-band-positive heterochromatin. The retention and/or amplification of telomeric (TTAGGG)(n) repeats at interstitial and centromeric sites may indicate the fusion of ancestral chromosomes. Compared with the macrochromosomes, the microchromosomes of most species are enriched with (TTAGGG)(n) sequences, displaying heterogeneous hybridization patterns. We propose that this high density of (TTAGGG)(n) repeats contributes to the exceptionally high meiotic recombination rate of avian microchromosomes.     

Electrochemical oxygen reduction mechanism on FeN<Subscript>2</Subscript>-graphene

Metal-coordinated nitrogen-doped carbons are highly active in promoting electrochemical oxygen reduction reactions (ORR). The detailed kinetic and thermodynamic ORR behavior on three different FeN₂-graphene [FeN₂–G (A), (B) and (C)] structures was investigated in this work. The results show that formation of these FeN₂–G configurations is energetically favorable; however, not all of them are effective for ORR. The higher HOMO energy and smaller HOMO–LUMO gap of FeN₂–G (A) and (C) make them have strong adsorption strengths to ORR intermediates, which leads to occupation the active sites on the catalysts during ORR, and thus loss of catalytic activity. Examination of the results of ?G of each reduction step also drew the same conclusion. The ?G of the elementary steps of the ORR at zero electrode potential vs. standard hydrogen electrode are downhill only on FeN₂–G (B). Throughout the entire four-electron ORR, the reduction of O to OH displays the highest reaction barrier. When the potential is >0.19 V, the reduction of OH species into water is uphill. Therefore, ORR activity is limited by two rate-determining steps on FeN₂–G (B) at high potential: O and OH reduction steps.     

Phenol and <Emphasis Type="Italic">n</Emphasis>-alkanes (C<Subscript>12</Subscript> and C<Subscript>16</Subscript>) utilization: influence on yeast cell surface hydrophobicity

This study was focused on the role of two types of diametrically different carbon sources, n-alkanes represented by a mixture of dodecane–hexadecane, and phenol on modification of the cell surface hydrophobicity. Capabilities of using either solely hydrocarbons or hydrocarbons in the mixture with phenol as well as phenol itself by yeast species Candida maltosa, Yarrowia lipolytica and Pichia guilliermondii were investigated. Studies were complemented by cell biomass formation measurements. The corresponding cell surface hydrophobicity was assessed by microbial adhesion to the hydrocarbon test (MATH). Degradation of phenol was examined using GC-SPE technique, whereas hydrocarbons were extracted prior to gravimetric determination. Results obtained indicated that the hydrophobic or hydrophilic nature of the carbon source had significant influence on the cell surface hydrophobicity. Although the results differed for some individual yeast strains, the generalization can be made that there is the correlation between the best hydrocarbon and phenol degradation and corresponding cell wall properties of the yeast examined.     

Ab initio study of MKr<Stack><Subscript>n</Subscript><Superscript>2+</Superscript></Stack>(M = Cu,Ag, and Au,n = 1-6) clusters

Quantum chemical calculations of the structures and stabilities of the title series at the CCSD(T) theoretical level are performed. Laplacian, electron density deformation, electron localization function and reduced density gradient analysis are investigated to explore the nature of the interaction. The results show that a covalent contribution occurs in the Kr-M²⁺ bonding.     

Immobilization of glucose oxidase on Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> magnetic nanoparticles

Glucose oxidase (GOD) was covalently immobilized onto Fe₃O₄/SiO₂ magnetic nanoparticles (FSMNs) using glutaraldehyde (GA). Optimal immobilization was at pH 6 with 3-aminopropyltriethoxysilane at 2% (v/v), GA at 3% (v/v) and 0.143 g GOD per g carrier. The activity of immobilized GOD was 4,570 U/g at pH 7 and 50°C. The immobilized GOD retained 80% of its initial activity after 6 h at 45°C while free enzyme retained only 20% activity. The immobilized GOD maintained 60% of its initial activity after 6 cycles of repeated use and retained 75% of its initial activity after 1 month at 4°C whereas free enzymes retained 62% of its activity.     

Effects of CO/CO<Subscript>2</Subscript>/NO on elemental lead adsorption on carbonaceous surfaces

The adsorption processes of elemental lead on carbonaceous surfaces which adsorbed CO/CO₂/NO flue gases were investigated to understand the effects of CO/CO₂/NO on elemental lead adsorption on carbonaceous surfaces with density functional theory. All calculations including optimizations, energies, and frequencies were conducted at B3PW91 density functional theory level, utilizing SDD basis set for lead and 6-31G(d) Pople basis set for other atoms. The results indicate that CO, CO₂, and NO can promote the adsorption of elemental lead on the carbonaceous surface, but probably compete for adsorption sites with elemental lead. The promotion effects on adsorption can be attributed to active sites on the carbonaceous surface rather than flue gas adsorption on the carbonaceous surface. In addition, the adsorption order of three kinds of flue gas on the carbonaceous surface is CO₂?>?NO?>?CO?>?Pb on average. Furthermore, the enhancement order of three kinds of flue gas on the elemental lead adsorption on carbonaceous surfaces is CO-CS?>?CO₂-CS?>?NO-CS?>?CS in general. In particular, atomic charge and adsorption energy have good linear relationship in the process of elemental lead adsorption.

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Graphical Abstract Competitive adsorption between flue gas and elemental lead on carbonaceous surfaces.

     

The encapsulated lithium effect on the first hyperpolarizability of C<Subscript>60</Subscript>Cl<Subscript>2</Subscript> and C<Subscript>60</Subscript>F<Subscript>2</Subscript>

In this paper, we report a study on the structure and first hyperpolarizability of C₆₀Cl₂ and C₆₀F₂. The calculation results show that the first hyperpolarizabilities of C₆₀Cl₂ and C₆₀F₂ were 172 au and 249 au, respectively. Compared with the fullerenes, the first hyperpolarizability of C₆₀Cl₂ increased from 0 au to 172 au, while the first hyperpolarizability of C₆₀F₂ increased from 0 au to 249 au. In order to further increase the first hyperpolarizability of C₆₀Cl₂ and C₆₀F₂, Li@C₆₀Cl₂ and Li@C₆₀F₂ were obtained by introducing a lithium atom to C₆₀Cl₂ and C₆₀F₂. The first hyperpolarizabilities of Li@C₆₀Cl₂ and Li@C₆₀F₂ were 2589 au and 985 au, representing a 15-fold and 3.9-fold increase, respectively, over those of C₆₀Cl₂ and C₆₀F₂. The transition energies of four molecules (C₆₀Cl₂, Li@C₆₀Cl₂, C₆₀F₂, Li@C₆₀F₂) were calculated, and were found to be 0.17866 au, 0.05229 au, 0.18385 au, and 0.05212 au, respectively. A two-level model explains why the first hyperpolarizability increases for Li@C₆₀Cl₂ and Li@C₆₀F₂.     

The influence of Sc doping on structural,electronic and optical properties of Be<Subscript>12</Subscript>O<Subscript>12</Subscript>, Mg<Subscript>12</Subscript>O<Subscript>12</Subscript> and Ca<Subscript>12</Subscript>O<Subscript>12</Subscript> nanocages: a DFT study

Density functional theory (DFT) calculations were used to study the effect of scandium doping on the structural, energetic, electronic, linear and nonlinear optical (NLO) properties of Be₁₂O₁₂, Mg₁₂O₁₂ and Ca₁₂O₁₂ nanoclusters. Scandium (Sc) doping on nanoclusters leads to narrowing of their E _g, which enhances their conductance greatly. Also, the polarizability (α) and first hyperpolarizability (β₀) of nanoclusters were dramatically increased as Be, Mg or Ca atoms are substituted with a Sc atom. Among all clusters, α and β₀ values for Sc-doped Ca₁₂O₁₂ were the largest. Consequently, the effect of the doping atom, as well as of cluster size, on electronic and optical properties was explored. Time dependent (TD)-DFT calculations were also carried out to confirm the β₀ values; the results show that the higher value of first hyperpolarizability belongs to Sc-doped Ca₁₂O₁₂, which has the smallest transition energy (ΔEgn). The results obtained show that these clusters can be candidates for using in electronic devices and NLO materials in industry.     

Effects of elevated atmospheric CO<Subscript>2</Subscript> on the nutritional ecology of C<Subscript>3</Subscript> and C<Subscript>4</Subscript> grass-feeding caterpillars

It is plausible that the nutritional quality of C₃ plants will decline more under elevated atmospheric CO₂ than will the nutritional quality of C₄ plants, causing herbivorous insects to increase their feeding on C₃ plants relative to C₄ plants. We tested this hypothesis with a C₃ and C₄ grass and two caterpillar species with different diet breadths. Lolium multiflorum (C₃) and Bouteloua curtipendula (C₄) were grown in outdoor open top chambers at ambient (370 ppm) or elevated (740 ppm) CO₂. Bioassays compared the performance and digestive efficiencies of Pseudaletia unipuncta (a grass-specialist noctuid) and Spodoptera frugiperda (a generalist noctuid). As expected, the nutritional quality of L. multiflorum changed to a greater extent than did that of B. curtipendula when grown in elevated CO₂; levels of protein (considered growth limiting) declined in the C₃ grass, while levels of carbohydrates (sugar, starch and fructan) increased. However, neither insect species increased its feeding rate on the C₃ grass to compensate for its lower nutritional quality when grown in an elevated CO₂ atmosphere. Consumption rates of P. unipuncta and S. frugiperda were higher on the C₃ grass than the C₄ grass, the opposite of the result expected for a compensatory response to the lower nutritional quality of the C₄ grass. Although our results do not support the hypothesis that grass-specialist insects compensate for lower nutritional quality by increasing their consumption rates more than do generalist insects, the performance of the specialist was greater than that of the generalist on each grass species and at both CO₂ levels. Mechanisms other than compensatory feeding, such as increased nutrient assimilation efficiency, appear to determine the relative performance of these herbivores. Our results also provide further evidence against the hypothesis that C₄ grasses would be avoided by insect herbivores because a large fraction of their nutrients is unavailable to herbivores. Instead, our results are consistent with the hypothesis that C₄ grasses are poorer host plants primarily because of their lower nutrient levels, higher fiber levels, and greater toughness.     

Selective effects of H<Subscript>2</Subscript>O<Subscript>2</Subscript> on cyanobacterial photosynthesis

The sensitivity of phytoplankton species for hydrogen peroxide (H₂O₂) was analyzed by pulse amplitude modulated (PAM) fluorometry. The inhibition of photosynthesis was more severe in five tested cyanobacterial species than in three green algal species and one diatom species. Hence the inhibitory effect of H₂O₂ is especially pronounced for cyanobacteria. A specific damage of the photosynthetic apparatus was demonstrated by changes in 77 K fluorescence emission spectra. Different handling of oxidative stress and different cell structure are responsible for the different susceptibility to H₂O₂ between cyanobacteria and other phytoplankton species. This principle may be potentially employed in the development of new agents to combat cyanobacterial bloom formation in water reservoirs.     

The polythiophene molecular segment as a sensor model for H<Subscript>2</Subscript>O,HCN, NH<Subscript>3</Subscript>, SO<Subscript>3</Subscript>, and H<Subscript>2</Subscript>S: a density functional theory study

Studying the interaction of some atmospheric gases (H₂O, HCN, NH₃, SO₃ and H₂S) with 3PT oligomers is important in the development of polymeric sensors for gas detection. In the present study, we studied the relaxed geometries, interaction energies, charge analysis, HOMO–LUMO orbital analysis, and UV–vis spectra of all interacted systems using first-principles density functional theory (DFT). All these analyses indicated the potential of polythiophene as an inexpensive polymeric sensor for the analytes mentioned. Interaction energy values of ?19.90, ?19.66, ?14.01, ?8.70, and ?4.76 kJ mol^?1 were achieved for adsorption of SO₃, H₂O, NH₃, HCN, and H₂S on 3PT, respectively. Consequently, clarification of their physical parameters became the major focus of this study.     

Calculations of the C<Subscript>2</Subscript> fragmentation energies of higher fullerenes C<Subscript>80</Subscript> and C<Subscript>82</Subscript>

The C₂ fragmentation energies of the most stable isolated-pentagon-rule (IPR) isomers of the C₈₀ and C₈₂ fullerenes were evaluated with second-order Møller-Plesset (MP2) theory, density-functional theory (DFT) and the semiempirical self-consistent charge density-functional tight-binding (SCC-DFTB) method. Zero-point energy, ionization energy and empirical C₂ corrections were included in the calculation of fragmentation energies for comparison with experimental C₂ fragmentation energies of the fullerene cations. In the case of the most probable Stone-Wales pathway of C₂ fragmentation of C₈₀, the calculated \(D_{0} {\left( {{\text{C}}_{{{\text{80}}}} ^{ + } } \right)}\) agree well with experimental data, whereas in the case of C₈₂ fragmentation, the calculated \(D_{0} {\left( {{\text{C}}_{{{\text{82}}}} ^{ + } } \right)}\) exceed by up to 1.2 eV the experimental ones, which suggests that other IPR isomers may be present in sufficient amounts in experimental samples. Computer-intensive MP2 calculations and DFT calculations with larger basis sets do not yield much improved C₂ fragmentation energies, compared to those reported earlier with B3LYP/3-21G. On the other hand, semiempirical approaches such as SCC-DFTB, which are orders of magnitude less intensive, yield satisfactory fragmentation energies for higher fullerenes and may become a method of choice for routine calculations of fullerenes and carbon nanotubes.

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Figure C₂ fragmentation energies of C₈₀ and C₈₂ fullerenes have been calculated with B3LYP/6-31G* model chemistry, with semiempirical self-consistent-charge density-functional tight-binding (SCC-DFTB) method and with the more rigorous MP2 method. The influence of basis set extension and level of theory on the resulting fragmentation energies is discussed

     

Effect of Prostaglandins E<Subscript>1</Subscript> and F<Subscript>1α</Subscript> on Biosynthesis of Collagen

THE prostaglandins (PG) are possible mediators of inflammation. Prostaglandins E and F are present in inflammatory exudates^1–3 and could be related to the increase of collagen biosynthesis associated with inflammation. Vane and his colleagues^4–6 recently observed that indomethacin, aspirin and sodium salicylate potently block the biosynthesis of prostaglandins. These anti-inflammatory drugs are also inhibitors of collagen biosynthesis^7,8. Morphological studies⁹ have revealed increased deposition of collagen or collagen-related elements in organ cultures of chick embryo skin containing prostaglandins E₁ and B₁. We report here results which indicate stimulation of collagen biosynthesis by prostaglandins E₁ and F_1α evaluated by hydroxylation of proline and lysine and glycosylation of hydroxylysine in 10 day chick embryo tibiae.     

Effects of exogenous H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the content of endogenous H<Subscript>2</Subscript>O<Subscript>2</Subscript>, activities of catalase and hydrolases,and cell ultrastructure in tobacco leaves

It was shown that tobacco leaf treatment with 100 mM H₂O₂ increased their content of endogenous H₂O₂ and activities of catalase and hydrolases (acid phosphatase, proteases, and RNase) and also caused various changes in the cell structure. In this case, programmed cell death (PCD) occurred in some cells, which was observed as chromatin condensation, cytoplasm collapse, etc. In the meantime, many cells displayed organelle activation rather than PCD. It is suggested that cells that undergo H₂O₂-dependent PCD release signaling molecules inducing protective mechanisms against oxidative stress in neighboring cells not exhibiting PCD.     

Characterization of Myelin Sheath F<Subscript>o</Subscript>F<Subscript>1</Subscript>-ATP Synthase and its Regulation by IF<Subscript>1</Subscript>

F_oF₁-ATP synthase is the nanomotor responsible for most of ATP synthesis in the cell. In physiological conditions, it carries out ATP synthesis thanks to a proton gradient generated by the respiratory chain in the inner mitochondrial membrane. We previously reported that isolated myelin vesicles (IMV) contain functional F_oF₁-ATP synthase and respiratory chain complexes and are able to conduct an aerobic metabolism, to support the axonal energy demand. In this study, by biochemical assay, Western Blot (WB) analysis and immunofluorescence microscopy, we characterized the IMV F_oF₁-ATP synthase. ATP synthase activity decreased in the presence of the specific inhibitors (olygomicin, DCCD, FCCP, valynomicin/nigericin) and respiratory chain inhibitors (antimycin A, KCN), suggesting a coupling of oxygen consumption and ATP synthesis. ATPase activity was inhibited in low pH conditions. WB and microscopy analyses of both IMV and optic nerves showed that the Inhibitor of F₁ (IF₁), a small protein that binds the F₁ moiety in low pH when of oxygen supply is impaired, is expressed in myelin sheath. Data are discussed in terms of the role of IF₁ in the prevention of the reversal of ATP synthase in myelin sheath during central nervous system ischemic events. Overall, data are consistent with an energetic role of myelin sheath, and may shed light on the relationship among demyelination and axonal degeneration.