Substituted six-membered ring carbenes: the effects of amino and cyclopropyl groups through DFT calculations

DFT calculations are employed to compare and contrast six-membered ring carbenes including 1,3-dimethyltetrahydropyrimidin-2-ylidene (1a), 1-methyl-3-cyclopropyltetrahydropyridine-2-ylidene (2a), and 1,3-dicyclopropylcyclohexane-2-ylidene (3a) as well as their unsaturated analogues 1b, 2b, 3b, and 2c. The amino groups exert singlet-triplet energy separation (?E_s−t) of 60.9 kcal/mol to 1a while cyclopropyls induce a ?E_s−t of 14.8 kcal/mol to 3a. The simultaneous presence of amino and cyclopropyl in 2a leads to a ?E_s−t of 43.3 kcal/mol. Unsaturation slightly increases the ?E_s−t of 1a and 3a but not that of 2a. Our thermodynamic, kinetic, and reactivity results are compared with those of synthetic five-membered ring N-heterocyclic carbenes.     

Role of Zr4+ cations in NO2 adsorption on Ce(1-x)Zr(x)O2 mixed oxides at ambient conditions

Mixed oxides Ce(1-x)Zr(x)O(2) prepared by slow coprecipitation in NaOH were tested for NO(2) adsorption in dynamic conditions at room temperature. The samples were characterized before and after exposure to NO(2) by XRD, N(2)-adsorption, thermal analysis, potentiometric titration, and FT-IR. Mixed oxides show a better NO(2) adsorption capacity than the parent materials (CeO(2) and Zr(OH)(4)). This effect is linked to the presence of reduced cerium and oxygen vacancies induced by the addition of Zr(4+) cations to the structure. The results indicate that NO(2) reacts with Ce(3+) to form nitrite and nitrate species on the surface. The NO retention increases with an increase in the Zr(OH)(4) content. A decrease in the density of -OH groups on the surface after the exposure to NO(2), suggests their involvement in reactive adsorption of NO and/or NO(2). From the structural point of view, no real difference was observed on the Ce(1-x)Zr(x)O(2) materials before and after exposure to NO(2).     

Synthesis, characterization, mechanochromism and photochromism of [Fe(dm4bt)3][FeCl4]2 and [Fe(dm4bt)3][FeBr4]2, along with the investigation of steric influence on spin state

The complexes [Fe(dm4bt)(3)][FeCl(4)](2) (1) and [Fe(dm4bt)(3)][FeBr(4)](2) (2) were prepared from the reaction of 2,2'-dimethyl-4,4'-bithiazole (dm4bt) with FeCl(3)·6H(2)O and FeBr(3), respectively, in methanol. Both complexes were characterized by IR, UV-Vis and (1)H NMR spectroscopy and their structures were studied by single-crystal diffraction. The methylated bithiazole led to high spin Fe(II) centers in the octahedral cation part of complexes 1 and 2 with Fe-N distance of 2.220 ?, in spite of the low spin octahedral Fe(II) complexes with unsubstituted bithiazole ligands. Crystal structure determination of 2 was performed at 90, 120 and 298 K. Temperature reduction to 90 K resulted in a decrease in the Fe-N bond length to 2.206 ? which is still in the range of high spin Fe(II). Complex 1 shows a reversible mechanochromic effect from the crystalline phase to powder form from red to yellow; it also displays reversible photochromism from yellow to green in solution under sunlight. The magnetic behaviour of the complexes was also studied at 2-300 K. The temperature dependence of χ(m)T curves for the two forms of 1, crystal and powder, demands some changes in their magnetic behavior, causing different colors i.e. red and yellow. At low temperatures, χ(m)T decreases where the decrease starts at around 65 K for compound 1, and at around 100 K for compound 2, due to different counterions. The two complexes exhibit antiferromagnetism at around 4 K.     

Newtonian and Shear-thinning Taylor flow heat transfer in wavy micro-tubes: a numerical study

Meccanica - In the present study, the two-phase gas–liquid convective heat transfer is numerically studied inside uniformly heated wavy micro-tubes in the Taylor flow regime. Both Newtonian...     

Solvent-free and room temperature synthesis of thiochromans in the presence of a catalytic amount of tungstophosphoric acid

Tungstophosphoric acid catalyzed rapid and good yielding reactions of α,β-unsaturated aldehydes with arenethiols to give the corresponding 4-thioaryl-1,2,3,4-tetrahydro-1-benzothiopyrans (thiochromans) under solvent-free and room temperature conditions.     

An efficient PDF calculation of flame temperature and major species in turbulent non-premixed flames

In spite of recent developments in the PDF calculations of turbulent flames, the high computational time required to implement PDF simulations makes it intractable in practical applications. Therefore, it is important to design and select different parameters for PDF calculation of most important quantities, i.e. temperature and major species means, in an efficient manner. The ingredients of the present model are a standard k$k$–ε$\epsilon$ turbulence closure for modeling flow field and a joint composition PDF closure for the scalar fields. A modified Curl model is applied to consider molecular mixing in PDF transport equation and a simplified two-step mechanism which lowers the computational cost is incorporated to describe the chemistry. The flow field is solved numerically using an upwind discretization for the convective terms and a central discretization for the diffusion terms by coupling it with an Eulerian Monte Carlo algorithm to solve PDF transport equation. To show the superiority of the current PDF calculations over traditional moment-closure methods commonly used in practical applications, simulation is also performed by RANS method which shows large discrepancies, especially in prediction of maximum flame temperature (on the basis of present results, predicted flame temperature has 26%$26\%$ error via RANS method and 8%$8\%$ error via PDF method). Stoichiometric flame length predicted by RANS has 10%$10\%$ error while, by PDF method, this error is negligible and about 0.6%$0.6\%$. The effect of coefficient _CΦ$C_{\Phi }$ on the modified Curl model is also investigated and it is concluded that the commonly used value _CΦ=2.0$C_{\Phi }=2.0$ is the best choice for the case of study. The numerical results obtained reveal that Westbrook–Drier mechanism is working very well in fuel-lean (F<_Fst$F<F_{\mathit{st}}$) non-premixed combustion and also it predicts the total heat released in methane combustion in a very good agreement with the experiment.     

Bone regeneration based on nano-hydroxyapatite and hydroxyapatite/chitosan nanocomposites: an in vitro and in vivo comparative study

Surface morphology, surface wettability, and size distribution of biomaterials affect their in vitro and in vivo bone regeneration potential. Since nano-hydroxyapatite has a great chemical and structural similarity to natural bone and dental tissues, incorporated biomaterial of such products could improve bioactivity and bone bonding ability. In this research, nano-hydroxyapatite (23 ± 0.09 nm) and its composites with variety of chitosan content [2, 4, and 6 g (45 ± 0.19, 32 ± 0.12, and 28 ± 0.12 nm, respectively)] were prepared via an in situ hybridization route. Size distribution of the particles, protein adsorption, and calcium deposition of powders by the osteoblast cells, gene expression and percentage of new bone formation area were investigated. The highest degree of bone regeneration potential was observed in nano-hydroxyapatite powder, while the bone regeneration was lowest in nano-hydroxyapatite with 6 g of chitosan. Regarding these data, suitable size distribution next to size distribution of hydroxyapatite in bone, smaller size, higher wettability, lower surface roughness of the nano-hydroxyapatite particles and homogeneity in surface resulted in higher protein adsorption, cell differentiation and percentage of bone formation area. Results obtained from in vivo and in vitro tests confirmed the role of surface morphology, surface wettability, mean size and size distribution of biomaterial besides surface chemistry as a temporary bone substitute.     

Nylon Intermediates from Bio‐Based Levulinic Acid

Use of ZrO₂/SiO₂ as a solid acid catalyst in the ring‐opening of biobased γ‐valerolactone with methanol in the gas phase leads to mixtures of methyl 2‐, 3‐, and 4‐pentenoate (MP) in over 95 % selectivity, containing a surprising 81 % of M4P. This process allows the application of a selective hydroformylation to this mixture to convert M4P into methyl 5‐formyl‐valerate (M5FV) with 90 % selectivity. The other isomers remain unreacted. Reductive amination of M5FV and ring‐closure to ?‐caprolactam in excellent yield had been reported before. The remaining mixture of 2‐ and 3‐MP was subjected to an isomerising methoxycarbonylation to dimethyl adipate in 91 % yield.     

An efficient one‐pot procedure for the preparation of 1,3,4‐thiadiazoles in ionic liquid [bmim]BF4 as dual solvent and catalyst

The one‐pot three component condensation of hydrazine hydrate with substituted phenylisothiocyanates followed by the addition of substituted benzaldehydes in the presence of ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄) and in the absence of any other catalyst under mild condition afforded 1,3,4‐thiadiazoles in excellent yields. The reaction workup is simple, and the ionic liquid was easily recovered from the reaction and reused. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:320–324, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20432     

Kinetic study of hydrogen sulfide decomposition on Pt(111) surface

In this work, kinetic of H₂S conversion to H₂ molecule on the surface of Pt(111) is studied using kinetic Monte Carlo simulation. The results of simulation were fitted to the experimental temperature-programed desorption spectra. The good agreement between the empirical and the simulated data confirms the proposed mechanism and kinetic data (activated energies and pre-exponential factors). The influence of variables such as temperature and concentrations of H₂S and H₂ on the overall results of hydrogen production is studied. The condition is proposed in which the best yield of reaction at minimum temperature is obtained. Results show that platinum is a perfect catalyst for converting H₂S to H₂ and it has a perfect performance (98%) after 5 μs at low temperature of 227°C.