Negative thermal expansion of water in hydrophobic nanospaces

The density and intermolecular structure of water in carbon micropores (w = 1.36 nm) are investigated by small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) measurements between 20 K and 298 K. The SAXS results suggest that the density of the water in the micropores increased with increasing temperature over a wide temperature range (20-277 K). The density changed by 10%, which is comparable to the density change of 7% between bulk ice (I(c)) at 20 K and water at 277 K. The results of XRD at low temperatures (less than 200 K) show that the water forms the cubic ice (I(c)) structure, although its peak shape and radial distribution functions changed continuously to those of a liquid-like structure with increasing temperature. The SAXS and XRD results both showed that the water in the hydrophobic nanospaces had no phase transition point. The continuous structural change from ice I(c) to liquid with increasing temperature suggests that water shows negative thermal expansion over a wide temperature range in hydrophobic nanospaces. The combination of XRD and SAXS measurements makes it possible to describe confined systems in nanospaces with intermolecular structure and density of adsorbed molecular assemblies.     

Chiral-Sc catalyzed asymmetric Michael addition/protonation of thiols with enones in water

Asymmetric Michael reactions and enantioselective protonations between enones and thiols were catalyzed by a Sc(OTf)(3)-chiral 2,2'-bipyridine complex in water. The remarkable governing of the enantioselectivity for simple introduction of protons despite their abnormally high mobility in water may provide us with new synthetic opportunities as well as significant chemical advances.     

New type of azacyclization: thermal preparation of 4,6-disubstituted 2-piperidinone from N-sulfonyldienamide and its substituent effect

The thermal 6-endo cyclization of N-sulfonyl-2,4-dienamide compounds to produce 4,6-disubstituted 2-piperidinone is described. The observed remarkable substituent effect due to the N-sulfonyl and C3 ethoxycarbonyl groups for acceleration of this 6-endo cyclization strongly suggests that the reaction would proceed via the 6π-azaelectrocyclization of the intermediary imidic acid. On the contrary, the corresponding 5-formyl and 5-acetyl derivatives rapidly cyclized at room temperature to produce the 5-exo cyclized products.     

Global Compensated Compactness Theorem for General Differential Operators of First Order

Let A ₁(x, D) and A ₂(x, D) be differential operators of the first order acting on l-vector functions ${u= (u_1, \ldots, u_l)}$ in a bounded domain ${\Omega \subset \mathbb{R}^{n}}$ with the smooth boundary ${\partial\Omega}$ . We assume that the H ¹-norm ${\|u\|_{H^{1}(\Omega)}}$ is equivalent to ${\sum_{i=1}^2\|A_iu\|_{L^2(\Omega)} + \|B_1u\|_{H^{\frac{1}{2}}(\partial\Omega)}}$ and ${\sum_{i=1}^2\|A_iu\|_{L^2(\Omega)} + \|B_2u\|_{H^{\frac{1}{2}}(\partial\Omega)}}$ , where B _i  = B _i (x, ν) is the trace operator onto ${\partial\Omega}$ associated with A _i (x, D) for i = 1, 2 which is determined by the Stokes integral formula (ν: unit outer normal to ${\partial\Omega}$ ). Furthermore, we impose on A ₁ and A ₂ a cancellation property such as ${A_1A_2^{\prime}=0}$ and ${A_2A_1^{\prime}=0}$ , where ${A^{\prime}_i}$ is the formal adjoint differential operator of A _i (i = 1, 2). Suppose that ${\{u_m\}_{m=1}^{\infty}}$ and ${\{v_m\}_{m=1}^{\infty}}$ converge to u and v weakly in ${L^2(\Omega)}$ , respectively. Assume also that ${\{A_{1}u_m\}_{m=1}^{\infty}}$ and ${\{A_{2}v_{m}\}_{m=1}^{\infty}}$ are bounded in ${L^{2}(\Omega)}$ . If either ${\{B_{1}u_m\}_{m=1}^{\infty}}$ or ${\{B_{2}v_m\}_{m=1}^{\infty}}$ is bounded in ${H^{\frac{1}{2}}(\partial\Omega)}$ , then it holds that ${\int_{\Omega}u_m\cdot v_m \,{\rm d}x \to \int_{\Omega}u\cdot v \,{\rm d}x}$ . We also discuss a corresponding result on compact Riemannian manifolds with boundary.     

Towards the development of an efficient low-NOx ammonia combustor for a micro gas turbine

Recent studies have demonstrated stable generation of power from pure ammonia combustion in a micro gas turbine (MGT) with a high combustion efficiency, thus overcoming some of the challenges that discouraged such applications of ammonia in the past. However, achievement of low NOx emission from ammonia combustors remains an important challenge. In this study, combustion techniques and combustor design for efficient combustion and low NOx emission from an ammonia MGT swirl combustor are proposed. The effects of fuel injection angle, combustor inlet temperature, equivalence ratio, and ambient pressure on flame stabilization and emissions were investigated in a laboratory high pressure combustion chamber. An FTIR gas analyser was employed in analysing the exhaust gases. Numerical modeling using OpenFOAM was done to better understand the dependence of NO emissions on the equivalence ratio. The result show that inclined fuel injection as opposed to vertical injection along the combustor central axis resulted to improved flame stability, and lower NH₃ and NOx emissions. Numerical and experimental results showed that a control of the equivalence ratio upstream of the combustor is critical for low NOx emission in a rich-lean ammonia combustor. NO emission had a minimum value at an upstream equivalence ratio of 1.10 in the experiments. Furthermore, NO emission was found to decrease with ambient pressure, especially for premixed combustion. For the rich-lean combustion strategy employed in this study, lower NOx emission was recorded in premixed combustion than in non-premixed combustion indicating the importance of mixture uniformity for low NOx emission from ammonia combustion. A prototype liner developed to enhance the control and uniformity of the equivalence ratio upstream of the combustor further improved ammonia combustion. With the proposed liner design, NOx emission of 42?ppmv and ammonia combustion efficiency of 99.5% were achieved at 0.3?MPa for fuel input power of 31.44?kW.     

Quantum phase transition in the itinerant antiferromagnet (V0.9Ti0.1)2O3

Quantum-critical behavior of the itinerant electron antiferromagnet (V0.9Ti0.1)2O3 has been studied by single-crystal neutron scattering. By directly observing antiferromagnetic spin fluctuations in the paramagnetic phase, we have shown that the characteristic energy depends on temperature as c1 +c2T3/2, where c1 and c2 are constants. This T3/2 dependence demonstrates that the present strongly correlated d-electron antiferromagnet clearly shows the criticality of the spin-density-wave quantum phase transition in three space dimensions.     

Formation of Anatase Nanocrystals in Sol-Gel Derived TiO2-SiO2 Thin Films with Hot Water Treatment

We have successfully prepared transparent and porous anatase nanocrystals-dispersed films by treating the sol-gel derived TiO₂-SiO₂ films containing poly(ethylene glycol), PEG, with hot water. This process was done at temperatures lower than 100°C under atmospheric pressure, and thus anatase nanocrystals-dispersed films can be formed on various kinds of substrates including organic polymers with poor heat resistance. The changes in structure and composition of the TiO₂-SiO₂ gel films with hot water treatment were related to the formation process of anatase nanocrystals in the TiO₂-SiO₂ gel films with hot water treatment. The formation of anatase nanocrystals was found to proceed to hydrolysis of Si–O–Ti bonds and dissolution of SiO₂ component. In addition, porous film structure formed by leaching of PEG with hot water treatment led to homogenous dispersion of anatase nonocrystals in the films.     

Efficient synthesis of cyclopropylhydrazine salts

An efficient procedure for the synthesis of cyclopropylhydrazine in the form of its salts is reported. The copper salt-catalyzed addition of cyclopropylboronic acid to the azo group of di-tert-butyl azodicarboxylate and subsequent deprotection gave the cyclopropylhydrazine salts in high yields.     

A link between quantum and classical Potts models

We study ground states of quantum Potts models. We construct ground states of certaind-dimensional quantum models as Gibbs measures of ad-dimensional classical spin system. Our results imply that various phenomena of classical spin systems can also be found in quantum ground states.     

Quadratic nonlinear optical properties of ruthenium (II)-bipyridine complexes in crystalline powders

Quadratic nonlinear optical properties for the crystalline powders of two types of ruthenium-bipyridine [Ru(bipy)₃] complexes were investigated. The nonlinear optical processes markedly depended on the molecular structures of the ruthenium complexes. Second harmonic generation (SHG) and very weak two-photon emission were observed for the alkylated ruthenium-bipyridine compexes with two long alkyl chains attached via amide bonds (RuC_nB), whereas only two-photon emission was observed for Ru(bipy)₃. The existence of two amide bonds in one bipyridine ligand for RuC_nB complexes most probably enhanced the molecular hyperpolarizability as compared with Ru(bipy)₃. The SHG intensity from RuC_nB complexes increased in the order RuC₁₈B < RuC₁₂B < RuC₁₆B. The order of SHG intensity from RuC_nB was ascribed to the difference in size of each crystalline powder estimated by X-ray diffraction methods.