Evidence of conformational equilibrium of 1-ethyl-3-methylimidazolium in its ionic liquid salts: Raman spectroscopic study and quantum chemical calculations

Raman spectra of liquid 1-ethyl-3-methylimidazolium (EMI+) salts, EMI(+)BF4-, EMI(+)PF6-, EMI(+)CF3SO3-, and EMI(+)N(CF3SO2)2-, were measured over the frequency range 200-1600 cm(-1). In the range 200-500 cm(-1), we found five bands originating from the EMI+ ion at 241, 297, 387, 430, and 448 cm(-1). However, the 448 cm(-1) band could hardly be reproduced by theoretical calculations in terms of a given EMI+ conformer, implying that the band originates from another conformer. This is expected because the EMI+ involves an ethyl group bound to the N atom of the imidazolium ring, and the ethyl group can rotate along the C-N bond to yield conformers. The torsion energy for the rotation was then theoretically calculated. Two local minima with an energy difference of ca. 2 kJ mol(-1) were found, suggesting that two conformers are present in equilibrium. Full geometry optimizations followed by normal frequency analyses indicate that the two conformers are those with planar and nonplanar ethyl groups against the imidazolium ring plane, and the nonplanar conformer is favorable. It elucidates that bands at 241, 297, 387, and 430 cm(-1) mainly originate from the nonplanar conformer, whereas the 448 cm(-1) band does originate from the planar conformer. Indeed, the enthalpy for conformational change from nonplanar to planar EMI+ experimentally obtained by analyzing band intensities of the conformers at varying temperatures is practically the same as that evaluated by theoretical calculations. We thus conclude that the EMI+ ion exists as either a nonplanar or planar conformer in equilibrium in its liquid salts.     

A practical synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid via organocatalytic asymmetric construction of a tetrasubstituted carbon center

[reaction: see text] A concise and enantioselective synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid as a key intermediate for (S)-oxybutynin is reported. The crucial asymmetric tetrasubstituted carbon center was constructed with excellent stereoselectivity through the proline-catalyzed direct asymmetric aldol reaction between cyclohexanone and ethyl phenylglyoxylate under mild conditions.     

Multi-step nonlinear conjugate gradient methods for unconstrained minimization

Conjugate gradient methods are appealing for large scale nonlinear optimization problems, because they avoid the storage of matrices. Recently, seeking fast convergence of these methods, Dai and Liao (Appl. Math. Optim. 43:87–101, 2001) proposed a conjugate gradient method based on the secant condition of quasi-Newton methods, and later Yabe and Takano (Comput. Optim. Appl. 28:203–225, 2004) proposed another conjugate gradient method based on the modified secant condition. In this paper, we make use of a multi-step secant condition given by Ford and Moghrabi (Optim. Methods Softw. 2:357–370, 1993; J. Comput. Appl. Math. 50:305–323, 1994) and propose two new conjugate gradient methods based on this condition. The methods are shown to be globally convergent under certain assumptions. Numerical results are reported.     

Effect of the chemical species of arsenic on sensitivity in graphite furnace atomic absorption spectrometry.

The sensitivity of graphite furnace atomic absorption spectrometry (GFAAS) to arsenobetaine (AB) was 1.3-times higher than to inorganic As. In order to understand the mechanism underlying this observation, the atomization processes for both chemical species were investigated in terms of the enthalpy change (DeltaH) during the atomization process in GFAAS. The enthalpy change of AB was slightly lower than that of inorganic As, which suggested that AB was atomized more efficiently than was inorganic As. Moreover, it was observed that some co-existing organic materials enhanced the analytical sensitivity of inorganic As. The sensitivity difference between inorganic As and AB depended upon the mechanisms of their atomization processes.     

Fundamental imaging properties of transillumination laser computed tomography based on coherent detection imaging method.

The coherent detection imaging (CDI) method uses the optical heterodyne detection technique. CW and single frequency lasers having long coherence lengths are used to exploit the maximum advantages of heterodyne detection, such as high directionality, selectivity and sensitivity. The CDI method based on optical heterodyne detection enables selective filtering of the directional coherence-retaining emergent photons, which leads to image reconstruction from projections, similar to X-ray computed tomography (CT). So far we have demonstrated the advantages and capabilities of the measurement technique for transillumination optical computed tomography in biomedicine. Here, we investigate the fundamental imaging properties of CDI method, such as its high directionality and quantitativeness, with preliminary physical phantom experiments. The results show that the CDI method satisfies the requirements for CT reconstruction under the first order approximation, and enables quantitative measurements in the sense that the relationship between estimated and actual concentration retains a satisfactory linearity.     

Rod-like liquid crystals of organic transition metal complexes. I. Reversible transformation between blue smectogen and red nematogen

Two novel types of transition-metal-containing liquid crystals, bis(p-n-koxydithiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)₂Ni), and (p-n-alkoxydithiobenzoato)(p-n-alkoxyperthiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)(C_nO-PTB)Ni), were synthesized. It was found that the (C_nO-DTB)₂Ni complex for n = 8 has smectic H and C mesophases, and that the (C_nO-DTB)₂Ni complexes for n = 4 and 8 easily transform into the corresponding monoperthio complexes, _nO-PTB)Ni, by heating at temperatures between 230°C and 285°C. It was confirmed that the transformation originates from an intermolecular reaction between the (C_nO-DTB)₂Ni complexes at high temperatures, and that the origin of the extra sulphurs in the resulting (C_nO-DTB)(C_nO-PTB)Ni complexes is the neighbouring (C_nO-DTB)₂Ni complexes. Interestingly, each of the (C_nO-DTB)(C_nO-PTB)Ni complexes (n = 4 and 8), has nematic mesophase and exhibits a unique double melting behaviour via the nematic phase, which is the first example in liquid crystals. The reversible transformation between the blue smectic rod-like (C_nO-DTB)₂Ni complex and the red nematic Λ-like (C_nO-DTB)(C_nO-PTB)Ni complex is possible.     

A non-D-space with large extent

We proved that ^?+ implies the existence of a non-D-space whose all closed subspace F satisfies e(F)=L(F). The existence of such a space under MA+¬CH or PFA is also discussed.     

Complexity of Body Movements during Sleep in Children with Autism Spectrum Disorder

Recently, measuring the complexity of body movements during sleep has been proven as an objective biomarker of various psychiatric disorders. Although sleep problems are common in children with autism spectrum disorder (ASD) and might exacerbate ASD symptoms, their objectivity as a biomarker remains to be established. Therefore, details of body movement complexity during sleep as estimated by actigraphy were investigated in typically developing (TD) children and in children with ASD. Several complexity analyses were applied to raw and thresholded data of actigraphy from 17 TD children and 17 children with ASD. Determinism, irregularity and unpredictability, and long-range temporal correlation were examined respectively using the false nearest neighbor (FNN) algorithm, information-theoretic analyses, and detrended fluctuation analysis (DFA). Although the FNN algorithm did not reveal determinism in body movements, surrogate analyses identified the influence of nonlinear processes on the irregularity and long-range temporal correlation of body movements. Additionally, the irregularity and unpredictability of body movements measured by expanded sample entropy were significantly lower in ASD than in TD children up to two hours after sleep onset and at approximately six hours after sleep onset. This difference was found especially for the high-irregularity period. Through this study, we characterized details of the complexity of body movements during sleep and demonstrated the group difference of body movement complexity across TD children and children with ASD. Complexity analyses of body movements during sleep have provided valuable insights into sleep profiles. Body movement complexity might be useful as a biomarker for ASD.     

Origins of hole doping and relevant optoelectronic properties of wide gap p-type semiconductor, LaCuOSe

LaCuOSe is a wide band gap (～2.8 eV) semiconductor with unique optoelectronic properties, including room-temperature stable excitons, high hole mobility ～8 cm(2)/(Vs), and the capability of high-density hole doping (up to 1.7 × 10(21) cm(-3) using Mg). Moreover, its carrier transport and doping behaviors exhibit nonconventional results, e.g., the hole concentration increases with decreasing temperature and the high hole doping does not correlate with other properties such as optical absorption. Herein, secondary ion mass spectroscopy and photoemission spectroscopy reveal that aliovalent ion substitution of Mg at the La site is not the main source of hole doping and the Fermi level does not shift even in heavily doped LaCuOSe:Mg. As the hole concentration increases, the subgap optical absorption becomes more intense, but the increase in intensity does not correlate quantitatively. Transmission electron microscopy indicates that planar defects composed of Cu and Se deficiencies are easily created in LaCuOSe. These observations can be explained via the existence of a degenerate low-mobility layer and formation of complex Cu and Se vacancy defects with the assistance of generalized gradient approximation band calculations.