Two-dimensional Raman spectra of atomic solids and liquids

We calculate third- and fifth-order Raman spectra of simple atoms interacting through a soft-core potential by means of molecular-dynamics (MD) simulations. The total polarizability of molecules is treated by the dipole-induced dipole model. Two- and three-body correlation functions of the polarizability at various temperatures are evaluated from equilibrium MD simulations based on a stability matrix formulation. To analyze the processes involved in the spectroscopic measurements, we divide the fifth-order response functions into symmetric and antisymmetric integrated response functions; the symmetric one is written as a simple three-body correlation function, while the antisymmetric one depends on a stability matrix. This analysis leads to a better understanding of the time scales and molecular motions that govern the two-dimensional (2D) signal. The 2D Raman spectra show novel differences between the solid and liquid phases, which are associated with the decay rates of coherent motions. On the other hand, these differences are not observed in the linear Raman spectra.     

Structural scaffold of 18-crown-6 tetracarboxylic Acid for optical resolution of chiral amino acid: x-ray crystal analyses of complexes of D- and L-isomers of serine and glutamic acid

(+)-18-crown-6 tetracarboxylic acid (18C6H4) has been used as a chiral selector for D/L-amino acids in HPLC, where L-isomer is usually eluted prior to D-isomer, except for the case of serine. To clarify why serine exhibits the reverse order for the elusion, the chiral interactions of D- and L-serines with (+)-18C6H4 were investigated by the X-ray single crystal analyses, together with the case of D- and L-glutamic acids, which exhibit the usual elution order in HPLC. The backbone structures (amino, Calpha-H and carboxyl groups) of these four amino acids showed the nearly same interaction with (+)-18C6H4 despite their different chirality. In contrast, the hydroxyl group of L-serine side chain formed a hydrogen bond with the carboxyl group of (+)-18C6H4, whereas such a interaction was not formed for the side chain of D-serine and D- and L-glutamic acids. Thus, it was shown that the exception of D/L-serine from the first elution rule of L-isomer in HPLC is due to the presence and absence of a hydrogen bond formation of its side chain OH group.     

Creating Very True Quantum Algorithms for Quantum Energy Based Computing

An interpretation of quantum mechanics is discussed. It is assumed that quantum is energy. An algorithm by means of the energy interpretation is discussed. An algorithm, based on the energy interpretation, for fast determining a homogeneous linear function f(x) := s.x = s ₁ x ₁ + s ₂ x ₂ + ? + s _N x _N is proposed. Here x = (x ₁, … , x _N ), x _j ∈ R and the coefficients s = (s ₁, … , s _N ), s _j ∈ N. Given the interpolation values \((f(1), f(2),...,f(N))=\vec {y}\), the unknown coefficients \(s = (s_{1}(\vec {y}),\dots , s_{N}(\vec {y}))\) of the linear function shall be determined, simultaneously. The speed of determining the values is shown to outperform the classical case by a factor of N. Our method is based on the generalized Bernstein-Vazirani algorithm to qudit systems. Next, by using M parallel quantum systems, M homogeneous linear functions are determined, simultaneously. The speed of obtaining the set of M homogeneous linear functions is shown to outperform the classical case by a factor of N × M.     

New Method of Calculating a Multiplication by using the Generalized Bernstein-Vazirani Algorithm

We present a new method of more speedily calculating a multiplication by using the generalized Bernstein-Vazirani algorithm and many parallel quantum systems. Given the set of real values \(\{a_{1},a_{2},a_{3},\ldots ,a_{N}\}\) and a function \(g:\textbf {R}\rightarrow \{0,1\}\), we shall determine the following values \(\{g(a_{1}),g(a_{2}),g(a_{3}),\ldots , g(a_{N})\}\) simultaneously. The speed of determining the values is shown to outperform the classical case by a factor of \(N\). Next, we consider it as a number in binary representation; M₁ = (g(a₁),g(a₂),g(a₃),…,g(a _N )). By using \(M\) parallel quantum systems, we have \(M\) numbers in binary representation, simultaneously. The speed of obtaining the \(M\) numbers is shown to outperform the classical case by a factor of \(M\). Finally, we calculate the product; \( M_{1}\times M_{2}\times \cdots \times M_{M}. \) The speed of obtaining the product is shown to outperform the classical case by a factor of N × M.     

Detection of diminished response to cold pressor test in smokers: Assessment using phase-contrast cine magnetic resonance imaging of the coronary sinus

Purpose

The purposes of this study were to evaluate the reproducibility for measuring the cold pressor test (CPT)-induced myocardial blood flow (MBF) alteration using phase-contrast (PC) cine MRI, and to determine if this approach could detect altered MBF response to CPT in smokers.

Materials and methods

After obtaining informed consent, ten healthy male non-smokers (mean age: 28 ± 5 years) and ten age-matched male smokers (smoking duration ≥ 5 years, mean age: 28 ± 3 years) were examined in this institutional review board approved study. Breath-hold PC cine MR images of the coronary sinus were obtained with a 3 T MR imager with 32 channel coils at rest and during a CPT performed after immersing one foot in ice water. MBF was calculated as coronary sinus flow divided by the left ventricular (LV) mass which was given as a total LV myocardial volume measured on cine MRI multiplied by the specific gravity (1.05 g/mL).

Results

In non-smokers, MBF was 0.86 ± 0.25 mL/min/g at rest, with a significant increase to 1.20 ± 0.36 mL/min/g seen during CPT (percentage change of MBF (?MBF (%)); 39.2% ± 14.4%, p < 0.001). Inter-study reproducibility for ?MBF (%) measurements by different MR technologist was good, as indicated by the intraclass correlation coefficient of 0.93 and reproducibility coefficient of 10.5%. There was no significant difference between smokers and non-smokers for resting MBF (0.85 ± 0.32 mL/min/g, p = 0.91). However, ?MBF (%) in smokers was significantly reduced (-4.0 ± 32.2% vs. 39.2 ± 14.4%, p = 0.011).

Conclusion

PC cine MRI can be used to reproducibly quantify MBF response to CPT and to detect impaired flow response in smokers. This MR approach may be useful for monitoring the sequential change of coronary blood flow in various potentially pathologic conditions and for investigating its relationship with cardiovascular risk.     

Molecular origin of differences in hole and electron mobility in amorphous Alq3--a multiscale simulation study

In order to determine the molecular origin of the difference in electron and hole mobilities of amorphous thin films of Alq(3) (meridional Alq(3) (tris(8-hydroxyquinoline) aluminium)) we performed multiscale simulations covering quantum mechanics, molecular mechanics and lattice models. The study includes realistic disordered morphologies, polarized site energies to describe diagonal disorder, quantum chemically calculated transfer integrals for the off-diagonal disorder, inner sphere reorganization energies and an approximative scheme for outer sphere reorganization energies. Intermolecular transfer rates were calculated via Marcus-theory and mobilities were simulated via kinetic Monte Carlo simulations and by a Master Equation approach. The difference in electron and hole mobility originates from the different localization of charge density in the radical anion (more delocalized) compared to the radical cation (more confined). This results in higher diagonal disorder for holes and less favourable overlap properties for the hole transfer integrals leading to an overall higher electron mobility.     

Exploring chemistry with the fragment molecular orbital method

The fragment molecular orbital (FMO) method makes possible nearly linear scaling calculations of large molecular systems, such as water clusters, proteins and DNA. In particular, FMO has been widely used in biochemical applications involving protein-ligand binding and drug design. The method has been efficiently parallelized suitable for petascale computing. Many commonly used wave functions and solvent models have been interfaced with FMO. We review the historical background of FMO, and summarize its method development and applications.     

TiO2 synthesis inspired by biomineralization: control of morphology, crystal phase, and light-use efficiency in a single process

Hydroxyapatite is mineralized along the long axis of collagen fiber during osteogenesis. Mimicking such biomineralization has great potential to control inorganic structures and is fast becoming an important next-generation inorganic synthesis method. Inorganic matter synthesized by biomineralization can have beautiful and functional structures that cannot be created artificially. In this study, we applied biomineralization to the synthesis of the only photocatalyst in practical use today, titanium dioxide (TiO(2)). The photocatalytic activity of TiO(2) mainly relates to three properties: morphology, crystal phase, and light-use efficiency. To optimize TiO(2) morphology, we used a simple sequential peptide as an organic template. TiO(2) mineralized by a β-sheet peptide nanofiber template forms fiber-like shapes that are not observed for mineralization by peptides in the shape of random coils. To optimize TiO(2) crystal phase, we mineralized TiO(2) with the template at 400 °C to transform it into the rutile phase and at 700 °C to transform it into a mixed phase of anatase and rutile. To optimize light-use efficiency, we introduced nitrogen atoms of the peptide into the TiO(2) structure as doped elemental material during sintering. Thus, this biomineralization method enables control of inorganic morphology, crystal phase, and light-use efficiency in a single process.