Electronic stress tensor analysis of hydrogenated palladium clusters

We study the chemical bonds of small palladium clusters Pd _n (n?=?2?9) saturated by hydrogen atoms using electronic stress tensor. Our calculation includes bond orders which are recently proposed based on the stress tensor. It is shown that our bond orders can classify the different types of chemical bonds in those clusters. In particular, we discuss Pd?CH bonds associated with the H atoms with high coordination numbers and the difference of H?CH bonds in the different Pd clusters from viewpoint of the electronic stress tensor. The notion of ??pseudo-spindle structure?? is proposed as the region between two atoms where the largest eigenvalue of the electronic stress tensor is negative and corresponding eigenvectors forming a pattern which connects them.     

Simultaneous and group determination methods for designated substances by HPLC with multi-channel electrochemical detection and their application to real samples

Many psychotropic substances are illegally available on the streets and/or via the Internet. This wide distribution has become a serious social problem. To control this problem, many substances have been controlled as ‘designated substances’ (Shitei‐Yakubutsu) in Japan since April 2007 by the Pharmaceutical Affairs Law, including tryptamines, phenethylamines and piperazines. In the present study, simultaneous determination methods using HPLC with multi‐channel electrochemical detection (MECD) were developed for the designated substances. The proposed methods utilizing online electrochemical oxidation are the first report on the simultaneous determination of various designated substances. The methods involve direct determination and require no complicated pretreatments such as fluorescence labeling. The designated substances were separated by reversed‐phase chromatography using a TSK‐gel ODS‐100V (4.6 × 250 mm, i.d., 3 µm) and gradient elution by a mixture of potassium phosphate buffer, methanol and acetonitrile. The total separation of 31 designated substances was successfully performed but required long chromatographic run times. Thus, the designated substances were divided into three groups: (1) tryptamines, (2) phenethylamines and (3) piperazines and others. They were then analyzed by HPLC‐MECD as another separation method. The suitable applied voltages for each designated substance were determined based upon the hydrodynamic voltammogram. The limits of detection (signal‐to‐noise ratio of 3) of the designated substances for the most suitable voltages were in the range of 17.1 pg (5‐MeO‐MIPT) to 117 ng (indan‐2‐amine). The calibration curves based on the peak heights were linearly related to the amounts of the designated substances (R² > 0.999). Good accuracy and precision by intra‐day assay and inter‐day assay were also obtained using the present procedures. The proposed methods were applied to the analyses of the designated substance in several real samples. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of bicyclic bis(γ‐butyrolactone) derivatives bearing sulfide moieties and their alternating copolymers with epoxide

A series of bicyclic bis(γ‐butyrolactone)s (BBL) bearing sulfide moiety 2 were readily synthesized from a precursor BBL bearing isopropenyl group 1. This efficient and versatile synthesis of 2 was achieved by a highly reliable radical addition reaction of thiols to the C‐C double bond in the isopropenyl group 2 underwent anionic copolymerization with glycidyl phenyl ether in a 1:1 alternating manner to give a series of the corresponding polyester 3, of which side chains inherited the sulfide group from 2. The glass transition temperatures (T_g) of 3 showed clear dependence on the flexibility of the sulfide side chains. The scope of this copolymerization system was further expanded by synthesizing a bifunctional BBL 4 from 1 with using hexanedithiol and performing its copolymerization with bisphenol A diglycidyl ether 5. The copolymerization gave the corresponding networked polymer in high yield. During the copolymerization, the volume expanding nature of the double ring‐opening reaction of 4 contributed to the efficient compensation of the intrinsic volume shrinkage of the ring‐opening of epoxide to achieve a shrinkage‐free curing system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Analogues of Jacobi’s derivative formula II

In this work, we use Jacobi’s derivative formula to obtain analogues to theta constants with rational characteristics. Furthermore, we show that the analogues yield many product-series identities by only using the elementary fact that a holomorphic elliptic function is a constant.     

Comparison of FAIR technique with different inversion times and post contrast dynamic perfusion MRI in chronic occlusive cerebrovascular disease

The purpose of this study was to examine the signal change occurring with different inversion times (TIs) of the flow-sensitive alternating inversion recovery (FAIR) technique and to compare with the perfusion image obtained with Gd-DTPA injection. The subjects were 11 patients with unilateral occlusive cerebrovascular disease. Two FAIR images with different TIs (800 ms and 1600 ms) were measured for each patient and dynamic perfusion MRI was performed to produce four kinds of parameter maps: mean transit time (MTT), time to peak (TTP), relative cerebral blood flow (rCBF) and relative cerebral blood volume (rCBV) maps. Asymmetry ratios (ARs) between the affected and contra-lateral vascular sides were measured in both FAIR images and the four dynamic parameter maps. The AR of the MTT map of the four parameters showed the highest correlation with that of the FAIR images, especially with that of TI = 1600 ms (r = 0.829), and the AR of the rCBV map revealed the worst correlation with the FAIR images. The AR of the FAIR image with TI = 800 ms was less correlated with that of MTT than that with TI = 1600 ms. These results suggested that the signal intensity of the FAIR image was influenced by flow transition time and the change in TI could be used to select the flow with a different transition time. Our study suggested that a longer TI in the FAIR technique might be more useful than a shorter TI for evaluating chronic occlusive cerebrovascular disease in the clinical setting.     

Positive definite matrix approximation with condition number constraint

Positive definite matrix approximation with a condition number constraint is an optimization problem to find the nearest positive definite matrix whose condition number is smaller than a given constant. We demonstrate that this problem can be converted to a simpler one when we use a unitary similarity invariant norm as a metric. We can especially convert it to a univariate piecewise convex optimization problem when we use the Ky Fan p-k norm. We also present an analytical solution to the problem whose metric is the spectral norm and the trace norm.     

Solvent-induced switching of the macromolecular helicity of poly[(4-carboxyphenyl)acetylene] induced by a single chiral amino alcohol

Cis–transoidal poly[(4-carboxyphenyl)acetylene] (poly- 1 ) complexed with optically active amines and amino alcohols showed an induced circular dichroism (ICD) in the ultraviolet–visible region because of a predominantly one-handed helix formation in water and in dimethyl sulfoxide (DMSO). The Cotton effect signs of the poly- 1 /chiral amino alcohol complexes were inverted in the presence of water, whereas the ICD pattern of the poly- 1 /chiral amine complexes showed no change, regardless of the water content. These results demonstrated that the helix sense of poly- 1 induced by optically active amino alcohols through noncovalent acid–base interactions could be switched by changes in the solvent ratio in the DMSO–water mixtures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3625–3631, 2003     

Improvement in reliability of probabilistic test of significant differences in GeneChip experiments.

A probabilistic test (FUMI theory) for GeneChip experiments has been proposed for selecting the genes which show significant differences in the gene expression levels between a single pair of treatment and control. This paper describes that the reliability of the judgment by the FUMI theory can be enhanced, when the selected genes are referred to biomolecular-functional networks of a commercial database. The genes judged as being differently expressed are grouped into a cluster in the biomolecular networks. It is also demonstrated that false positive genes have a trend in the networks to be isolated from each other, and also away from the clustered genes, since the false positive genes are randomly selected.     

Exploiting sparsity in primal-dual interior-point methods for semidefinite programming

The Helmberg-Rendl-Vanderbei-Wolkowicz/Kojima-Shindoh-Hara/Monteiro and Nesterov-Todd search directions have been used in many primal-dual interior-point methods for semidefinite programs. This paper proposes an efficient method for computing the two directions when the semidefinite program to be solved is large scale and sparse.