Identification of hydrogen bonds using quantum electrodynamics

A method for the identification of hydrogen bonds was investigated from the viewpoint of the stress tensor density proposed by Tachibana and following other works in this field. Hydrogen bonds are known to exhibit common features with ionic and covalent bonds. In quantum electrodynamics, the covalent bond has been demonstrated to display a spindle structure of the stress tensor density. Importantly, this spindle structure is also seen in the hydrogen bond, although the covalency is considerably weaker than in a typical covalent bond. Distinguishing it from the ionic bond is most imperative for the identification of the hydrogen bond. In the present study, the directionality of the hydrogen bond is investigated as the ionic bond is nearly isotropic, while the hydrogen bond exhibits the directionality. It was demonstrated that the hydrogen bond can be distinguished from the ionic bond using the angle dependence of the largest eigenvalue of the stress tensor density.     

Chiral Vinyl Sulfoxides as Useful Reagents for the Synthesis of β-Amino Acid Derivatives

(S)- and (R)-β-amino acid derivatives were synthesized by the asymmetric conjugate addition of ammonia and piperidazine to t-butyl (E)-2-[(R)- and (S)-p-tolylsulfinyl]cinnamates, respectively.     

Grafting of Polymers onto a Crosslinked Polymer Carrying Carboxyl Groups as a Model Compound for Carbon Black

Abstract

A cation-exchange resin (a crosslinked polymer carrying carboxyl groups) was used as a model compound for carbon black, and the grafting of several polymers to the resin was investigated. Reaction of acyl chloride groups that had been placed on the ion-exchange resin with polymers having hydroxyl or amino groups, such as polypropylene glycol, polyethylene glycol, polybutadiene glycol, polyvinyl alcohol, silicone diol, silicone diamine, and polyethyleneimine, resulted in grafting to the ion-exchange resin. In further experiments, primary amino groups were placed on the cation-exchange resin by reaction of acyl chloride groups with ethylenediamine. It was found that ring-opening polymerization of γmethyl L-glutamate N-carboxyanhydride is initiated by the amino groups on the resin, and polypeptide was grafted from the cation-exchange resin. Therefore, the reactivity of carboxyl groups on the resin was found to be similar to that on carbon black. However, carboxyl groups on the resin failed to initiate the cationic polymerization of vinyl monomers, in contrast to those on carbon black. This suggested that the acidity of carboxyl groups on carbon black is greater than on the cation-exchange resin.     

Strong Positive Allosterism which Appears in Molecular Recognition with Cerium(IV) Double Decker Porphyrins: Correlation between the Number of Binding Sites and Hill Coefficients

Abstract

Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63 × 1011M-4 and n = 3.9 for L-4 and K = 2.75 × 109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals.     

Color-modulation by Additives for Photochromism of Cyclic Viologen Derivatives

Abstract

Two cyclic viologen derivatives were prepared in order to investigate their photochromic properties in a thin polymer film. The absorption peaks of photoreduced cyclic viologen units were shifted to the red side by the inclusion of indole or 1,4-dimethoxybenzene, although those of photoreduced acyclic analogues were not shifted in the presence of the guests.     

Novel Attempts to Change the Colour of Dye Molecules Utilizing the Aggregation Mode of Saccharides

Ten saccharide-dye (azophenol and azonaphthol) conjugate molecules and four methylated reference compounds were synthesized. The purpose of the present study using these molecules is to change the colour of the common dye moiety, both in solution and in solid by the structural difference in the saccharide moieties and eventually to mimic the colour creation mechanism in a nature's flower family. In azophenol derivatives, the solution (THF) colour was more or less the same but the solid colour was significantly different (yellow-orange-pink). The XRD study established that the colour change is correlated to the crystallinity of the solid samples: the u max shifts to shorter wavelength with the increase in the crystallinity. In azonaphthol derivatives, the solution colour was more different than the solid colour. The spectroscopic studies established that this change is due to an azo-hydrazone tautomerism. The colour changes were quantitatively expressed by the CIE L * a * b * colourimetric system. The foregoing results indicate that the colour of the dye molecules can be changed utilizing the intra- and intermolecular hydrogen-bonding interactions among the appended saccharide moieties.     

Automatic Implementation of Elasto-plastic Incremental Formulations at Finite Strains using Hyper-Dual Numbers

Numerical simulation of standard dissipative materials undergoing finite strains remains an important and challenging topic in computational mechanics. The incremental variational formulation (IVF), firstly proposed by Ortiz et al. [1], provides a general variational framework which is suitable for the implementation of a broad range of constitutive laws for standard dissipative materials. The IVF recasts the inelasticity theory as an equivalent optimization problem where the incremental stress potential is minimized with respect to the internal variables. However, their implementation often requires more effort than classical formulations due to high-order tensor derivatives. In this contribution, a novel implementation of IVFs is presented to arrive at a fully automatic and robust scheme with computer accuracy using hyper-dual numbers (HDNs). The HDNs, which are originally developed by Fike [2], derive exact and automatic derivative calculations without any cumbersome choice of perturbation values. Its uncomplicated implementation for associative finite strain elasto-plasticity and its performance is illustrated by a representative numerical example. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparative intelligibility investigation of single-channel noise-reduction algorithms for Chinese, Japanese, and English

A large number of single-channel noise-reduction algorithms have been proposed based largely on mathematical principles. Most of these algorithms, however, have been evaluated with English speech. Given the different perceptual cues used by native listeners of different languages including tonal languages, it is of interest to examine whether there are any language effects when the same noise-reduction algorithm is used to process noisy speech in different languages. A comparative evaluation and investigation is taken in this study of various single-channel noise-reduction algorithms applied to noisy speech taken from three languages: Chinese, Japanese, and English. Clean speech signals (Chinese words and Japanese words) were first corrupted by three types of noise at two signal-to-noise ratios and then processed by five single-channel noise-reduction algorithms. The processed signals were finally presented to normal-hearing listeners for recognition. Intelligibility evaluation showed that the majority of noise-reduction algorithms did not improve speech intelligibility. Consistent with a previous study with the English language, the Wiener filtering algorithm produced small, but statistically significant, improvements in intelligibility for car and white noise conditions. Significant differences between the performances of noise-reduction algorithms across the three languages were observed.     

Wavelength-addressed intra-board optical interconnection by plug-in alignment with a micro hole array

Intra-board interconnection between optical waveguide channels is suitable for assembling high-speed optoelectronic printed wiring boards (OE-PWB). Here, we propose a novel optical interconnection method combining techniques for both wavelength-based optical waveguide addressing and plug-in optical waveguide alignment with a micro-hole array (MHA). This array was fabricated by the mask transfer method. For waveguide addressing, we used a micro passive wavelength selector (MPWS) module, which is a type of Littrow mount monochromator consisting of an optical diffraction grating, a focusing lens, and the MHA. From the experimental results, we found that the wavelength addressing operation of the MPWS module was effective for intra-board optical interconnection.     

Demazure Modules and Perfect Crystals

We give a criterion for the Demazure crystal defined by Kashiwara to have a tensor product structure. We study the symmetric tensor case, and see some Demazure characters are expressed using Kostka-Foulkes polynomials. Received: 29 August 1996 / Accepted: 18 July 1997