Intermolecular forces for D2, N2, O2, F2 and CO2

The intermolecular potentials for D₂, N₂, O₂, F₂ and CO₂ are determined on the basis of the second virial coeffincients, the polarizabilities parallel and perpendicular to the molecular axes, and the electric quadrupole moment. The repulsive parts of the potentials are taken from the corresponding Kihara core-potentials. Effects of the octopolar induction are taken into consideration in a unique way. The potential depends on relative orientations of the two molecules as well as the distance r between the molecular centers. This dependence is shown in graphs. A measure of the anisotropy of the potential depth is 0.72 for CO₂ 0.36 for D₂, and smaller than 0.27 for N₂ O₂ and F₂. The remarkable anisotropy for CO₂ and D₂ is due to strong electrostatic quadrupole interactions.     

INTERCONVERSION OF BACTERIOCHLOROPHYLL c AGGREGATES IN SOLID FILMS UPON ORGANIC VAPOR TREATMENT

Bacteriochlorophyll c (BChl c) solid films were prepared from a carbon tetrachloride solution on CaF₂ plates as artificial aggregates. Effects of organic vapor such as acetone and tetrahydrofuran (THF) on the BChl c films were studied by absorption and Fourier-transform infrared spectroscopy. Two major homologs (R[E,E]BChl c_F and R[P,E]BChl c_F) and one minor homolog (S[I,E]BChl c) isolated from the green photosynthetic bacterium Chlorobium limicola strain 6230 were examined for the experiments. The BChl c polymeric aggregates absorbing at739–753 nm similar to those in the chlorosome were induced for all homologs upon the treatment of BChl c solid film with acetone vapor. The 13¹-keto C=O stretching band in the R[E,E]BChl c_F solid film showed a downward shift from 1651 cm^?1to 1643 cm^?1 with a concomitant shift of the 3¹-OH stretching bands from 3337 and 3238 cm^?1 to 3163 cm^?1. It was suggested that the lower aggregates brought about by Mg…O=C(13¹) and (3¹)O…O=C(13¹) bonds were transformed into the higher aggregates strongly hydrogen-bonded in a Mg…(3¹)O-H…O=C(13^l) interaction. They were transformed to a monomer-like form absorbing at 667 nm upon exposure to THF vapor and were reversibly converted to the higher aggregates upon removal of THF molecules in vacuo.     

Thermo-sensitive colloidal crystals of silica spheres in the presence of large spheres with poly (N-isopropyl acrylamide) shells

Thermo-sensitive colloidal crystals are prepared simply by mixing colloidal silica spheres and large thermo-sensitive gel spheres. The thermo-reversible change in the lattice spacing of colloidal crystals of monodisperse silica spheres (CS82, 103 nm in diameter) depends on the size of the admixed temperature-sensitive gel spheres. For spheres with sizes less and greater than that of the silica spheres, the lattice spacing upon temperature increase above the lower critical solution temperature of poly(N-isopropyl acrylamide) decreases (cf. Okubo et al. Langmuir 18:6783, 2002) and increases, respectively. A mechanism, which is able to explain these experimental findings, is proposed. Moreover, crystal growth rates and the rigidities of the thermo-sensitive colloidal crystals are studied.     

Enantiomorphism in the super helices of poly-γ-benzyl-glutamate

Summary Aggregates of poly--benzyl-d (orl-glutamate were precipitated by mixing of its solution in dimethylformamide or dioxane with propionic acid. Electron micrographs showed that the aggregates were composed of well-developed helical fibrils. The sence of helix was right-handed for thed-isomer and left-handed for thel-isomer; an enantiomorphic relation was shown for the helical aggregate of optical active macromolecule. Two recent publications have given conflicting results for the helical sense of the aggregate. This seems to be ascribed to carelessness in determining the helical sense from the electron micrographs.

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Zusammenfassung Es wurden Aggregate von Poly--benzyl-d (oderl)-glutamat durch Mischung von deren Lösung in Dimethylformamid oder Dioxan mit Propionsäure ausgefällt. Die elektronenmikroskopischen Bilder zeigen, daß die Aggregate aus gut ausgebildeten Helixfibrillen bestehen. Der Drehsinn der Helix war rechtsläufig für dasd-Isomer und linksläufig für dasl-Isomer. Eine enantiomorphe Beziehung läßt sich für die Helix-Aggregate zu den optisch aktiven Strukturen der Makromoleküle zeigen. Zwei kürzliche Veröffentlichungen ergaben zu dem hier Festgestellten widersprüchliche Ergebnisse über den Schraubensinn der Helices der aggregate. Dies scheint der Sorglosigkeit bei der Bestimmung des Schraubensinns von elektronenmikroskopischen Bildern zuzuschreiben zu sein.

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With 1 figure in 3 details     

Linear Multiselenium Interactions in Dicationic Oligomers of 1,5-(Diselena)canes: Behavior of Semc σ(mcc-nee) (6≤mc≤16) Elucidated with QTAIM Dual Functional Analysis

The intrinsic dynamic and static nature m_c center-n_e electron interactions of the σ-type σ(m_cc-n_ee) were elucidated for the Se-Se interactions in dicationic oligomers of Se(CH₂CH₂CH₂)₂Se ( 1 (Se, Se)) [ n ²⁺ (Se, Se): n=1–8], especially for m_c≥6, where n ²⁺ (Se, Se: n=1–8) are abbreviated by n ²⁺ (n=1–8), respectively. QTAIM dual functional analysis (QTAIM-DFA) was applied to the interactions. Perturbed structures generated using coordinates derived from the compliance constants (C_ii) were employed for QTAIM-DFA. Each Se-*-Se in 1 ²⁺ and 2 ²⁺ has the nature of CT-TBP (trigonal bipyramidal adduct formation through CT) and Cov-w (weak covalent), respectively, which supply the starting points of the investigations. The asterisk emphasizes the existence of a bond critical point on the interaction. All Se-*-Se in 3 ²⁺ are classified by the regular closed shell (r-CS) interactions and characterized as CT-MC (molecular complex formation through CT), which are denoted as r-CS/CT-MC, except for the central interaction, of which nature is r-CS/CT-TBP. Most interactions in 4 ²⁺– 8 ²⁺ are r-CS/t-HB_wc (typical-HB with covalency) but some are pure-CS/t-HB_nc (t-HB with no covalency). The linear Se_2n²⁺ interactions in 2 ²⁺– 8 ²⁺ seem close to those without any limitations, since the nature of Se-*-Se inside and outside of (CH₂CH₂CH₂)₂ are very similar with each other. The linear Se_2n²⁺ interactions in 3 ²⁺– 8 ²⁺ are shown to be analyzed as σ(m_cc-n_ee: 6≤m_c≤16), not by the accumulated σ(3c–4e).     

ESR study of molecular dynamics and orientation of TEMPO included in organic 1-D nanochannel

A mixture of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical and 2,2,6,6-tetramethyl-1-piperidine (TEMP) was included into organic 1-D nanochannels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) crystal. Dilution of the paramagnetic TEMPO radical was achieved with excess TEMP, thereby isolating a TEMPO molecule in the nanochannel. For inclusion compounds of TPP with TEMPO and TEMP (TEMPO/all guest compounds = 0.017, and 0.15), temperature-dependent electron spin resonance (ESR) spectra were observed to investigate their molecular dynamics and orientation. In the temperature range from 112 K to room temperature, the spectra depended remarkably on the temperature. Temperature dependence was well interpreted by uniaxial rotation, suggesting that TEMPO molecules undergo uniaxial rotation about a channel axis with a molecular orientation in which the N-O bond in the nitroxide group is perpendicular to the channel axis. The activation energy of uniaxial rotation was evaluated as 4.5 +/- 0.3 kJ mol(-1).     

High-speed solubility screening assay using ultra-performance liquid chromatography/mass spectrometry in drug discovery

Ultra-performance liquid chromatography (UPLC) was investigated as an alternative to high-performance liquid chromatography (HPLC) for analyzing pharmaceutical drug candidates. We previously developed a 96-well-based high-speed solubility assay system (HSSOL) using HPLC/UV and a LogD assay system (HSLogD) using HPLC/MS [Y. Dohta, T. Yamashita, S. Horiike, T. Nakamura, T. Fukami, Anal. Chem. 79 (2007) 8312]. We have introduced the UPLC/MS system into this previously developed HSSOL system to increase throughput. Results obtained by the UPLC/MS and HPLC/UV systems showed good agreement, validating the usefulness of the UPLC/MS system. A high-speed solubility assay system was developed employing the UPLC/MS system, thereby tripling the throughput.     

The unexpected isolation of CTP-431, a novel thiopyrone from the sponge Cacospongia mycofijiensis

A reinvestigation of a Fijian collection of Cacospongia mycofijiensis has yielded the known mycothiazole and a novel heterocyclic, CTP-431 (1). Its structure including absolute configuration as 8R,9R,10S,13S was established using NMR data, calculated DFT (13)C chemical shifts and results from X-ray crystallography. It is possible that the tricyclic skeleton of CTP-431 (1) is biosynthetically related to the macrolide latrunculin A, however the thiopyrone moiety of 1 has no previous precedent in natural products chemistry.     

Formation mechanism of one-dimensional Si islands on a H/Si(001) surface

The formation mechanism of one-dimensional Si islands on a H/Si(001)-(2x1) surface is studied using scanning tunneling microscopy/spectroscopy and first-principles calculations. We observed that one-dimensional islands that are made from dimer chains are formed at the initial growth stages similar to the bare Si(001) surface. It is found that the number of odd-numbered dimer chains is larger than that of even-numbered dimer chains. We propose the growth processes of the two types of growth edges to explain the observation.