Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Classical two-slit interference effects in double photoionization of molecular hydrogen at high energies

Recent experiments on double photoionization of H2 with photon energies between 160 and 240 eV have revealed body-frame angular distributions that suggest classical two-slit interference effects may be present when one electron carries most of the available energy and the second electron is not observed. We report precise quantum mechanical calculations that reproduce the experimental findings. They reveal that the interpretation in terms of classical diffraction is only appropriate at substantially higher photon energies. At the energies considered in the experiment we offer an alternative explanation based on the mixing of two nondiffractive contributions by circularly polarized light.     

Fine-tuning of boron complexes with cage-shaped ligand geometry: rational design of triphenolic ligand as a template for structure control

Boron complexes surrounded with organic cages were controlled precisely by a remote atom placed at the bottom of the cage. A replacement of the bottom tether atom (carbon or silicon) changed the characteristics (kinetic and thermodynamic factors) of boron complexes by geometric effects. A theoretical study shows that the bottom atoms also control eigenvalues of MO. This cage complex will provide a systematic template for fine-tuning of metal complexes to create various properties.     

Novel hierarchical classification and visualization method for multiobjective optimization of drug properties: application to structure-activity relationship analysis of cytochrome P450 metabolism

In the lead optimization process, medicinal chemists must consider various chemical properties of active compounds, including ADME/Tox properties, and find the best compromise among these. This study presents a novel data mining method for multiobjective optimization of chemical properties, which consists of the hierarchical classification and visualization of multidimensional data. A hierarchical classification tree model is generated by an extension of recursive partitioning that utilizes averaged information gains for multiple objective variables as a quality-of-split criterion. All the hierarchically structured data objects are represented using a large-scale data visualization technique. The technique is an extension of HeiankyoView, which displays data objects as colored icons and group nodes as rectangular borders. Each icon is divided into subregions with different colors, so that it can present multidimensional data according to brightness of the colors. The proposed method was applied to the structure-activity relationship analysis for cytochrome P450 (CYP) substrates. The substrate specificity of six CYP isoforms was successfully delineated: e.g., CYP2C9 substrates are anionic compounds, while CYP2D6 substrates are cationic; and CYP2E1 substrates are smaller compounds, while CYP3A4 substrates are larger compounds.     

Hydrolytic Degradation and Monomer Recovery of Poly(butylene succinate) and Poly(butylene succinate/adipate) in the Melt

Aliphatic dicarboxylic acid/aliphatic diol‐derived polyesters, poly(butylene succinate) and poly(butylene succinate/adipate), have been hydrolytically degraded in the melt in high‐temperature and high‐pressure water over a wide temperature range of 180–300 °C for periods of up to 30 min. The formation/decomposition of succinic acid (SA), adipic acid (AA), and butane‐1,4‐diol (BD), plus the molecular weight change of PBS and PBSA were then investigated. SA and AA were recovered at maximum yields of 65–80%, whereas BD was recovered at a maximum yield of only 30%, probably because of its decomposition. The obtained results were compared with those reported for aliphatic hydroxycarboxylic acid‐derived polyesters and aromatic dicarboxylic acid/aliphatic diol‐derived polyesters.

     

Synthesis of Heptagon-Containing Polyarenes by Catalytic C−H Activation

Nanocarbons incorporating non-hexagonal aromatic rings - such as five-, seven-, and eight-membered rings - have various intriguing physical properties such as curved structures, unique one-dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven-membered rings via a palladium-catalyzed intramolecular Ar−H/Ar−Br coupling. In addition to all-hydrocarbon scaffolds, heteroatom-embedded heptagon-containing polyarenes can be efficiently constructed with this method. Rhodium- and palladium-catalyzed sequential six- and seven-membered ring formations also afford complex heptagon-containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven-membered ring formation by a concerted metalation-deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven-membered ring-containing molecular nanocarbons.     

Preparation of hollow poly(divinyl benzene) particles with multiple holes in the shell by microsuspension polymerization with the SaPSeP method

Hollow polymer particles with multiple holes in the shell were prepared by aqueous microsuspension polymerization of micrometer-sized, monodisperse divinylbenzene/n-hexadecane droplets in the presence of sodium dodecyl sulfate (SDS) at concentrations above 4 mM utilizing the Self-assembling Phase-Separated Polymer (SaPSeP) method developed by the authors. The total surface area of the holes per particle increased with an increase in the SDS concentration. At [SDS] = 10 mM, “flower-like” non-spherical particles were formed. Part CCCXV of series “Studies on Suspension and Emulsion”     

Liposome modified with Mn-porphyrin complex can simultaneously induce antioxidative enzyme-like activity of both superoxide dismutase and peroxidase

An antioxidative liposome catalysis that mimics both superoxide dismutase (SOD) and peroxidase (POD) activities has been developed by using the liposomes modified with lipophilic Mn-(5,10,15,20-tetrakis[1-hexadecylpyridium-4-yl]-21H,23H-porphyrin) (Mn-HPyP). The SOD- and POD-like activities of the Mn-HPyP-modified liposome were first investigated by varying the type of phospholipid, such as 1,2-distearyl-sn-glycero-3-phosphocholine (DSPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC). Higher SOD-like activity was obtained in the case of DLPC and DMPC liposomes, in which the ligands were well-dispersed on the membrane in the liquid crystalline phase. The POD-like activity was maximal in the case of DMPC liposome, in which the Mn-HPyP complex was appropriately clustered on the membrane in the gel phase. On the basis of the above results, the co-induction of the SOD and POD activities to eliminate the superoxide and also hydrogen peroxide as a one-pot reaction was finally performed by using the Mn-HPyP-modified DMPC liposome, resulting in an increase in the efficiency of the elimination of both superoxide and hydrogen peroxide.     

One-pot amidation of olefins through Pd-catalyzed coupling of alkylboranes and carbamoyl chlorides

A one-pot synthesis of C1-elongated amides starting from olefins and carbamoyl chlorides has been developed. Alkylboranes, generated by hydroboration of terminal olefins with 9-BBN-H, underwent smooth coupling with carbamoyl chlorides in the presence of palladium catalyst and Cs2CO3.     

Synthesis of chiral oxime ethers based on regio- and enantioselective allylic substitution catalyzed by iridium-pybox complex

The oxygen atom of oximes acts as a reactive nucleophile in the iridium-catalyzed allylic substitution of unsymmetrical substrates to give the branched oxime ethers. Among several chiral ligands evaluated, the iridium complex of pybox ligand having phenyl group catalyzed the allylic substitution of phosphates with high activity to form the branched oxime ethers with good enantioselectivities.