Polymorphisms of 4,5-Bis(4-Methoxyphenyl)-2-(3-Nitrophenyl)-1H-Imidazole as Studied by Solid State NMR

Abstract

Solid state NMR measurements are carried out for polymorphs and inclusion complexes of 4,5-bis(4-methoxyphenyl)-2-(3-nitrophenyl)-1H-imidazole. Observed ¹³C and ¹⁵N chemical shifts are characteristic of each polymorph A, B, C and D. In addition, ¹⁵N chemical shift was a good index for understanding hydrogen bond. VT measurements revealed that B transforms to C between 93 and 113°C. From PSTMAS and ¹H solid echo measurements for AcOET inclusion complex, host molecules have almost same structure as B and guest molecules have the highest mobility of all inclusion complexes.     

Photoreactivity of amino acids: tryptophan-induced photochemical events via reactive oxygen species generation.

Tryptophan (Trp), an aromatic amino acid, is a constituent of peptides/proteins and is also a precursor of serotonin, kynurenine derivatives, and nicotinamide adenine dinucleotides. There have been a number of reports on photochemical reactions involving peptides/proteins which contain Trp that showed significant photodegradation, dimerization, and photoionization. The photochemical properties of Trp have not been fully elucidated, and this would provide novel insight into the handling of Trp-containing peptides/proteins. Consequently, we have been trying to evaluate the photochemical properties of Trp, as well as other essential amino acids, focusing on their photosensitivity, photodegradation, and their ability to induce lipid peroxidation. Among all the essential amino acids tested, Trp exhibited the maximal level of superoxide anion generation under 18 h of light exposure (30000 lux). UV spectral analysis of Trp suggested the absorbability of UVA/B light, and exposure of Trp, in both solid and solution states, to UVA/B light resulted in significant photodegradation (t(0.5): 18 h) and gradual color changes. In addition, photoirradiated Trp generated lipoperoxidant, a causative agent of photoirritation, and this might be associated with ROS generation.     

Revisiting the Bromination of CH Bonds with Molecular Bromine by Using a Photo‐Microflow System

The photobromination of C?H bonds by using molecular bromine was reinvestigated under microfluidic conditions. The continuous‐flow method suppressed the production of dibrominated compounds and effectively produced the desired monobrominated products with high selectivity. Rapid bromination of benzylic substrates containing a photoaffinity azide group was achieved without any decomposition.     

A novel impact three-point bend test method for determining dynamic fracture-initiation toughness

A novel impact three-point bend test method has been developed for determining the dynamic fracture-initiation toughness,K _Id, over the range of loading rates . The split-Hopkinson pressure-bar technique is used to measure dynamic loads applied to a bend specimen with a fatigue precrack. The stress-intensity-factor histories for the bend specimen are evaluated by means of a dynamic finite-element technique and the standard formula (ASTM E 399-83) based on the measured dynamic loads. The time of crack initiation is determined using a strain gage mounted near a crack tip. The results for 7075-T6 aluminum alloy and Ti−6A1−2Sn−4Zr−6Mo alloy indicate that the reliableK _Id data can only be obtained by evaluation procedures which take the inertial effects into account. It is shown that the novel impact bend test method in conjunction with dynamic finite-element analysis provides an effective means of characterizing the dynamic fracture-toughness parameterK _Id.     

Self-assembly of semifluorinated dendrons attached to electron-donor groups mediates their pi-stacking via a helical pyramidal column

Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce pi-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal domains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals.     

Pseudorotaxane-type fluorescent receptor exhibiting unique response to saccharides

Pseudorotaxane formed by reacting beta-cyclodextrin bearing a phenylboronic acid residue with 1-heptyl-4-(4'-dimethylaminostyryl)pyridinium functioned as a novel fluorescent saccharide receptor having unique responses.     

Separation of a Slater Determinant Wave Function with a Neck Structure into Spatially Localized Subsystems

A method of separating a Slater determinant wave function with a two-center neck structure into spatially localized subsystems is proposed, and it is applied to α + α Margenau–Brink cluster wave functions and antisymmetrized molecular dynamics wave functions of the ground state in ¹⁰Be and a negative-parity largely deformed state in ³⁵S.     

Discrimination of isomers by liquid ionization mass spectrometry with techniques of collisional activation and adduct ion formation

Liquid ionization mass spectrometry is a soft ionization technique used with liquid samples under atmospheric pressure. It facilitates the handling of reagents and the observation of ion–molecule reactions in the ion source. The differentiation of isomers by characteristic fragment ions, for example those resulting from asymmetrical cleavage of a cyclobutane ring, and by molecular adduct ion formation was studied. The samples studied were cyclobutane derivatives, alkyl 4-(3-oxo-3-pIienyl-l-aIkenyl)benzoate dimers, and reagents having two functional groups were used to produce adduct ions to clarify the difference between isomers. The reagents act on a sample molecule at two functional groups to form hydrogen bonds. Some correlations were observed between the structure of the sample and the relative abundances of molecular adduct ions and also fragment ions produced by collisionally activated dissociation.