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.     

Tris(1,10‐phenanthroline‐N,N′)­iron(II) di­thio­cyanate tri­hydrate

The title mononuclear iron(II) complex, [Fe(C₁₂H₈N₂)₃](NCS)₂·3H₂O, has a slightly distorted octa­hedral coordination. One of the thio­cyanate ions and one of the water mol­ecules of crystallization show positional disorder.     

Thermo-responsive mending of polymers crosslinked by thermally reversible covalent bond: Polymers from bisfuranic terminated poly(ethylene adipate) and tris-maleimide

Remending properties of a network polymer with reversible reactivity are described. The network structure is constructed by a Diels-Alder (DA) reaction between furyl-telechelic poly(ethylene adipate) (PEAF₂) and a tris-maleimide, M₃. When a film sample was cut into two pieces and the cut surfaces were kept in contact with each other at 60 °C, rejoining of the cut pieces was observed. This mending was induced by the reversible cross-linking reaction bridging the cut surfaces. At the cut front, the “weak” DA adducts are selectively dissociated sacrificially to release the stress so as to protect the chemical structure of the prepolymer and the linker against the scission or degradation. The dissociated furan and maleimide readily reconnect by forward DA reaction to mend the material. The remending was also observed for the samples kept at room temperature after melting at 60 °C. So, the PEAF₂ network polymer is a thermo-responsive mendable material in which crack healing is induced by a prompt thermal stimulus.     

X‐ray irradiation induces local rearrangement of silica particles in swollen rubber

X‐ray photon correlation spectroscopy (XPCS) of swollen rubber containing spherical silica nanoparticles is reported. It is shown that irradiation by intense X‐rays leads to the breakdown of cross‐links, thereby inducing the local rearrangement of silica nanoparticles. This rearrangement process depends on the cross‐link density and is characterized by a compressed exponential relaxation with aging behaviour, which resembles a common feature of complex fluids observed with XPCS.     

Cationic starch derivatives as dynamic coating additives for protein analysis in capillary electrophoresis

Positively charged starch derivatives were used to modify the inner surface of fused-silica capillaries by addition to running buffer, which were subsequently employed in capillary electrophoresis (CE). Capillaries coated with the cationic starch derivatives were shown to generate a stable, reversed electroosmotic flow (EOF) in the investigated pH range of 3-9. The presented coating procedure was fast, based on a simple rinsing protocol where the polymer created a physically adsorbed, cationic polymer layer. Among the additives studied, a quaternary ammonium starch derivative showed a fast EOF mobility and effectively suppressed the adsorption of proteins. The intra- and inter-day reproducibility of the coating referring to the EOF mobility were satisfactory with relative standard deviation (RSD) of 0.27 and 1.67%, respectively. The coating enabled separation of some protein mixtures including basic proteins within l3 min with efficiencies up to 280,000 plates/m. In addition, this cationic starch derivative possessed a good solubility (about 100mg/mL), and it does not significantly contribute to the background adsorption in the UV region of 190-400 nm.     

Perfectly straight nanowires of fullerenes bearing long alkyl chains on graphite

Fullerene derivatives bearing long alkyl chains epitaxially adsorb on the basal plane of graphite forming well-ordered one-dimensional lamellae. Within the lamellae, the C60 moieties are organized in a zigzag-type fashion. The ordering is mainly governed by the substitution pattern and chain length of the alkyl chains. The electrochemical activity of the C60 groups is fully maintained in the surface-confined assemblies.     

Stereo structure-controlled and electronic structure-controlled estrogen-like chemicals to design and develop non-estrogenic bisphenol A analogs based on chemical hardness concept

The aim of this study was to elucidate the structure-activity relationship of bisphenol A (BPA) analogs using absolute hardness (eta) and absolute electronegativity (chi) (chemical hardness) and to design a non-estrogen active BPA. To determine the structure-activity relationships of BPA analogs, we investigated MCF-7 cell proliferation stimulated by BPA analogs and an eta-chi diagram based on the electronic structure of the BPA analogs. The results show that the actions of the environmental hormones BPA analogs have two chemical properties; (i) 'stereo structure-controlled' and (ii) 'electronic structure-controlled' estrogen-like chemical activities. Therefore, we designed and synthesized BPA analogs which do not possess these 2 characteristics, ((i) and (ii)), and demonstrate the non-estrogen activity of the analog.     

Organocatalytic direct asymmetric aldol reactions in water

We have developed direct asymmetric cross-aldol reactions that can be performed in water without addition of organic solvents. A bifunctional catalyst with a long hydrophobic alkyl chain efficiently catalyzed the reactions and afforded the desired aldol products in excellent yield with high enantiomeric excess, even when only an equal molar ratio of the donor and acceptor was used. These results reveal an effective design strategy for the development of aqueous organocatalytic systems.     

A highly practical instant catalyst for cyclotrimerization of alkynes to substituted benzenes

[reaction: see text] A 2-(2,6-diisopropylphenyl)iminomethylpyridine (1a)/CoCl(2).6H(2)O/Zn reagent has been developed as an effective instant catalyst for the intra- and intermolecular cyclotrimerization of alkynes to substituted benzenes, making the method extremely practical since the reagent, 1a/CoCl(2).6H(2)O/Zn, is inexpensive and easy to handle and the reaction is less sensitive to moisture and is reasonably general.