Quantitative estimation of interaction between carbohydrates and concanavalin A by surface plasmon resonance biosensor

We measured the affinity of more than 20 sugars with concanavalin A (ConA) by an optical biosensor (surface plasmon resonance sensor) using asialofetuin (ASF) as an immobilized binding partner of ConA. We determined kinetic parameters of the effects of sugars on the dissociation of ConA from ASF quantitatively, and the structural requirements of the functional groups of sugars for binding with ConA. We found that the affinity of ConA for sugars is dependent on its conformation induced by interaction with the binding partner. In addition, the results showed that optical biosensor system is well mimics the interaction of ConA with sugars in biomembrane.     

Dosimetry of fast neutrons in 1W nuclear reactor with plastic nuclear-track detectors

A nuclear reactor at Kinki University is operated at the maximum of 1W. It produces fission neutrons as much as gamma-rays. To facilitate its use for neutron radiobiology, fast neutrons inside the reactor were measured with nuclear-track detectors TS 16 N and a pair of ion chambers. The angular dependence of TS 16 N response, an anisotropy of fast neutron fluxes in the reactor and misuse of the kerma factor assumed for radiation protection business are the major causes of discrepancy is measured doses by the two methods. Correction factors for the three causes are proposed. After correction, neutron doses estimated with TS 16 N and chambers agree within 5%. The dose-rate at the reactor's center is about 20 tissue-cGy/h. This is the first in situ dosimetry of fast neutrons in a reactor with track detectors attached to biologic samples. Our routine usage has demonstrated that, if used with caution, TS 16 N elements are handy, reliable monitors for fast neutron dosimetry as they are insensitive to contaminated gamma-rays and small enough to be attached to biologic samples.     

Polymerization of tetraallyl ammonium chloride

The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion.     

Upward temperature shift of the intrinsic phase lag of the magnetization of Bis(phthalocyaninato)terbium by ligand oxidation creating an S = 1/2 spin

An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons.     

Reaction of enaminones with carbon disulfide: Synthesis of heterocycles using enamino dithiocarboxylates

Reaction of various types of enaminones, which are prepared by the condensation of 1,3-dicarbonyl compounds with aromatic amines, with carbon disulfide in the presence of sodium hydroxide as the base in dimethyl sulfoxide to give the corresponding enamino dithiocarboxylates, 1,3-thiazines and trithiones. Enamino dithiocarboxylates are cyclized under refluxing in diphenyl ether to give the fused quinoline derivatives. The reaction of 6-arylamino-1,3-dimethyluracils with excess carbon disulfide in the presence of sodium hydroxide and subsequent methylation with dimethyl sulfate gave directly the corresponding 1,3-dimethyl-5-methylthiopyrimido[4,5-b]quinoline-2,4(1H,3H)-diones.     

NMR and MO Studies on the Molecular Structure of a Fluoranthene-Benzene Complex

Summary. Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The ¹H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the ¹H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of C_S symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the ¹H NMR spectral shifts mentioned above and the experimentally predicted C_S structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure.