Study on the structures of 2-substituted iminothiazolidine derivatives

The reaction of 2-bromoethylamine 1 with methylisothiocyanate 2 under mild condition gave 2-methyl-amino-2-thiazoline 3 as the major product together with two kinds of byproducts, 3-(N-methylthiocar-bamoyl)-2-methyliminothiazolidine 4 and N,N′-dimethyl-N-(2-thiazolin-2-yl)thiourea 5. Thermal isomer-ization of 5 to 4 was observed. The structures of the byproducts were confirmed by X-ray crystallography.     

Dansyl-Modified γ-Cyclodextrin as a fluorescent sensor for molecular recognition

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C₁₂H₁₇N₄OS⁺·I^– · 1.5 H₂O, monoclinic,P2₁/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) ų,Z=8,D _c=1.606 g cm^–3,R=0.045 for 3328 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages).     

Synthesis of polystyenes with different stereoregularities by anionic polymerization

The stereoregularity of polystyrene prepared by anionic polymerization was determined by means of ¹³C-NMR spectroscopy. The stereoregularity changed with such polymerization conditions as catalyst, solvent, and temperature. Sodium naphthalene as catalyst gave a syndiotactic-rich polystyrene of 66–68% syndiotactic dyads independently of solvent and temperature, while potassium and cesium naphthalenes as catalyst produced polystyrenes with different stereoregularities ranging from syndiotactic-rich to isotactic-rich configurations, depending on solvent and temperature. The mechanism of anionic polymerization which caused the difference in stereoregularity was discussed from the viewpoint of growing ionic species.     

Application of 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate in the synthesis of 7a-substituted hexahydro-1h-pyrrolizines

The method for preparing 7a-substituted hexahydro-1H-pyrrolizines 2 from 1,2,3,5,6,7-hexahydropyrrol-izinium Perchlorate (3) was investigated, by which introduction of a wide variety of functionalities on C(7a) could be achieved easily.     

Simple indole alkaloids and those with a non-rearranged monoterpenoid unit

This review covers newly isolated simple indole alkaloids, structure determinations, total syntheses and biological activities reported in the literature in 2003.     

Electron microscopic study of dehydration transformations. I. Twin formation and mosaic structure in hematite derived from goethite

A study by means of electron microscopy at high resolution has enabled the analysis of the microstructure of hematite as produced by dehydration from goethite. The apparently “polycrystalline” structure is found to consist of aggregates of well-oriented twin-related hematite crystals, separated by regularly spaced H(001) walls of voids resulting from the loss of water. The material is thus broken up into blocks with sizes smaller than 50 Å. The crystallography of the twinned structure can be analyzed by electron diffraction data and dark-field imaging. These aggregates of hematite crystals provide an ideal mosaic structure. In particular the effect of this mosaic structure on the individual reflections of the diffraction patterns has been analyzed and discussed.     

Structure of a 1:1 molecular complex of trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with ethanol

X-ray analysis of the title complex revealed hydrogen-bonded chains comprising two crystallographically independent types of $\text{trans}$-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene molecules, in which the central 1,4-cyclohexadiene rings are respectively flat and very slightly puckered, with the ethanol molecules attached exclusively to the latter type.     

Autorecycling oxidation of alcohol catalyzed by 1,3,7,9,11,12,14-heptazapentacene-2,4,8,10 (14H,3H,9H,12H)-tetraones (mixed flavins)

1,3,7,9,11,12,14-Heptazapentacene-2,4,8,10 (14$\text{H}$,3$\text{H}$,9$\text{H}$,12$\text{H}$)-tetraones (mixed flavins) were prepared by the cyclization of 1,5-dihydro-8-[N-alkyl-N-(5-nitrouracil-6-yl)-amino-5-deazaflavins with Vilsmeier reagent. The mixed flavins oxidized alcohol under neutral condition in sunlight and a remarkable autorecycling was observed.     

Membrane permeation-controlled transdermal delivery system design. Influence of controlling membrane and adhesive on skin permeation of isosorbide dinitrate

A membrane permeation-controlled transdermal delivery system (MC-TDS) of isosorbide dinitrate (ISDN), a model drug, was prepared from polyvinyl alcohol aqueous gel containing the drug, a membrane consisting of ethylene-vinyl acetate copolymer membrane and acrylic adhesive (EV-a). The permeability of ISDN through the EV-a membrane was 2.5 times higher than that through excised hairless rat skin. The ratio of plasma concentration of ISDN after application of MC-TDS on stripped (damaged) skin relative to intact skin was lower than that after application of Frandol tape-S, a marketed ISDN TDS, which suggests that the EV-a membrane might work as a control membrane for overall delivery rate of ISDN to the body. When MC-TDS stored at 30 degrees C for 13.5-48h was applied to the damaged skin, however, the initial plasma concentration of ISDN was very much higher than the expected therapeutic level and was not controlled by the EV-a membrane. The initial high plasma concentration of ISDN after application of the stored MC-TDS on the damaged skin was due to migration of ISDN from the reservoir to the adhesive during storage at 30 degrees C. The migration of drugs into the adhesive might be an important problem in developing efficient MC-TDS.