Synthesis of new peptidic glycoclusters derived from β-alanine

The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs.     

Highly sensitive assay for tyrosine hydroxylase activity by high-performance liquid chromatography.

A highly sensitive assay for tyrosine hydroxylase (TH) activity by high-performance liquid chromatography (HPLC) with amperometric detection was devised based on the rapid isolation of enzymatically formed DOPA by a double-column procedure, the columns fitted together sequentially (the top column of Amberlite CG-50 and the bottom column of aluminium oxide). DOPA was adsorbed on the second aluminium oxide column, then eluted with 0.5 M hydrochloric acid, and assayed by HPLC with amperometric detection. D-Tyrosine was used for the control. alpha-Methyldopa was added to the incubation mixture as an internal standard after incubation. This assay was more sensitive than radioassays and 5 pmol of DOPA formed enzymatically could be measured in the presence of saturating concentrations of tyrosine and 6-methyltetrahydropterin. The TH activity in 2 mg of human putamen could be easily measured, and this method was found to be particularly suitable for the assay of TH activity in a small number of nuclei from animal and human brain.     

Partial degradation and biological activities of an antitumor polysaccharide from rice bran.

A rice bran polysaccharide designated RON was subjected either to partial hydrolysis with formic acid or to partial degradation by ultrasonic irradiation. A significant change in the molecular size was also observed during simple chromatography of RON on a strongly acidic ion exchange resin, although the apparent molecular weight of RON had been assumed to be more than 1 x 10(6) daltons (Da). This fact indicates that RON exists as molecular aggregates, presumably mediated by metal cations. Degradation products with average molecular weights above ca. 1 x 10(4) Da which were obtained by any of the three methods still retained the following activities of RON: in vivo antitumor activity against Meth-A fibrosarcoma in mice by oral administration, and in vitro macrophage stimulatory effects to induce tumoricidal activity and interleukin 1 production. This molecular size was proven to be the minimum requisite for these activities because smaller fragments were scarcely active. The aggregation was characteristic of RON but not essential for its antitumor activity because definite, though slightly reduced, activity was exhibited even by the smaller fragments obtained after the ion exchange resin treatment.     

Effects of the intramolecular NH...S hydrogen bond in mononuclear platinum(II) and palladium(II) complexes with 2,2'-bipyridine and benzenethiol derivatives

A series of complexes, [M(bpy)(SAr)2] (M = platinum(II) or palladium(II), bpy = 2,2'-bipyridine, SAr = 2- or 4-(acylamino)benzenethiolate, or 2-(alkylcarbamoyl)benzenethiolate), were synthesized and characterized on the basis of 1H NMR, IR, and electrochemical properties. The structures of [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) and [Pt(bpy)(S-2-t-BuNHCOC6H4)2] (3) were determined by X-ray analysis. The complexes have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom. A weak NH...S hydrogen bond in these complexes and [Pd(bpy)(S-2-Ph3CCONHC6H4)2] (4) is detected from the 1H NMR spectra and the IR spectra in chloroform and in the solid state. [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) exhibits a remarkably high-energy-shifted lowest-energy band in UV-visible spectra and has a positively shifted oxidation potential. The blue-shift of 42 nm and the positive shift of +0.24 V, as compared to those of [Pt(bpy)(SC6H5)2), are due to the effect of the NH...S hydrogen bond.     

Simultaneous determination of tetrahydro-β-carbolines and β-carbolines

Summary Reversed-phase ion-pair HPLC with fluorimetric detectors connected in series was studied for the simultaneous determination of two tetrahydro--carbolines and two -carbolines. After additon of internal standards the samples were reacted with fluorescamine, and then subjected to serial extractions to remove their precursor (tryptamine) from the analytical system. This treatment not only suppressed the artefactual formation of tetrahydro--carbolines and -carbolines during analysis, but also effectively purified them. Under optimum conditions, using trifluoroacetic acid as counter ion, all analytes were separated within 14 min and without major interfering peaks. The quantitative ranges were 0.25–80.0 ng mL^–1 for both tetrahydro--carbolines and 0.1–30.0 ng mL^–1 for both -carbolines. Replicate spiking experiments showed that recovery from most of the samples tested was over 90% and the relative standard deviation ranged from 0.7 to 10.4% within and between assays. The proposed method was applicable to various materials such as soy sauce, vinegar, ketchup, tabasco, beer, wine, sake, whisky, brandy, cows' milk, coffee, cocoa, cheese, cigarette smoke and urine.     

Determination of nickel in standard rocks and glasses by photon activation analysis with 30-MeV bremsstrahlung

The determination of nickel in various silicate rocks and glasses by photon activation analysis with a linear electron accelerator is described. Simultaneous irradiation of the sample and comparative standards produces the ⁵⁸Ni(γ, n)⁵⁷Ni reaction, and a post-irradiation chemical separation is used in conjunction with Ge(Li) γ-spectrometry. Nickel abundances for ten standard silicate rocks and two elementally doped glasses are presented and compared with the data previously published. The method is quite simple and gives good reproducible results for nickel down to sub-p.p.m. levels.     

Adsorption and reactions of NO on clean and CO-precovered Ir(111)

Adsorption and reactions of NO on clean and CO-precovered Ir(111) were investigated by means of X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HR-EELS), infrared reflection absorption spectroscopy (IRAS), and temperature-programmed desorption (TPD). Two NO adsorption states, indicative of fcc-hollow sites and atop sites, were present on the Ir(111) surface at saturation coverage. NO adsorbed on hollow sites dissociated to Na and Oa at temperatures above 283 K. The dissociated Na desorbed to form N2 by recombination of Na at 574 K and by a disproportionation reaction between atop-NO and Na at 471 K. Preadsorbed CO inhibited the adsorption of NO on atop sites, whereas adsorption on hollow sites was not affected by the coexistence of CO. The adsorbed CO reacted with dissociated Oa and desorbed as CO2 at 574 K.     

Electron-phonon interactions in charged cubic fluorocarbon cluster, (CF)8

Electron-phonon interactions in the charged cubic fluorocarbon, (CF)8 are studied, and compared with those in charged (CH)8 and (CD)8. The A1g mode of 1470 cm(-1) much more strongly couples to the a1g lowest unoccupied molecular orbitals (LUMO) than the A1g mode of 554 cm(-1) in (CF)8. The T2g mode of 1030 cm(-1), the Eg mode of 980 cm(-1), and the A1g mode of 1470 cm(-1) strongly couple to the t2u highest occupied molecular orbitals (HOMO) in (CF)8. The total electron-phonon coupling constants for the monoanion (l(-1)) and monocation (l(+1)) of (CF)8 are estimated to be 0.932 and 0.585 eV, respectively. The logarithmically averaged phonon frequencies for the monoanion (omega(ln,-1)) and monocation (omega(ln,+1)) of (CF)8 are estimated to be 1365 and 998 cm(-1), respectively. The l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution in cubane. The larger displacements of carbon atoms in the high frequency vibronic active mode in (CF)8 than those in (CD)8 due to larger atomic mass of fluorine than that of deuterium, and the unchanged electron distributions in the LUMO somewhat localized on carbon atoms as a consequence of H-F and H-D substitution in cubane, are the main reason why the l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution. The l(+1) and omega(ln,+1) values less significantly change than the l(-1) and omega(ln,-1) values by H-F substitution as well as by H-D substitution in cubane. This is because the t2u HOMO in (CF)8 and the t2g HOMO in (CH)8 are somewhat localized on fluorine atoms, and thus, the high frequency vibronic active modes in which the displacements of carbon atoms are large cannot necessarily very strongly couple to the HOMO somewhat localized on fluorine atoms in (CF)8.     

Insoluble monolayers of irisresorcinol at the air/water interface

Monolayer properties of irisresorcinol [5-(cis-10-heptadecenyl) resorcinol] were measured at the air/water interface. TheA-T isobars of the monolayers at 10 and 15 mN/m gave two-dimensional thermal expansivities of 1.4 × 10^–4/K and 1.3 × 10^–4/K at a temperature span from 7–40 C, respectively. The- A isotherms of the material showed only a little dependence on temperature from 5–35 C and onpH except at highpH, where monolayers expanded by ionization of resorcinol headgroups. Some types of saccharose in the subphase exhibited a characteristic interaction with irisresorcinol in monolayers, and there is a possibility that this material will be used for molecular recognition of some saccharoses.