Mössbauer spectroscopic study of ferrocene derivatives in the adsorption and liquid-crystalline states

Mössbauer spectra of ferrocene derivatives in the solid, adsorption and liquidcrystalline states were measured at temperatures ranging from 78 to 423 K. The peak intensities of the Mössbauer spectra of ferrocene derivatives adsorbed on silica gel decreased markedly with an increase in temperature. The Mössbauer absorption of [4-(4-methoxyphenoxycarbonyl)-phenoxycarbonyl]alkyl 4-ferrocenylbenzoate at 295 K during the cooling process was observed in what was assumed to be the liquid-crystalline state.     

Asymmetric total synthesis of octalactin B using a new and rapid lactonization

A method for the synthesis of octalactin B is established via a new and quite effective mixed-anhydride lactonization for the synthesis of an eight-membered ring moiety using 2-methyl-6-nitrobenzoic anhydride with DMAP. Both an optically active linear precursor of the lactone and a side chain of octalactins are prepared by the enantioselective aldol reaction of ketene silyl acetals with aldehydes.     

Synthesis of isoxazolo[2,3-a]quinoxalines and pyrrolo[1,2-a]quinoxalines by 1,3-dipolar cycloaddition reaction

The isoxazolo[2,3-a]quinoxalines 11a,b and pyrrolo[1,2-a]quinoxalines 12a,b were selectively synthesized from the 2-substituted 6-chloroquinoxaline 4-oxides 10a,b . The pyrrolo[1,2-a]quinoxalines 12a,b were clarified to be produced by the ring transformation of the isoxazolo[2,3-a]quinoxalines 11a,b . The pyrrolo[1,2-a]quinoxalines 14a,b were obtained from both 2,6-dichloroquinoxaline 4-oxide 9 and compounds 12a,b .     

Synthesis of stable and cell-type selective analogues of cyclic ADP-ribose, a Ca(2+)-mobilizing second messenger. Structure--activity relationship of the N1-ribose moiety

We previously developed cyclic ADP-carbocyclic ribose (cADPcR, 2) as a stable mimic of cyclic ADP-ribose (cADPR, 1), a Ca(2+)-mobilizing second messenger. A series of the N1-ribose modified cADPcR analogues, designed as novel stable mimics of cADPR, which were the 2"-deoxy analogue 3, the 3"-deoxy analogue 4, the 3"-deoxy-2"-O-(methoxymethyl) analogue 5, the 3"-O-methyl analogue 6, the 2",3"-dideoxy analogue 7, and the 2",3"-dideoxydidehydro analogue 8, were successfully synthesized using the key intramolecular condensation reaction with phenylthiophosphate-type substrates. We investigated the conformations of these analogues and of cADPR and found that steric repulsion between both the adenine and N9-ribose moieties and between the adenine and N1-ribose moieties was a determinant of the conformation. The Ca(2+)-mobilizing effects were evaluated systematically using three different biological systems, i.e., sea urchin eggs, NG108-15 neuronal cells, and Jurkat T-lymphocytes. The relative potency of Ca(2+)-mobilization by these cADPR analogues varies depending on the cell-type used: e.g., 3"-deoxy-cADPcR (4) > cADPcR (2) > cADPR (1) in sea urchin eggs; cADPR (1) > cADPcR (2) approximately 3"-deoxy-cADPcR (4) in T-cells; and cADPcR (2) > cADPR (1) > 3"-deoxy-cADPcR (4) in neuronal cells, respectively. These indicated that the target proteins and/or the mechanism of action of cADPR in sea urchin eggs, T-cells, and neuronal cells are different. Thus, this study represents an entry to cell-type selective cADPR analogues, which can be used as biological tools and/or novel drug leads.     

Highly sensitive spectrophotometric determination of osmium(VIII) with pyrogallolphthalein and hydrogen peroxide in the presence of Brij 35

Summary A highly sensitive determination of osmium(VIII) is based on the decolouring reaction with pyrogallolphthalein (gallein) and hydrogen peroxide in the presence of Brij 35. Beer's law was obeyed in the range of 0–0.5 ng of osmium(VIII) per 10 ml and the apparent decomposed absorption coefficient was 2.5×10⁹ l mol^–1 cm^–1 at 535 nm.Application of xanthene derivatives in analytical chemistry. Part XCIII. Part XCII see ref. [1]     

Indole alkaloids from Kopsia jasminiflora

Seven new indole alkaloids (aspidofractinine type 1–3, kopsine type 5, strychnos type 6, and vincamine type 7, 8) were isolated from Kopsia jasminiflora (Apocynaceae) collected in Thailand. 5-Oxokopsinic acid (4) was isolated from nature for the first time. The structures of the new alkaloids were determined by spectroscopic analyses and chemical transformation of a known alkaloid. 5,6-Secokopsinine (1) possesses a dialdehyde function that is formed by oxidative cleavage of the C-5–C-6 bond of kopsinine (9). New vincamine-type alkaloid 8 showed potent inhibitory activity toward human cancer cell lines (A549, HT29, HCT116).     

Scaling of anomalous hall resistivity in Nd2(Mo(1-x)Nb(x))2O7 with spin chirality

We have investigated scaling of anomalous Hall resistivity with longitudinal resistivity (rho(xx)) in pyrochlore type Nd2(Mo(1-x)Nb(x))2O7 with spin chirality. Scattering rate of the conduction electron on the Mo sublattice can be varied with x from band transport to polaron hopping, while keeping the two-in-two-out structure of the Nd moments intact. The anomalous part of the Hall resistivity arising from the Mo spin chirality (rho(H)(chi)) shows a clear scaling behavior with rho(xx) (rho(H)(chi) proportional to rho(xx)0.39), in accord with a recent theoretical result based on the Berry phase mechanism in the hopping conduction regime.     

Evaluation of the Efficiency of the Macrolactonization Using MNBA in the Synthesis of Erythromycin A Aglycon

Various intermediates for the synthesis of erythronolide A, an aglycon of erythromycin A, are prepared from the corresponding seco‐acids using 2‐methyl‐6‐nitrobenzoic anhydride (MNBA) in the presence of 4‐(dimethylamino)pyridine (DMAP) with or without triethylamine. The efficiency of the MNBA lactonization is assessed by studying this method and comparing the results with those of the other established macrocyclization protocols. It has been finally concluded that (i) the conformationally appropriate substrate for the monomeric cyclization gave the desired lactone in excellent yield under mild reaction conditions in the presence of MNBA and DMAP, (ii) the highly‐strained substrate for the cyclization also afforded the monomeric lactone in relatively good yield at 100°C in toluene, and (iii) the seco‐acid having stable linear conformation, which preferred dimerizing more than forming the monomeric lactone, provided the corresponding diolide in high yield with the constant ratio of the monomer to dimeric lactone (approximately 1/5). © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 305–320; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900017     

Preparation of Porous Protein-Based Hydogel for Highly Sensitive Protein Chips

Summary: Protein chips are important tools for high-throughput analysis of biological events. We have developed a novel method to prepare a protein-based hydrogel, that is, a “Three-Dimensional Nano-structured Protein Hydrogel” (3-D NPH), which is composed of protein and polymer nano-particles. The 3-D NPH could be easily prepared by dispensing a protein and polymer mixture on a substrate. Surprisingly, gold particles conjugated with protein A diffused into the 3-D NPH which was made of mouse IgG through the pores. We have shown that the protein chips made with our 3-D NPH method has tremendously improved sensitivity in detecting protein-protein interactions compared with that of direct protein immobilization methods.