Use of thiosulfonate for the protection of thiol groups in peptide ligation by the thioester method

Use of thiosulfonate for protecting thiol (-SH) groups in peptide ligation by the thioester method was examined. Thiosulfonate was introduced and was stable in the presence of silver ion, 4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine, and diisopropylethylamine. Based on these results, a strategy for using the thioester method and the native chemical ligation method in the synthesis of a single polypeptide is described.     

Pd(0)‐catalyzed polyaddition of bifunctional vinyloxiranes with 1,3‐dicarbonyl compounds: The synthesis of polymers containing hydroxy and carbonyl groups

The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh₃ and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh₃ and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd₂(dba)₃ · CHCl₃/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002     

Radical ring-opening polymerization behavior of vinylcyclopropanes derived from dienes and chloroform

1,1-Dichloro-2-vinylcyclopropane ( Ia ), 1,1-dichloro-2-methyl-2-vinylcyclopropane ( Ib ), 1,1,2-trichloro-2-vinylcyclopropane ( Ic ) were prepared from the corresponding dienes and chloroform in the presence of a phase transfer catalyst (PTC), R₄N⁺Cl^?. Monomers Ia – Ic underwent a clean 1,5-type radical ring-opening process to afford the corresponding polymers in good yield. Further, the relative rate of polymerization and reaction of ( I ) with thiophenol were studied.     

A multi-mode-driven molecular shuttle: photochemically and thermally reactive azobenzene rotaxanes

The shuttling process of alpha-CyD in three rotaxanes (1-3) containing alpha-cyclodextrin (alpha-CyD) as a ring, azobenzene as a photoactive group, viologen as an energy barrier for slipping of the ring, and 2,4-dinitrobenzene as a stopper was investigated. The trans-cis photoisomerization of 1 by UV light irradiation occurred in both DMSO and water due to the movement of alpha-CyD toward the ethylene group, while the photoisomerization of 2 occurred in DMSO, but not in water. No photoisomerization was observed for 3 in both water and DMSO. The activation parameters of 1 and 1-ref in DMSO are subject to a compensation relation between deltaS(double dagger) and deltaH(double dagger); however, in water, the deltaS(double dagger) terms are not compensated by the deltaH(double dagger) terms. Alternating irradiation of the UV and visible lights resulted in a reversible change in the induced circular dichroism (ICD) bands of trans-1 and cis-1. In contrast, after the UV light irradiation, the ICD band of trans-2 decreased without the appearance of any bands of cis-2. The NMR spectra of 2 in DMSO showed coalescence of the split signals for the methylene and for the viologen protons due to the shuttling of alpha-CyD. Both the NOE differential spectra for cis-1 in water after UV light irradiation and 2 in DMSO after heating to 120 degrees C showed the negative NOE peaks assigned to interior protons of alpha-CyD, suggesting that alpha-CyD in cis-1 exists at the one ethylene moiety, and alpha-CyDs in cis-2 and 2 heated in DMSO exist at the propylene moieties.     

Classical Valence Similarity in Fullerene Derivatives

Summary.  The generalized Pauling bond order was enumerated in the C₆₀ fullerene cage molecule (truncated icosahedral symmetry). This index measures chemical similarity in fullerene derivatives such as dihydrofullerene (C₆₀H₂), anionized monohydrofullerene (C₆₀H⁻), N-substituted monohydrofullerene (C₅₉NH), the fullerene dimer ((C₆₀)₂), and the dianionic fullerene dimer ((C₆₀)₂ ²⁻). It is also useful in judging the chemical stability of isomers. Received October 9, 2001. Accepted November 9, 2001     

High-Pressure Synthesis and Crystal Structure of B2S3

Two new high-pressure phases of binary boron-sulfur compounds, B₂S₃-II and B₂S₃-III, were synthesized at 3-6.2 GPa. A single crystal of B₂S₃-III was grown and the structure was determined (tetragonal, space group I4₁/a, a=16.086(2) Å, c=30.488(4) Å; V=7888(1) ų, Z=100, R=3.0% and R_w=2.8% for 3047 observed data [I>3.00σ(I)]. The structure of B₂S₃-III consists of two kinds of macrotetrahedra built up from 20 and 34 BS₄-tetrahedra. These macrotetrahedra connect each other to form an interpenetrating zincblende-type structure by sharing BS₄-tetrahedra at the corners of those. B₂S₃-III is anticipated having a rather disordered structure. From the UV-Vis diffuse reflectance spectrum, the optical band gap of B₂S₃-III was estimated to be 3.7 eV.     

Mechanism of antioxidative activity of fluvastatin-determination of the active position

In order to clarify the mechanism of action for the antioxidative activity of fluvastatin sodium (FLV, (+/-)-sodium (3RS, 5RS, 6E)-7-[3-(4-fluorophenyl)-1-(1-methylethyl)-1H-indol-2-yl]-3, 5-dihydroxy-6-heptanoate) and its derivatives, reaction of the corresponding methyl ester of FLV with di-tert-butyl diperoxyoxalate was examined, and the corresponding keto derivative was isolated from the reaction mixture. On the basis of this result, it was concluded that the active site is the allylic carbon conjugated with the indole ring.     

Anticoagulant activity of immobilized thrombomodulin

Bovine lung thrombomodulin was partially purified, and immobilized on agarose gel (Sepharose 4B). Immobilized thrombomodulin inhibited the procoagulant activity of thrombin, and enhanced the thrombin-catalyzed protein C activation. The plasma recalcification time test showed that immobilized thrombomodulin prolonged plasma clotting time. It is suggested that the immobilization of thrombomodulin will provide an antithrombogenic biomaterial able to convert thrombin from a procoagulant to an anticoagulant enzyme.     

Structures of Ganoderic Acid A and B,Two New Lanostane Type Bitter Triterpenes from Ganoderma lucidum (FR.) KARST.

The structures of two new bitter triterpenes, ganoderic acid A and B. isolated from a mushroom Ganoderma lucidum (FR.) Karst. (Polyporaceae) were determined as 1 and 2 on the basis of spectral data. Ganoderic acid A is a novel highly oxidized triterpene bearing a boat-shaped A-ring of lanostane.     

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.