Rhodium-catalyzed cyclization of 1,6-enynes triggered by addition of arylboronic acids

1,6-Enynes reacted with arylboronic acids in the presence of a catalytic amount of a rhodium(I) complex under mild conditions to give (Z)-1-(1-arylethylidene)-2-vinylcyclopentanes. The regioselective addition of an arylrhodium(I) species across the carbon-carbon triple bond triggered the cyclization process. Intramolecular carborhodation onto the pendent alkene in a 5-exo mode furnished a five-membered ring. Finally, the rhodium(I) methoxide generated by beta-methoxy elimination reacted with the arylboronic acid to promote the next catalytic cycle.     

Three-way-output response system by electric potential: UV-vis, CD, and fluorescence spectral changes upon electrolysis of the chiral ester of tetracyanoanthraquinodimethane

The newly prepared tetracyanoanthraquinodimethane (TCNAQ) derivatives 1a,b with a chiral auxiliary are good electron acceptors and exhibit weak circular dichroism (CD) based on the absorption of TCNAQ. The twin-type electron acceptor 1c with two TCNAQ units shows larger ellipticity by exciton coupling. UV-vis, CD, and fluorescence spectra were changed drastically upon electrochemical reduction of 1c, which demonstrates the unprecedented three-way-output response system.     

Fluorescence modification of Gb3 oligosaccharide and rapid synthesis of oligosaccharide moieties using fluorous protective group

The use of the bisfluorous chain-type propanoyl (Bfp) group as a fluorous protective group made it possible to rapidly synthesize the Gb2 and Gb3 oligosaccharide derivatives by a simple fluorous-organic extraction purification. Furthermore, the fluorescence-labeled Gb2 and Gb3 oligosaccharides were prepared as a potential Vero Toxins detecting reagent.     

Multi‐input–Multi‐output Molecular Response System Based on Dynamic Redox Behavior of Hexaphenylethane‐type Electron Donors with the Tetrahydrophenanthrazepine Skeleton: Strong Chiroptical Signals through the Transmission of Point Chirality to Helicity

The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H⁺, Δ) and two‐way‐output (UV/Vis, CD) response systems.     

Thermosensitive biodegradable polydepsipeptide

A poly(N-isopropylacrylamide) (PNIPAAm)-like biodegradable thermosensitive polydepsipeptide, poly[Glc-Asn(N-isopropyl)], was synthesized by introducing an isopropyl amide group into poly[Glc-Asn]. Poly[Glc-Asn(N-isopropyl)] was degraded in vitro by cleavage of the ester bonds in the main chain in water at room temperature. The non-toxic nature of the polymer and its degradation products, coupled with a cloud point at 29 degrees C in water, make this polymer attractive for biomedical implant applications.     

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.     

Synthesis of cationic water-soluble esters of chlorin e6

Two esters of chlorin e₆ have been synthesized by esterification with aminoalcohols via the formation of acid chloride using oxalyl chloride and converted to the corresponding cationic water-soluble esters of chlorin e₆. The visible absorption and circular dichroism spectra have revealed that these two cationic chlorin e₆ esters synthesized are readily soluble in water as a monomer.