Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Angular position of nodes in the superconducting gap of quasi-2D heavy-fermion superconductor CeCoIn5

The thermal conductivity of the heavy-fermion superconductor CeCoIn5 has been studied in a magnetic field rotating within the 2D planes. A clear fourfold symmetry of the thermal conductivity which is characteristic of a superconducting gap with nodes along the ( +/- pi,+/- pi) directions is resolved. The thermal conductivity measurement also reveals a first-order transition at H(c2), indicating a Pauli limited superconducting state. These results indicate that the symmetry most likely belongs to d(x(2)-y(2)), implying that the anisotropic antiferromagnetic fluctuation is relevant to the superconductivity.     

All-optical image processing by means of a photosensitive nonlinear liquid-crystal film: edge enhancement and image addition-subtraction

We demonstrate two simple yet efficient all-optical image-processing techniques that use nonlinear photosensitive dye-doped nematic liquid-crystal films, namely, edge enhancement and image addition-subtraction operations. These films require no external bias and function at much lower optical powers and shorter response times than other conventional methods.     

Synthesis of substituted 3-iodopyrroles by electrophilic cyclization of propargylic aziridines

The electrophilic cyclization of propargylic aziridines is described. 3-Iodopyrroles having a variety of substituents were conveniently synthesized by the reaction of propargylic aziridines with iodine. The resulting substituted 3-iodopyrrole was further functionalized to the tri-substituted pyrroles with high efficiency.     

Stereoselective synthesis of cyclic hemiacetals from 4-formylbenzoates and α,β-unsaturated aldehydes using a sulfoalkyl-substituted N-heterocyclic carbene catalyst

N-Heterocyclic carbene-catalyzed transformation of 4-formylbenzoates and α,β-unsaturated aldehydes to cyclic hemiacetals is described. The reaction proceeded smoothly when the sulfopropyl-substituted imidazolium salt was used as the catalyst. Various substrates were converted to the corresponding cyclic hemiacetals in a stereoselective manner.     

Fragmentation reactions of optically active trisubstituted cyclopropylcarbinyl radicals.

Fragmentation reactions of optically active trisubstituted cyclopropylcarbinyl radicals and their application to the synthesis of natural products are described. Preparation of the optically pure substrates for radical fragmentation reactions was efficiently accomplished by lipase-mediated desymmetrization of sigma-symmetrical 3-substituted-1,2-cyclopropanedimethanols. In the presence of a radical stabilizing group, e.g., aryl, ester, or alpha,beta-unsaturated ester, the fragmentation occurs selectively to generate the radical on the alpha-carbon of the group and provide the optically pure alkene derivatives. These derivatives possess three chemically distinct functionalities, making them excellent chiral building blocks for the construction of biologically active molecules. The synthetic usefulness of the procedure developed here has been demonstrated by an application to the enantioselective synthesis of both enantiomers of the key intermediate, 4-(3,4-methylenedioxybenzyl)dihydrofuran-2(3H)-one (54), for the total synthesis of biologically active lignans.     

Efficient and enantioselective total syntheses of heliannuols A and K

The second-generation enantioselective synthesis of heliannuol A and the first enantioselective total synthesis of heliannuol K (via two routes) have both been accomplished efficiently; (heliannuol A, nine steps and 25% yield; heliannuol K, seven steps and 47% yield). Highlights of our synthetic strategy include a substrate-controlled chirality transfer in the Lewis acid mediated Claisen rearrangement of the allyl aryl ether for the key construction of a tertiary stereogenic center at the benzylic position followed by, for heliannuol A, ring-closing metathesis, diastereoselective epoxidation, and regioselective cleavage of the epoxide; and for heliannuol K, ring-closing metathesis and conjugate reduction of the eight-membered enone.     

Enantiocontrolled total syntheses of breviones A, B, and C

Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an α-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization.