Regiocontrolled rearrangement of isobenzofurans

The regioselective alkylation and oxidative rearrangement of isobenzofurans has been achieved to generate substituted 4,8-dihydroxyisochromanones in good yields and with complete regiocontrol.     

The Eilenberg-Moore Category and a Beck-type Theorem for a Morita Context

The Eilenberg-Moore constructions and a Beck-type theorem for pairs of monads are described. More specifically, a notion of a Morita context comprising of two monads, two bialgebra functors and two connecting maps is introduced. It is shown that in many cases equivalences between categories of algebras are induced by such Morita contexts. The Eilenberg-Moore category of representations of a Morita context is constructed. This construction allows one to associate two pairs of adjoint functors with right adjoint functors having a common domain or a double adjunction to a Morita context. It is shown that, conversely, every Morita context arises from a double adjunction. The comparison functor between the domain of right adjoint functors in a double adjunction and the Eilenberg-Moore category of the associated Morita context is defined. The sufficient and necessary conditions for this comparison functor to be an equivalence (or for the moritability of a pair of functors with a common domain) are derived.     

Preparation of submicron‐scale,electrospun cellulose fibers via direct dissolution

Cellulose nonwoven mats of submicron‐sized fibers (150 nm–500 nm in diameter) were obtained by electrospinning cellulose solutions. A solvent system based on lithium chloride (LiCl) and N,N‐dimethylacetamide (DMAc) was used, and the effects of (i) temperature of the collector, (ii) type of collector (aluminum mesh and cellulose filter media), and (iii) postspinning treatment, such as coagulation with water, on the morphology of electrospun fibers were investigated. The scanning electron microscopy (SEM) and X‐ray diffraction studies of as‐spun fibers at room temperature reveal that the morphology of cellulose fibers evolves with time due to moisture absorption and swelling caused by the residual salt and solvent. Although heating the collector greatly enhances the stability of the fiber morphology, the removal of salt by coagulation and DMAc by heating the collector was necessary for the fabrication of dry and stable cellulose fibers with limited moisture absorption and swelling. The presence and removal of the salt before and after coagulation have been identified by electron microprobe and X‐ray diffraction studies. When cellulose filter media is used as a collector, dry and stable fibers were obtained without the coagulation step, and the resulting electrospun fibers exhibit good adhesion to the filter media. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1673–1683, 2005     

Self-assembled shells composed of colloidal particles: fabrication and characterization

We construct shells with tunable morphology and mechanical response with colloidal particles that self-assemble at the interface of emulsion droplets. Particles self-assemble to minimize the total interfacial energy, spontaneously forming a particle layer that encapsulates the droplets. We stabilize these layers to form solid shells at the droplet interface by aggregating the particles, connecting the particles with adsorbed polymer, or fusing the particles. These techniques reproducibly yield shells with controllable properties such as elastic moduli and breaking forces. To enable diffusive exchange through the particle shells, we transfer them into solvents that are miscible with the encapsulant. We characterize the mechanical properties of the shells by measuring the response to deformation by calibrated microcantilevers.     

Convergent synthesis of (2R,3R,8R,9R)-N-Boc-ADDA

The convergent synthesis of N-Boc-(2R,3R,8R,9R,4E,6E)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldecadenoic acid (enantio-N-Boc-ADDA) is reported. Our flexible approach takes advantage of highly efficient non-aldol aldol and cross-metathesis methodologies.     

Microwave, photo- and thermally responsive PNIPAm-gold nanoparticle microgels

Microwave-, photo- and thermo-responsive polymer microgels that range in size from 500 to 800 microm and are swollen with water were prepared by a novel microarray technique. We used a liquid-liquid dispersion technique in a system of three immiscible liquids to prepare hybrid PNIPAm- co-AM core-shell capsules loaded with AuNPs. The spontaneous encapsulation is a result of the formation of double oil-in-water-in-oil (o/w/o) emulsion. It is facilitated by adjusting the balance of the interfacial tensions between the aqueous phase (in which a water-soluble drug may be dissolved), the monomer phase and the continuous phase. The water-in-oil (w/o) droplets containing 26 wt% NIPAm and Am monomers, 0.1 wt% Tween-80 surfactant, FITC fluorescent dye and colloidal gold nanoparticles spontaneously developed a core-shell morphology that was fixed by in situ photopolymerization. The results demonstrate new reversibly swelling and deswelling AuNP/PNIPAm hybrid core-shell microcapsules and microgels that can be actuated by visible light and/or microwave radiation (相似文献   

Comprehensive structural studies of 2',3'-difluorinated nucleosides: comparison of theory, solution, and solid state

The conformations of three 2',3'-difluoro uridine nucleosides were studied by X-ray crystallography, NMR spectroscopy, and ab initio calculations in an attempt to define the roles that the two vicinal fluorine atoms play in the puckering preferences of the furanose ring. Two of the compounds examined contained fluorine atoms in either the arabino or xylo dispositions at C2' and C3' of a 2',3'-dideoxyuridine system. The third compound also incorporated fluorine atoms in the xylo configuration on the furanose ring but was substituted with a 6-azauracil base in place of uracil. A battery of NMR experiments in D 2O solution was used to identify conformational preferences primarily from coupling constant and NOE data. Both (1)H and (19)F NMR data were used to ascertain the preferred sugar pucker of the furanose ring through the use of the program PSEUROT. Compound-dependent parameters used in the PSEUROT calculations were newly derived from complete sets of conformations calculated from high-level ab initio methods. The solution and theoretical data were compared to the conformations of each molecule in the solid state. It was shown that both gauche and antiperiplanar effects may be operative to maintain a pseudodiaxial arrangement of the C2' and C3' vicinal fluorine atoms. These data, along with previously reported data by us and others concerning monofluorinated nucleoside conformations, were used to propose a model of how fluorine influences different aspects of nucleoside conformations.     

Time-resolved spectroscopy of silver nanocubes: observation and assignment of coherently excited vibrational modes

The response of single crystal, cubic silver particles to ultrafast laser-induced heating has been examined experimentally and theoretically. The transient absorption traces display clear modulations due to coherently excited vibrational modes. Nanocube samples with edge lengths smaller than 50 nm show a single modulation, whereas samples larger than 50 nm show two vibrational modes. The results are compared to finite element calculations, where the cubes are modeled as having cubic crystal symmetry with the principal axes parallel to the sides of the particle. The action of the laser pulse is treated in two ways, first, as creating a uniform initial strain. In this case the predominant mode excited is the breathing mode. The period of this mode is in reasonable agreement with the vibrational periods measured for the smaller cubes and with the higher frequency modulation observed for the larger cubes. A nonuniform initial strain is also considered, which could arise from nonuniform heating for particles larger than the optical skin depth of the metal. In this case the predominant mode excited is a nontotally symmetric mode. The calculated periods from this analysis are in reasonable agreement with the lower frequency modulations observed for the larger samples. The results from this study show that, to within the accuracy of these measurements, the elastic constants of cubic silver nanoparticles are the same as bulk silver.