Study of the peak effect phenomenon in single crystals of 2H-NbSe2

The weakly pinned single crystals of the hexagonal 2H-NbSe₂ compound have emerged as prototypes for determining and characterizing the phase boundaries of the possible order-disorder transformations in the vortex matter. We present here a status report based on the ac and dc magnetization measurements of the peak effect phenomenon in three crystals of 2H-NbSe₂, in which the critical current densities vary over two orders of magnitude. We sketch the generic vortex phase diagram of a weakly pinned superconductor, which also utilizes theoretical proposals. We also establish the connection between the metastability effects and pinning.     

Enantioselective total syntheses of manzamine a and related alkaloids

As a prelude to undertaking the total syntheses of the complex manzamine alkaloids, a series of model studies were conducted to establish the scope and limitations of intramolecular [4 + 2] cycloadditions of N-acylated vinylogous ureas with the trienic substrates 17a,b, 28a,b, and 34. These experiments clearly demonstrated that the geometry of the internal double bond and the presence of an electron-withdrawing group on the diene moiety were essential for the facile and stereoselective formation of the desired cycloadducts. The enantioselective syntheses of the manzamine alkaloids ircinol A (75), ircinal A (5), and manzamine A (1) were then completed by employing a convergent strategy that featured a novel domino Stille/Diels-Alder reaction to construct the tricyclic ABC ring core embodied in these alkaloids. Thus, the readily accessible chiral dihydropyrrole 58 was first converted in a single chemical operation into the key tricyclic intermediate 60. Two ring-closing metathesis reactions were then used to form the 13- and 8-membered rings leading to Z-72 and 74, the latter of which was quickly elaborated into ircinal A (5) via ircinol A (75). The synthetic 5 thus obtained was converted into manzamine A (1) following literature precedent. This concise synthesis of ircinal A required a total of 24 operations from commercially available starting materials with the longest linear sequence being 21 steps.     

Generation and characterization of phenylsulfanylcarbene

A photosensitive precursor (1) to phenylsulfanylcarbene 2 has been synthesized. Laser flash photolysis (308 nm) of 1 and chemical trapping studies of 2 are reported. [structure: see text]     

A Self-Assembled Cage with Endohedral Acid Groups both Catalyzes Substitution Reactions and Controls Their Molecularity

A self-assembled Fe₄L₆ cage complex internally decorated with acid functions is capable of accelerating the thioetherification of activated alcohols, ethers and amines by up to 1000-fold. No product inhibition is seen, and effective supramolecular catalysis can occur with as little as 5 % cage. The substrates are bound in the host with up to micromolar affinities, whereas the products show binding that is an order of magnitude weaker. Most importantly, the cage host alters the molecularity of the reaction: whereas the reaction catalyzed by simple acids is a unimolecular, S_N1-type substitution process, the rate of the host-mediated process is dependent on the concentration of nucleophile. The molecularity of the cage-catalyzed reaction is substrate-dependent, and can be up to bimolecular. In addition, the catalysis can be prevented by a large excess of nucleophile, where substrate inhibition dominates, and the use of tritylated anilines as substrates causes a negative feedback loop, whereby the liberated product destroys the catalyst and stops the reaction.     

Composition Operators and Endomorphisms

If b is an inner function, then composition with b induces an endomorphism, β, of L^￥(\mathbbT){L^\infty({\mathbb{T}})} that leaves H^￥(\mathbbT){H^\infty({\mathbb{T}})} invariant. We investigate the structure of the endomorphisms of B(L²(\mathbbT)){B(L^2({\mathbb{T}}))} and B(H²(\mathbbT)){B(H^2({\mathbb{T}}))} that implement β through the representations of L^￥(\mathbbT){L^\infty({\mathbb{T}})} and H^￥(\mathbbT){H^\infty({\mathbb{T}})} in terms of multiplication operators on L²(\mathbbT){L^2({\mathbb{T}})} and H²(\mathbbT){H^2({\mathbb{T}})} . Our analysis, which is based on work of Rochberg and McDonald, will wind its way through the theory of composition operators on spaces of analytic functions to recent work on Cuntz families of isometries and Hilbert C*-modules.     

Novel materials for bioanalytical and biomedical applications: Environmental response and binding/release capabilities of amphiphilic hydrogels with shape‐persistent dendritic junctions

The binding and release capabilities of a hydrogel series, constructed of hydrophilic poly(ethylene glycol) segments and hydrophobic dendritic junctions [poly (benzyl ether)s], are evaluated in aqueous media. The environmental response of the amphiphilic networks is also tested in water at three pH values: 1.5, 7.0, and 10.1. The highest swelling ratio is observed under acidic conditions and varies between 3.7 and 6.5, depending on the crosslinking density and dendrimer generation. Gel specimens with embedded indicators react within 3–6 s with a clear color switch to the change in the pH of the surrounding medium. The experiments with model anionic and cationic indicators and stains show that the hydrogels have basic interiors. The gel binding capabilities depend on the water solubility of the substrate and on the size of the incorporated dendritic fragments. Model release studies have been performed at 37 °C and pHs 1.5, 7.0, and 10.1. The observed phenomena are explained by the transformations in the structure and charge that both the networks and the model compounds undergo with the changes in the pH of the aqueous medium. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4017–4029, 2005     

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis,characterization, and investigation of their electrochemical,photochemical and computational properties

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,¹H,¹³C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)¹H and¹³C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6–31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.     

Inhibitors of plasmin that extend into both the S and S' binding sites: cooperative interactions between S1 and S2

A new procedure for the synthesis of cyclohexanone-based inhibitors of serine proteases is reported. In this procedure the reactive ketone functionality is carried through the synthesis in masked form as a TBDMS-protected alcohol. Deprotection followed by oxidation of the alcohol generates the final form of the inhibitor. Two new inhibitors, which interact with the S1-S3 and S2' subsites of plasmin, are synthesized using this procedure. Inhibitors 1 and 2 have IC50 values against plasmin of 20 and 24 microM, respectively. The inhibition studies show that cooperative binding of inhibitors in the S1 and S2 subsites of plasmin is important for determining inhibitor selectivity.