Organo tin nucleophiles IV. Palladium catalyzed conjugate reduction with tin hydride

Highly chemoselective conjugate reduction of α,β-unsaturated carbonyl compounds is now possible by using tributyl tin hydride with Pd(PØ₃)₄; an optimization study puts forth the importance of added radical scavenger and proton source in these reductions.     

On Isotypic Decompositions for Non-Semisimple Hopf Algebras

In this paper we study the isotypic decomposition of the regular module of a finite-dimensional Hopf algebra over an algebraically closed field of characteristic zero. For a semisimple Hopf algebra, the idempotents realizing the isotypic decomposition can be explicitly expressed in terms of characters and the Haar integral. In this paper we investigate Hopf algebras with the Chevalley property, which are not necessarily semisimple. We find explicit expressions for idempotents in terms of Hopf-algebraic data, where the Haar integral is replaced by the regular character of the dual Hopf algebra. For a large class of Hopf algebras, these are shown to form a complete set of orthogonal idempotents. We give an example which illustrates that the Chevalley property is crucial.

     

The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations

The nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H₅O₂⁺ prepared in room‐temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump‐probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H⁺ transfer vibration and its combination and overtones. Vibrational lifetimes of H₅O₂⁺ are found to be in the sub‐100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low‐frequency modes continuously modify the proton binding site while affecting its motions.     

Juntas in the ℓ1‐grid and Lipschitz maps between discrete tori

We show that if , then is ‐close to a junta depending upon at most coordinates, where denotes the edge‐boundary of in the ‐grid. This bound is sharp up to the value of the absolute constant in the exponent. This result can be seen as a generalisation of the Junta theorem for the discrete cube, from [6], or as a characterisation of large subsets of the ‐grid whose edge‐boundary is small. We use it to prove a result on the structure of Lipschitz functions between two discrete tori; this can be seen as a discrete, quantitative analogue of a recent result of Austin [1]. We also prove a refined version of our junta theorem, which is sharp in a wider range of cases. © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 49, 253–279, 2016     

Identities of cofinal sublattices

If V is a variety of lattices and L a free lattice in V on uncountably many generators, then any cofinal sublattice of L generates all of V. On the other hand, any modular lattice without chains of order-type +1 has a cofinal distributive sublattice. More generally, if a modular lattice L has a distributive sublattice which is cofinal modulo intervals with ACC, this may be enlarged to a cofinal distributive sublattice. Examples are given showing that these existence results are sharp in several ways. Some similar results and questions on existence of cofinal sublattices with DCC are noted.This work was done while the first author was partly supported by NSF contract MCS 82-02632, and the second author by an NSF Graduate Fellowship.     

Solvent-dependent photoacidity state of pyranine monitored by transient mid-infrared spectroscopy.

We investigate with femtosecond mid-infrared spectroscopy the vibrational-mode characteristics of the electronic states involved in the excited-state dynamics of pyranine (HPTS) that ultimately lead to efficient proton (deuteron) transfer in H2O (D2O). We also study the methoxy derivative of pyranine (MPTS), which is similar in electronic structure but does not have the photoacidity property. We compare the observed vibrational band patterns of MPTS and HPTS after electronic excitation in the solvents: deuterated dimethylsulfoxide, deuterated methanol and H2O/D2O, from which we conclude that for MPTS and HPTS photoacids the first excited singlet state appears to have charge-transfer (CT) properties in water within our time resolution (150 fs), whereas in aprotic dimethylsulfoxide the photoacid appears to be in a non-polar electronic excited state, and in methanol (less polar and less acidic than water) the behaviour is intermediate between these two extremes. For the fingerprint vibrations we do not observe dynamics on a time scale of a few picoseconds, and with our results obtained on the O-H stretching vibration we argue that the dynamic behaviour observed in previous UV/Vis pump-probe studies is likely to be related to solvation dynamics.     

Stability and omitting types

We give a complete solution to the following question: when does a superstable theory have a model of powerκ omitting a partial typeq? In particular, for fixedq, if there is such a model of power ?₁ then there is one of power 2^? ₀; and if there is a model omittingq of power ?₁, then there are arbitrarily large ones. For stable theories, a model of power ? _ω ⁺ , omittingq implies one of power 2^? ₀, and this is sharp. Several improvements and some negative results are listed in the introduction.     

PSORALEN-MEDIATED VIRUS PHOTOINACTIVATION IN PLATELET CONCENTRATES: ENHANCED SPECIFICITY OF VIRUS KILL IN THE ABSENCE OF SHORTER UVA WAVELENGTHS

Abstract— Treatments with psoralens and long-wavelength ultraviolet radiation (UVA, 320–400 nm; PUVA) have shown efficacy for virus sterilization of platelet concentrates (PC). Our laboratory has employed the psoralen derivative 4'-aminomethyl-4, 5', 8-trimethylpsoralen (AMT), and we have found that platelet integrity is best preserved when rutin, a flavonoid that quenches multiple reactive oxygen species, is present during AMT/UVA treatment of PC. In this report, we examine the effects of different UVA spectra under our standard PC treatment conditions (i.e. 50 μg/mL AMT, 0.35 mM rutin and 38 J/cm² UVA). Added vesicular stomatitis virus (VSV; ≥5.5 log₁₀) was completely inactivated with the simultaneous maintenance of the platelet aggregation response (>90% of control) when a UVA light source with transmission mainly between 360 and 370 nm (narrow UVA1) was used. In contrast, with a broad-band UVA (320–400 nm; broad UVA) light source, the aggregation response was greatly compromised (<50% of control) with only a minor increase in the rate of VSV kill. With this lamp, platelet function could be improved to about 75% of the control by adding a long-pass filter, which reduced the transmission of shorter (≤345 nm) UVA wavelengths (340–400 nm; UVA1). At equivalent levels of virus kill, aggregation function was always best preserved when narrow UVA1 was used for PUVA treatment. Even in the absence of AMT, and with or without rutin present, narrow UVA 1 irradiation was better tolerated by platelets than was broad UVA. Our results suggest that for PUVA treatment of PC, the UVA dose range in which complete virus kill is obtained with the simultaneous maintenance of in vitro platelet function is smallest with broad UVA irradiation and largest with narrow UVA1. Thus, the virus specificity of PC treatment with AMT, UVA and quenchers can be further enhanced by the exclusion of the shorter UVA wavelength range.     

Coexistence of domains with distinct order and polarity in fluid bacterial membranes

In this study we sought the detection and characterization of bacterial membrane domains. Fluorescence generalized polarization (GP) spectra of laurdan-labeled Escherichia coli and temperature dependencies of both laurdan's GP and fluorescence anisotropy of 1,3-diphenyl-1,3,5-hexatriene (DPH) (rDPH) affirmed that at physiological temperatures, the E. coli membrane is in a liquid-crystalline phase. However, the strong excitation wavelength dependence of rlaurdan at 37 degrees C reflects membrane heterogeneity. Time-resolved fluorescence emission spectra, which display distinct biphasic redshift kinetics, verified the coexistence of two subpopulations of laurdan. In the initial phase, <50 ps, the redshift in the spectral mass center is much faster for laurdan excited at the blue edge (350 nm), whereas at longer time intervals, similar kinetics is observed upon excitation at either blue or red edge (400 nm). Excitation in the blue region selects laurdan molecules presumably located in a lipid domain in which fast intramolecular relaxation and low anisotropy characterize laurdan's emission. In the proteo-lipid domain, laurdan motion and conformation are restricted as exhibited by a slower relaxation rate, higher anisotropy and a lower GP value. Triple-Gaussian decomposition of laurdan emission spectra showed a sharp phase transition in the temperature dependence of individual components when excited in the blue but not in the red region. At least two kinds of domains of distinct polarity and order are suggested to coexist in the liquid-crystalline bacterial membrane: a lipid-enriched and a proteolipid domain. In bacteria with chloramphenicol (Cam)-inhibited protein synthesis, laurdan showed reduced polarity and restoration of an isoemissive point in the temperature-dependent spectra. These results suggest a decrease in membrane heterogeneity caused by Cam-induced domain dissipation.     

Amyloids: not only pathological agents but also ordered nanomaterials

Amyloid fibers constitute one of the most abundant and important naturally occurring self-associated assemblies. A variety of protein and peptide molecules with various amino acid sequences form these highly stable and well-organized assemblies under diverse conditions. These assemblies display phase states ranging from liquid crystals to rigid nanotubes. The potential applications of these supramolecular assemblies exceed those of synthetic polymers since the building blocks may introduce biological function in addition to mechanical properties. Here we review the structural characteristics of amyloidal supramolecular assemblies, their potential use as either natural or de novo designed sequences, and the range of applications that have been demonstrated so far.