Mono- and dicarbonyl-bridged tricyclic heterocyclic acceptors: synthesis and electronic properties

A series of trialkylsilyl-substituted 2,2'-dithiophene, 4,4'-di-n-hexyl-2,2'-dithiophene, 5,5'-dithiazole, and 2,2'-diselenophene with carbonyl (2a-d) and α-dicarbonyl bridges (3a-d) were prepared from readily available dihalides, using double lithiation followed by trapping with N,N-dimethylcarbamoyl chloride or diethyl oxalate (or N,N-dimethylpiperazine-2,3-dione), respectively. Cyclic voltammetry reveals that the first half-wave reduction potentials for this series of compounds span a wide range, from -1.87 to -0.97 V vs the ferrocene/ferrocenium couple at 0 V (0.1 M (n)Bu(4)NPF(6) in THF). A significant increase of the first half-wave reduction potential (by 0.50-0.67 V) was observed on substitution of the monocarbonyl bridge with α-dicarbonyl. Adiabatic electron affinity (AEA, gas phase) trends determined via density functional theory (DFT) calculations are in good agreement with the electrochemical reduction potentials. UV-vis absorption spectra across the series show a weak absorption band in the visible range, corresponding to the HOMO→LUMO transition within a one-electron picture, followed by a more intense, high-energy transition(s). Single-crystal X-ray structural analyses reveal molecular packing features that balance the interplay of the presence of the bulky substituents, intermolecular π-stacking interactions, and S···O intermolecular contacts, all of which affect the DFT-evaluated intermolecular electronic couplings and effective charge-carrier masses for the crystals of the tricyclic cores.     

Promoting peptide α-helix formation with dynamic covalent oxime side-chain cross-links

Covalent side-chain cross-linking has been shown to be a viable strategy to control peptide folding. We report here that an oxime side-chain linkage can elicit α-helical folds from peptides in aqueous solution. The bio-orthogonal bridge is formed rapidly under neutral buffered conditions, and the resulting cyclic oximes are capable of dynamic covalent exchange.     

Investigation of self-immolative linkers in the design of hydrogen peroxide activated metalloprotein inhibitors

A series of self-immolative boronic ester protected methyl salicylates and metal-binding groups with various linking strategies have been investigated for their use in the design of matrix metalloproteinase proinhibitors.     

Solvent relaxation of a room-temperature ionic liquid [bmim][PF6] confined in a ternary microemulsion

In this paper we have reported the solvent and rotational relaxation of 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF₆]) confined in tween 20/([bmim][PF₆]/water microemulsion using coumarin 153 (C-153) as probe. The most interesting feature of our experiment was that we observed an increase in solvent relaxation time with increase in R (R = tween 20-to-[bmim][PF₆] molar ratio). This is due to the fact that with increase in [bmim][PF₆] content of the microemulsions, the microviscosity of the pool of the microemulsions increases, and motion of ions of [bmim][PF₆] is hindered in the pool of microemulsions. Since motion of ions is responsible for solvation in room-temperature ionic liquids (RTILs), solvent-relaxation time increases with increase in R.     

Large relativistic effects in molecular properties of the hydride of superheavy element 111

Relativistic and electron correlation contributions in the hydride of the recently discovered superheavy element 111 were studied using ab-initio methods within different relativistic approaches. Relativistic effects decrease the (111)H bond distance by 0.42 Å. As a result of this large bond contraction, the bond distance of (111)H (1.51 Å) is comparable to that of the hydride of its lighter congener AuH (1.52 Å), but below that of AgH (1.60 Å). The dissociation energy is relativistically increased by approximately 1.2 eV and the stretching force constant is more than quadrupled from 1.1 mdyn/Å at the nonrelativistic level to 5.0 mdyn/Å at the relativistic level.     

Applications of wavelength-modulation spectroscopy in resolution of pressure and modulation broadened spectra

Theoretical and experimental results for modulation absorption spectroscopy (with simultaneous amplitude and wavelength modulations) are given, with particular emphasis on the effects of pressure and modulation broadening. As expected, such broadening effects result in a loss of resolution of nearly overlapping lines, whether these are from one or more absorbing species. The effects of phase-sensitive detection at harmonics greater than the commonly used second are investigated. It is shown that when detection is performed at higher harmonics, one is able to counter the loss of resolution due to pressure and modulation broadening. Applications in measurements of congested spectra, and in the simultaneous measurement of more than one species, are discussed. Other general characteristics of signals obtained by using higher-harmonic detection are also discussed, together with corresponding applications.     

Algebraic geometry of Gaussian Bayesian networks

Conditional independence models in the Gaussian case are algebraic varieties in the cone of positive definite covariance matrices. We study these varieties in the case of Bayesian networks, with a view towards generalizing the recursive factorization theorem to situations with hidden variables. In the case when the underlying graph is a tree, we show that the vanishing ideal of the model is generated by the conditional independence statements implied by graph. We also show that the ideal of any Bayesian network is homogeneous with respect to a multigrading induced by a collection of upstream random variables. This has a number of important consequences for hidden variable models. Finally, we relate the ideals of Bayesian networks to a number of classical constructions in algebraic geometry including toric degenerations of the Grassmannian, matrix Schubert varieties, and secant varieties.     

Isotropic-cholesteric phase transition in colloidal suspensions of filamentous bacteriophage fd

The co-existence concentrations of the isotropic and cholesteric liquid crystalline phases of the semi-flexible rod-like virus fd in aqueous suspension were measured as a function of ionic strength at room temperature. At several ionic strengths the magnetic-field-induced birefringence, which is proportional to the number of particles in a correlation volume N_corr, was measured for fd concentrations spanning the entire isotropic region. From this data the limiting concentration of stability (spinodal) of the isotropic phase, ρ*, was obtained. The co-existence concentrations and ρ* versus ionic strength compare well with predictions based on the theory of Khokhlov and Semenov, modified to include the effects of charge. A theoretical expression for the magnetic birefringence of persistent polymers was derived and agreed well with the data with the exception that N_corr at the isotropic to liquid crystal transition was smaller than predicted.