Anomalous excited-state dynamics of lucifer yellow CH in solvents of high polarity: evidence for an intramolecular proton transfer

The photophysics of the fluorescent probe Lucifer yellow CH has been investigated using fluorescence spectroscopic and computational techniques. The nonradiative rate is found to pass through a minimum in solvents of intermediate empirical polarity. This apparently anomalous behavior is rationalized by considering the possibility of predominance of different kinds of nonradiative processes, viz. intersystem crossing (ISC) and excited-state proton transfer (ESPT), in solvents of low and high empirical polarity, respectively. The feasibility of the proton transfer is examined by the structure determined by the density functional theory (DFT) calculations. The predicted energy levels based on the time-dependent density functional theory (TD-DFT) method in the gas phase identifies the energy gap between the S(1) and nearest triplet state to be close enough to facilitate ISC. Photophysical investigation in solvent mixtures and in deuterated solvents clearly indicates the predominance of the solvent-mediated intramolecular proton transfer in the excited state of the fluorophore in protic solvents.     

Deformation and failure mechanism of secondary cell wall in Spruce late wood

The deformation and failure of the secondary cell wall of Spruce wood was studied by in-situ SEM compression of micropillars machined by the focused ion beam technique. The cell wall exhibited yield strength values of approximately 160 MPa and large scale plasticity. High resolution SEM imaging post compression revealed bulging of the pillars followed by shear failure. With additional aid of cross-sectional analysis of the micropillars post compression, a model for deformation and failure mechanism of the cell wall has been proposed. The cell wall consists of oriented cellulose microfibrils with high aspect ratio embedded in a hemicellulose-lignin matrix. The deformation of the secondary wall occurs by asymmetric out of plane bulging because of buckling of the microfibrils. Failure of the cell wall following the deformation occurs by the formation of a shear or kink band.     

Phase evolution on heat treatment of sodium silicate water glass

Heat treatment of sodium silicate water glass of the nominal composition Na₂O/SiO₂ = 1:3 was carried out from 100 °C up to 800 °C and the advancement of the resulting phases was followed up by powder X-ray diffraction, scanning electron microscopy and thermogravimetry along with differential thermal analysis. The water glass, initially being an amorphous solid, starts to form crystals of β-Na₂Si₂O₅ at about 400 °C and crystallizes the SiO₂ modification cristobalite at about 600 °C that coexists along with β-Na₂Si₂O₅ up to 700 °C. At 750 °C Na₆Si₈O₁₉ appears as a separate phase and beyond 800 °C, the system turns into a liquid.     

Crystal structure of bis(triphenylphosphine)-cyclopentadienyl-ruthenium-phenylacetylide chloro-copper(I) acetone solvate

The product of the reaction of (-C₅ H₅)Ru(PPh₃)₂ Cl and CuC₂Ph has been characterized by single-crystal x-ray diffraction techniques and shown to have stoichiometry (-C₅ H₅)Ru(PPh₃)₂Cu(C₂Ph)Cl-(CH₃)₂CO(I). The compound contains a phenylethynyl group -bonded to the ruthenium atom and simultaneously -bonded to a terminal Cu-Cl bond. Crystals of this compound from acetone are monoclinic,P2₁/c, witha = 12.914, = 22.111,c = 16.534 Å, = 110.77 °, andZ — 4. Full-matrix least-squares refinement constraining the phenyl rings of the triphenylphosphines, the cyclopentadienyl ring, and the solvent of crystallization (acetone) as rigid groups yieldedR and weightedR values of 0.084 and 0.075, respectively.     

Strain-stiffening response in transient networks formed by reverse wormlike micelles

Strain-stiffening, that is, an increase in material stiffness at large deformations, is a property of many biological materials. Currently, model systems for the study of this phenomenon are elastic networks (gels) of semiflexible filamentous biopolymers such as actin, keratin, or fibrin. Here, we demonstrate strain-stiffening in a class of viscoelastic solutions, comprising reverse wormlike micelles. These structures are formed by the coassembly of the physiological surfactants, lecithin and bile salt, in an organic solvent, cyclohexane. In contrast to the biopolymer gels, the networks here are transient and are formed by the physical entanglement of relatively flexible worms. Our results suggest that neither a permanent network nor a high filament rigidity is required for strain-stiffening. We suggest a different origin, based on a temporary strain-induced increase in the volume fraction of entangled worms. Our system can also serve as a convenient synthetic model for future studies into this phenomenon.     

A facile route for creating "reverse" vesicles: insights into "reverse" self-assembly in organic liquids

Reverse vesicles are spherical containers in organic liquids (oils) consisting of an oily core surrounded by a reverse bilayer. They are the organic counterparts to vesicles in aqueous solution and could potentially find analogous uses in encapsulation and controlled release. However, few examples of robust reverse vesicles have been reported, and general guidelines for their formation do not exist. We present a new route for forming stable unilamellar reverse vesicles in nonpolar organic liquids, such as cyclohexane and n-hexane. The recipe involves mixing short- and long-chain lipids (lecithins) with a trace of a salt such as sodium chloride. The ratio of short- to long-chain lecithin controls the type and size of self-assembled structure. As this ratio is increased, a spontaneous transition from reverse micelles to reverse vesicles occurs. Small-angle neutron scattering (SANS) and transmission electron microscopy (TEM) confirm the presence of unilamellar vesicles in the corresponding solutions. Average vesicle diameters can be tuned from 60 to 250 nm depending on the sample composition.     

Surfactant vesicles for high-efficiency capture and separation of charged organic solutes

We demonstrate the unique ability of catanionic vesicles, formed by mixing single-tailed cationic and anionic surfactants, to capture ionic solutes with remarkable efficiency. In an initial study (Wang, X.; Danoff, E. J.; Sinkov, N. A.; Lee, J.-H.; Raghavan, S. R.; English, D. S. Langmuir 2006, 22, 6461) with vesicles formed from cetyl trimethylammonium tosylate (CTAT) and sodium dodecylbenzenesulfonate (SDBS), we showed that CTAT-rich (cationic) vesicles could capture the anionic solute carboxyfluorescein with high efficiency (22%) and that the solute was retained by the vesicles for very long times (t1/2 = 84 days). Here we expand on these findings by investigating the interactions of both anionic and cationic solutes, including the chemotherapeutic agent doxorubicin, with both CTAT-rich and SDBS-rich vesicles. The ability of these vesicles to capture and hold dyes is extremely efficient (>20%) when the excess charge of the vesicle bilayer is opposite that of the solute (i.e., for anionic solutes in CTAT-rich vesicles and for cationic solutes in SDBS-rich vesicles). This charge-dependent effect is strong enough to enable the use of vesicles to selectively capture and separate an oppositely charged solute from a mixture of solutes. Our results suggest that catanionic surfactant vesicles could be useful for a variety of separation and drug delivery applications because of their unique properties and long-term stability.     

Baryogenesis in the early Universe

We review various attempts to create the observed baryon asymmetry of the Universe. In particular, we consider models of GUT baryogenesis, baryogenesis via leptogenesis, the Affleck-Dine mechanism, electroweak baryogenesis and baryogenesis via topological defects and primordial black holes.     

Time and Space Fractional Diffusion in Finite Systems

Spatiotemporal nonlocal diffusion in a bounded system is addressed by considering fractional diffusion in a linear, composite system. By considering limiting conditions, solutions for combinations of Neumann and Dirichlet boundary conditions (either zero or nonzero) at the ends of a finite system are derived in terms of Mittag–Leffler functions by the Laplace transformation. Computational viability is demonstrated by inverting the solutions numerically and comparing resulting calculations with asymptotic solutions. Time and space fractional derivatives, defined by variables \(\alpha \) and \(\beta \), respectively, are employed in the Caputo sense; a single-sided, asymmetric space derivative is used. Inspection of the asymptotic solutions leads to insights on the structure of the solutions that may not be available otherwise; the resulting deductions are verified through the numerical inversions. For pure superdiffusion, characteristics of some of the solutions presented here are very similar to those of classical diffusion but combined effects for the corresponding situation result in power-law behaviors. Incidentally, to our knowledge, the pressure distribution for space fractional diffusion at long enough times in a finite system is derived based on first principles for the first time.