A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution

An effective state specific (SS) model for the inclusion of solvent effects in time dependent density functional theory (TD-DFT) computations of excited electronic states has been developed and coded in the framework of the so-called polarizable continuum model (PCM). Different relaxation time regimes can be treated thus giving access to a number of different spectroscopic properties together with solvent relaxation energies of paramount relevance in electron transfer processes. SS and conventional linear response (LR) models have been compared for two benchmark systems (coumarin 153 and formaldehyde in different solvents) and in the limiting simple case of a dipolar solute embedded in a spherical cavity. The results point out the complementarity of LR and SS approaches and the advantages of the latter model especially for polar solvents. The favorable scaling properties of PCM-TD-DFT models in both SS and LR variants and their availability in effective quantum mechanical codes pave the route for the computation of reliable spectroscopic properties of large molecules of technological and/or biological interest in their natural environments.     

On the traction problem of classical elastostatics

We prove that the traction problem of homogeneous and isotropic elastostatics has a unique classical solution in bounded and exterior domains of class C^2,α for continuous boundary data.     

On a Fractional $$ p \& q$$ Laplacian Problem with Critical Sobolev–Hardy Exponents

We consider the following fractional \( p \& q\) Laplacian problem with critical Sobolev–Hardy exponents

$$\begin{aligned} \left\{ \begin{array}{ll} (-\Delta )^{s}_{p} u + (-\Delta )^{s}_{q} u = \frac{|u|^{p^{*}_{s}(\alpha )-2}u}{|x|^{\alpha }}+ \lambda f(x, u) &{} \text{ in } \Omega \\ u=0 &{} \text{ in } \mathbb {R}^{N}{\setminus } \Omega , \end{array} \right. \end{aligned}$$

where \(0<s<1\), \(1\le q<p<\frac{N}{s}\), \((-\Delta )^{s}_{r}\), with \(r\in \{p,q\}\), is the fractional r-Laplacian operator, \(\lambda \) is a positive parameter, \(\Omega \subset \mathbb {R}^{N}\) is an open bounded domain with smooth boundary, \(0\le \alpha <sp\), and \(p^{*}_{s}(\alpha )=\frac{p(N-\alpha )}{N-sp}\) is the so-called Hardy–Sobolev critical exponent. Using concentration-compactness principle and the mountain pass lemma due to Kajikiya [23], we show the existence of infinitely many solutions which tend to be zero provided that \(\lambda \) belongs to a suitable range.

     

Shear-induced deformation of surfactant multilamellar vesicles

Surfactant multilamellar vesicles (SMLVs) play a key role in the formulation of many industrial products, such as detergents, foodstuff, and cosmetics. In this Letter, we present the first quantitative investigation of the flow behavior of single SMLVs in a shearing parallel plate apparatus. We found that SMLVs are deformed and oriented by the action of shear flow while keeping constant volume and exhibit complex dynamic modes (i.e., tumbling, breathing, and tank treading). This behavior can be explained in terms of an excess area (as compared to a sphere of the same volume) and of microstructural defects, which were observed by 3D shape reconstruction through confocal microscopy. Furthermore, the deformation and orientation of SMLVs scale with radius R in analogy with emulsion droplets and elastic capsules (instead of R(3), such as in unilamellar vesicles). A possible application of the physical insight provided by this Letter is in the rationale design of processing methods of surfactant-based systems.     

Experimental observation of impossible-to-beat quantum advantage on a hybrid photonic system

Quantum resources outperform classical ones for certain communication and computational tasks. Remarkably, in some cases, the quantum advantage cannot be improved using hypothetical postquantum resources. A class of tasks with this property can be singled out using graph theory. Here we report the experimental observation of an impossible-to-beat quantum advantage on a four-dimensional quantum system defined by the polarization and orbital angular momentum of a single photon. The results show pristine evidence of the quantum advantage and are compatible with the maximum advantage allowed using postquantum resources.     

Fluorine Interactions in a Post‐Metallocene Titanium Catalyst: An ab initio Study

The stability of weak fluorine bonds in homogeneous catalyst is studied at the ab initio level for an arylpyridine post‐metallocene complex. The Ti···F···H_β interaction scheme, involving the agostic bond with titanium and the H‐bond with an H_β in the growing chain, is found to be the the most stable one. A possible optimal overlap involving the fluorine lone pairs is proposed. This three‐center interaction could play a role in the inhibition of H_β transfer to the metal or to the monomer in the termination reactions.

     

Enhanced mobility in P3HT-based OTFTs upon blending with a phenylene-thiophene-thiophene-phenylene small molecule

An enhancement in charge transport capacity in a poly(3-hexylthiophene) (P3HT) semicrystalline film, up to field-effect mobilities approaching 0.1 cm(2) V(-1) s(-1), has been achieved by co-deposition with a small molecule, i.e. 5,5'-bis(4-n-hexylphenyl)-2,2'-bithiophene (dH-PTTP), forming highly ordered crystals bridging large polymeric domains.     

Synthesis and biological evaluation of unprecedented ring-expanded nucleosides (RENs) containing the imidazo[4,5-d][1,2,6]oxadiazepine ring system

A small collection of ring-expanded nucleosides (RENs), containing the unprecedented bis-alkylated imidazo[4,5-d][1,2,6]oxadiazepine heterocyclic ring system, has been synthesized through a new general approach. Results of preliminary cytotoxicity tests on breast (MCF-7) and lung (A549) cancer cell lines are also reported.     

MS-based characterization of α(s2) -casein isoforms in donkey's milk

The primary structure of four α(s2) -casein (CN) isoforms, present as minor components in the dephosphorylated CN fraction of a milk sample collected in Eastern Sicily from an individual donkey belonging to the Ragusano breed at middle lactation stage, was determined, using the known donkey's α(s2) -CN (GenBank Acc. No. CAV00691; M(r) 26?028?Da) as reference. Proteins, with experimentally measured M(r) of 25?429, 21?939, 25?203 and 21?713?Da, were isolated by the combined use of reversed-phase high-performance liquid chromatography (RP-HPLC) and two-dimensional polyacrylamide gel electrophoresis. The major spot of each gel, corresponding to a single protein, was digested by trypsin, α-chymotrypsin and endoproteinase Glu-C. The resulting peptide mixtures were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and capillary RP-HPLC/nano-electrospray ionization tandem mass spectrometry, and the data obtained were used for the sequence determination. The isoforms are produced from differential splicing events involving exons 4, 5 and 6 and parts of the exon 17. Copyright ? 2012 John Wiley & Sons, Ltd.