Organocatalytic trifluoromethylation of imines using phase-transfer catalysis with phenoxides. A general platform for catalytic additions of organosilanes to imines

A new approach to additions of silicon nucleophiles to imines was developed. The method is based on the phase-transfer of phenoxides by ammonium catalysts, overcoming the inability of amide adducts in promoting the reactions.     

WQ*-algebras of measurable operators

Every C*-algebra $\mathfrak{A}$ has a faithful *-representation π in a Hilbert space $\mathcal{H}$ . Consequently it is natural to pose the following question: under which conditions, the completion of a C*-algebra in a weaker than the given one topology, can be realized as a quasi *-algebra of operators? The present paper presents the possibility of extending the well known Gelfand — Naimark representation of C*-algebras to certain Banach C*-modules.     

Monte Carlo analysis of polymer translocation with deterministic and noisy electric fields

Polymer translocation through the nanochannel is studied by means of a Monte Carlo approach, in the presence of a static or oscillating external electric voltage. The polymer is described as a chain molecule according to the two-dimensional “bond fluctuation model”. It moves through a piecewise linear channel, which mimics a nanopore in a biological membrane. The monomers of the chain interact with the walls of the channel, modelled as a reflecting barrier. We analyze the polymer dynamics, concentrating on the translocation time through the channel, when an external electric field is applied. By introducing a source of coloured noise, we analyze the effect of correlated random fluctuations on the polymer translocation dynamics.     

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.     

The Post-Minkowskian Limit of <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>)-gravity

We formally discuss the post-Minkowskian limit of f(R)-gravity without adopting conformal transformations but developing all the calculations in the original Jordan frame. It is shown that such an approach gives rise, in general, together with the standard massless graviton, to massive scalar modes whose masses are directly related to the analytic parameters of the theory. In this sense, the presence of massless gravitons only is a peculiar feature of General Relativity. This fact is never stressed enough and could have dramatic consequences in detection of gravitational waves. Finally the role of curvature stress-energy tensor of f(R)-gravity is discussed showing that it generalizes the so called Landau-Lifshitz tensor of General Relativity. The further degrees of freedom, giving rise to the massive modes, are directly related to the structure of such a tensor.     

Efficient generation of N-photon binomial states and their use in quantum gates in cavity QED

A high-fidelity scheme to generate N-photon generalized binomial states (NGBSs) in a single-mode high-Q cavity is proposed. A method to construct superpositions of exact orthogonal NGBSs is also provided. It is then shown that these states, for any value of N, may be used for a realization of a controlled-NOT gate, based on the dispersive interaction between the cavity field and a control two-level atom. The possible implementation of the schemes is finally discussed.     

Synthetic approaches to bridgehead nitrogen methanesulfonamide derivatives of 3‐amino‐2‐thioxo‐2,3‐dihydrothieno[2,3‐d]pyrimidin‐4(1H)‐ones,potential cox‐2 selective inhibitors

Methane sulfonamide derivatives of 3‐amino‐2‐thioxo‐2,3‐dihydrothieno[2,3‐d]pyimidin‐4(1H)‐one, potential selective COX‐2 inhibitors, were synthesized and their structural elucidation is here reported. Some derivatives, at 10 μM concentration, showed a significant percentage of inhibition in some in vitro experiments.     

Atomistic mechanism of boron diffusion in silicon

B diffuses in crystalline Si by reacting with a Si self-interstitial (I) with a frequency g and so forming a fast migrating BI complex that can migrate for an average length lambda. We experimentally demonstrate that both g and lambda strongly depend on the free hole concentration p. At low p, g has a constant trend and lambda increases with p, while at high p, g has a superlinear trend and lambda decreases with p. This demonstrates that BI forms in the two regimes by interaction with neutral and double positive I, respectively, and its charge state has to change by interaction with free holes before diffusing.     

Isospectral Twirling and Quantum Chaos

We show that the most important measures of quantum chaos, such as frame potentials, scrambling, Loschmidt echo and out-of-time-order correlators (OTOCs), can be described by the unified framework of the isospectral twirling, namely the Haar average of a k-fold unitary channel. We show that such measures can then always be cast in the form of an expectation value of the isospectral twirling. In literature, quantum chaos is investigated sometimes through the spectrum and some other times through the eigenvectors of the Hamiltonian generating the dynamics. We show that thanks to this technique, we can interpolate smoothly between integrable Hamiltonians and quantum chaotic Hamiltonians. The isospectral twirling of Hamiltonians with eigenvector stabilizer states does not possess chaotic features, unlike those Hamiltonians whose eigenvectors are taken from the Haar measure. As an example, OTOCs obtained with Clifford resources decay to higher values compared with universal resources. By doping Hamiltonians with non-Clifford resources, we show a crossover in the OTOC behavior between a class of integrable models and quantum chaos. Moreover, exploiting random matrix theory, we show that these measures of quantum chaos clearly distinguish the finite time behavior of probes to quantum chaos corresponding to chaotic spectra given by the Gaussian Unitary Ensemble (GUE) from the integrable spectra given by Poisson distribution and the Gaussian Diagonal Ensemble (GDE).     

Distribution of low-density lipoprotein-bound low-molecular-weight thiols: a new analytical approach

We have recently demonstrated that low-density lipoprotein (LDL) apoprotein is able to bind the most concentrated plasma thiols such as cysteine, cysteinylglycine, and homocysteine by disulfide linkage. However, the LIF CE assay employed to measure linked thiols was not sensitive enough to verify whether low concentrated plasma thiols as glutathione and glutamylcysteine are also linked to apoprotein. By modifying sample treatment and electrophoretic parameters we set up a new method with an LOQ of about 1.5 nmol/L, by which we demonstrate that LDL apoprotein binds all physiological plasma thiols. The increased sensitivity was obtained by drying released apoB thiols after reduction treatment, dissolving them directly in a low volume of derivatization buffer and decreasing the dilution factor of derivatized sample before CE injection. Moreover, by increasing the concentration of the electrolyte buffer, we improved the selectivity of peaks, in particular between glutathione (GSH) and the impurity peak derived from unreacted 5-iodoacetamidofluorescein, which in the previous electrophoretic conditions were overlapped. The method optimization, reached by searching the best combination between sample matrix and CE run buffer, is fully described. Given the potential pathologic significance of protein thiolation, the proposed method may be useful to understand the mechanisms and the balances that regulate the interaction between thiols and -SH free groups of proteins.