A high-capacity cathode based on silicates material for advanced lithium batteries

Silicate materials have been proposed as alternative cathodes for Li-ion battery applications. A novel mixture of silicates, labelled Li₆MnSi₅, based on the molar ratio among the Li/Mn/Si precursors, with promising electrochemical properties as positive electrode material is synthesized through a solid-state reaction. The results indicate the proposed synthetic method as effective for preparation of nanostructured silicate powders with average particle diameter of 30 nm. Structural morphology of the samples was determined using X-ray powder diffraction (XRPD), XPS and FESEM analysis. A joint analysis by XRPD data and by density functional theory (DFT) identified LiHMn₄Si₅O₁₅, Li₂Mn₄Si₅O₁₅, Li₂Si₂O₅ and Li_0.125Mn_0.875SiO₄ as components of Li₆MnSi₅ mixture. The electrochemical performance of Li₆MnSi₅ was evaluated by charge/discharge testing at constant current mode. Li₆MnSi₅ discharge behaviour is characterized by high capacity value of 480 mA h g^?1, although such capacity fades gradually on cycling. Ex situ XPS studies carried out on the electrode in both full charged and discharged states pointed out that Li₂Si₂O₅ is decisive for achieving such high capacity. The discharge/charge plateau is most probably related to the change in the oxidation state of silicon at the surface of the silica material.     

Functionalized Proline‐Rich Peptides Bind the Bacterial Second Messenger c‐di‐GMP

c‐di‐GMP is an attractive target in the fight against bacterial infections since it is a near ubiquitous second messenger that regulates important cellular processes of pathogens, including biofilm formation and virulence. Screening of a combinatorial peptide library enabled the identification of the proline‐rich tetrapeptide Gup‐Gup‐Nap‐Arg, which binds c‐di‐GMP selectively over other nucleotides in water. Computational and CD spectroscopic studies provided a possible binding mode of the complex and enabled the design of a pentapeptide with even higher binding strength towards c‐di‐GMP. Biological studies showed that the tetrapeptide inhibits biofilm growth by the opportunistic pathogen P. aeruginosa.     

Bayesian Stopping Rules for Greedy Randomized Procedures

A greedy randomized adaptive search procedure (GRASP) is proposed for the approximate solution of general mixed binary programming problems (MBP). Examples are provided of practical applications that can be formulated as MBP requiring the solution of a large number of problem instances. This justifies, from both a practical and a theoretical perspective, the development of stopping rules aimed at controlling the number of iterations in a GRASP. To this end, a bayesian framework is laid down, two different prior distributions are proposed and stopping conditions are explicitly derived in analytical form. Numerical evidence shows that the stopping rules lead to an optimal trade-off between accuracy and computational effort, saving from unneeded iterations and still achieving good approximations.     

A comprehensive characterization of the set of polynomial curves with rational rotation-minimizing frames

A rotation–minimizing frame (f ₁,f ₂,f ₃) on a space curve r(ξ) defines an orthonormal basis for \(\mathbb {R}^{3}\) in which \(\mathbf {f}_{1}=\mathbf {r}^{\prime }/|\mathbf {r}^{\prime }|\) is the curve tangent, and the normal–plane vectors f ₂, f ₃ exhibit no instantaneous rotation about f ₁. Polynomial curves that admit rational rotation–minimizing frames (or RRMF curves) form a subset of the Pythagorean–hodograph (PH) curves, specified by integrating the form \(\mathbf {r}^{\prime }(\xi )=\mathcal {A}(\xi )\,\mathbf{i} \,\mathcal {A}^{*}(\xi )\) for some quaternion polynomial \(\mathcal {A}(\xi )\). By introducing the notion of the rotation indicatrix and the core of the quaternion polynomial \(\mathcal {A}(\xi )\), a comprehensive characterization of the complete space of RRMF curves is developed, that subsumes all previously known special cases. This novel characterization helps clarify the structure of the complete space of RRMF curves, distinguishes the spatial RRMF curves from trivial (planar) cases, and paves the way toward new construction algorithms.     

Stereoselective Synthesis of 1,3-Disaccharides through Diels-Alder Reactions: Part 2[ 1 ]: Convenient Protecting Groups for Heterodienes and Conformational Evaluations

Improved synthesis of 1,3-disaccharides, obtained diastereomerically pure by [4+2] hetero cycloadditions between glycals and α -thiono-β -keto-δ -lactones, has been reported. The choice of appropriate protecting groups for β -keto-δ -lactones, stable under cycloaddition conditions employed, sensibly shortened the synthesis of heterodienic precursors. The first example of a β -oxy-imino-δ -lactone synthesized from β -keto-δ -lactones was also reported. Molecular modeling and conformational evaluations about the cycloaddition features allowed tentatively rationalizing the experimental results.     

Reconstruction of cosmic and beam-halo muons with the CMS detector

The powerful muon and tracker systems of the CMS detector together with dedicated reconstruction software allow precise and efficient measurement of muon tracks originating from proton-proton collisions. The standard muon reconstruction algorithms, however, are inadequate to deal with muons that do not originate from collisions. This note discusses the design, implementation, and performance results of a dedicated cosmic muon track reconstruction algorithm, which features pattern recognition optimized for muons that are not coming from the interaction point, i.e., cosmic muons and beam-halo muons. To evaluate the performance of the new algorithm, data taken during Cosmic Challenge phases I and II were studied and compared with simulated cosmic data. In addition, a variety of more general topologies of cosmic muons and beam-halo muons were studied using simulated data to demonstrate some key features of the new algorithm.     

An interpolation scheme for designing rational rotation-minimizing camera motions

When a moving (real or virtual) camera images a stationary object, the use of a rotation-minimizing directed frame (RMDF) to specify the camera orientation along its path yields the least apparent rotation of the image. The construction of such motions, using curves that possess rational RMDFs, is considered herein. In particular, the construction entails interpolation of initial/final camera positions and orientations, together with an initial motion direction. To achieve this, the camera path is described by a rational space curve that has a rational RMDF and interpolates the prescribed data. Numerical experiments are used to illustrate implementation of the method, and sufficient conditions on the two end frame orientations are derived, to ensure the existence of exactly one interpolant. By specifiying a sequence of discrete camera positions/orientations and an initial motion direction, the method can be used to construct general rotation-minimizing camera motions.     

Niosomes from 80s to present: The state of the art

Efficient and safe drug delivery has always been a challenge in medicine. The use of nanotechnology, such as the development of nanocarriers for drug delivery, has received great attention owing to the potential that nanocarriers can theoretically act as “magic bullets” and selectively target affected organs and cells while sparing normal tissues. During the last decades the formulation of surfactant vesicles, as a tool to improve drug delivery, brought an ever increasing interest among the scientists working in the area of drug delivery systems. Niosomes are self assembled vesicular nanocarriers obtained by hydration of synthetic surfactants and appropriate amounts of cholesterol or other amphiphilic molecules. Just like liposomes, niosomes can be unilamellar or multilamellar, are suitable as carriers of both hydrophilic and lipophilic drugs and are able to deliver drugs to the target site. Furthermore, niosomal vesicles, that are usually non-toxic, require less production costs and are stable over a longer period of time in different conditions, so overcoming some drawbacks of liposomes.     

Bivariate hierarchical Hermite spline quasi-interpolation

Spline quasi-interpolation (QI) is a general and powerful approach for the construction of low cost and accurate approximations of a given function. In order to provide an efficient adaptive approximation scheme in the bivariate setting, we consider quasi-interpolation in hierarchical spline spaces. In particular, we study and experiment the features of the hierarchical extension of the tensor-product formulation of the Hermite BS quasi-interpolation scheme. The convergence properties of this hierarchical operator, suitably defined in terms of truncated hierarchical B-spline bases, are analyzed. A selection of numerical examples is presented to compare the performances of the hierarchical and tensor-product versions of the scheme.     

Thermodynamics and biological properties of the aqueous solutions of new glucocationic surfactants

Thermodynamic properties of aqueous solutions of newly synthesized compounds, namely, N-[2-(beta-D-glucopyranosyl)ethyl]-N,N-dimethyl-N-alkylammonium bromides with hydrophobic tails of 12 (C12DGCB) and 16 (C16DGCB) carbon atoms, determined as a function of concentration by means of direct methods, are reported here. Dilution enthalpies, densities, and sound velocities were measured at 298 K, allowing for the determination of apparent and partial molar enthalpies, volumes, and compressibilities. Changes in thermodynamic quantities upon micellization were derived using a pseudophase-transition approach. From a comparison with the corresponding acetylated compounds N-[2-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)ethyl]-N,N-dimethyl-N-dodecylammonium bromide (C12AGCB) and N-[2-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyanosyl)ethyl]-N,N-dimethyl-N-hexadecylammonium bromide (C16AGCB), the role played in the micellization process by the acetylated glycosyl moiety was inferred: it enhances the hydrophobic character of the molecule and lowers the change in enthalpy of micelle formation by about 1.5 kJ mol(-1). By comparing the volume of C12DGCB with those of DEDAB and DTAB, the volumes taken up by the (beta- d-glucopyranosyl)ethyl and beta- d-glucopyranosyl groups were found to be 133 and 99 cm3 mol(-1), respectively. Regarding the interaction with DPPC membranes, it seems that the sugar moiety of the hexadecyl deacetylated compound gives rise to hydrogen bonds with the oxygen atoms of the lipid phosphates, shifting the phase transition of DPPC from a bilayer gel to a bilayer liquid crystal to lower temperatures. C16AGCB induces significantly greater changes than C16DGCB in the structure of liposomes, suggesting the formation of domains. The interaction is strongly enhanced by the presence of water. Neither compound interacts strongly with DNA or compacts it, as shown by EMSA assays and AFM images. Only C16AGCB is able to deliver little DNA inside cells when coformulated with DOPE, as shown by the transient transfection assay. This might be related to the ability of C16AGCB to form surfactant-rich domains in the lipid structure.