Observation of three behaviors in confined liquid water within a nanopool hosting proton-transfer reactions

In this contribution, we report on studies of rotational and diffusional dynamics of 7-hydroxyquinoline (7HQ) within a reverse micelle (RM) containing different amounts of water. Analyzed in terms of the wobbling-in-a-cone model, the data reveal structural and dynamical properties of the nanopool. We clearly observed three regions in the behavior of confined water molecules within the RM hosting a double proton-transfer reaction between the probe and water. This observation remarkably reproduces the change of calculated water density within this life-mimicking medium. The number of water molecules per AOT head in the transition regions changes from 2 to 5, the latter being very near to the full solvation number (6) of the RM heads. Moreover, the H-bonds breaking and making within the RM to give new structures of the probe strongly affect the environment fluidization in different extents, reflected in different relaxation times of these structures; however, they are of similar sizes. We discuss the role of RM confinement and the proton-transfer dynamics on the behavior of water and their relationships to the packing of water molecules in the studied range of concentrations.     

Acylation,cyanoethylation and alkylation of methyl and phenyl indolylmagnesium salts: Influence of the substituents on the c- and N-reaction products

Analysis of the influence of the substitution on indolylmagnesium salts in the reaction with benzoyl chlo ride, acrylonitrile and methyl iodide, giving the C- and N-derivatives, have been carried out. The yield in the C- and N-product depends upon the electronic character and position of the substituent (methyl or phenyl) on the indole ring and of the ethereal solvent as well as the concentration and molar ratio of the reagents. The 2- or 3-phenyl substituted indolylmagnesium salts with acrylonitrile always gave the 1-(2-cyanoethyl)indole derivative.     

Fast imaging of the plume expansion produced by laser ablation of LiNbO3

Fast photography of the plume produced by laser ablation of LiNbO₃ in vacuum has been performed using an image intensified CCD (ICCD) camera in a time interval up to 2 7s after the laser pulse. Two differently oriented single crystalline LiNbO₃ targets were used. The results show that although the emission intensity of the laser-generated plume initially depends on the crystalline orientation of the target, it reaches a stationary state after several minutes which is the same for both targets orientations. Under these stationary conditions, the angular distribution of the Li atoms is found to be broader than that of Nb atoms. The observed less forward directed expansion of the Li species may explain the poor Li content normally observed in films grown by laser ablation of LiNbO₃ in vacuum.     

Critical parameters influencing the material distribution produced by pulsed laser deposition

The parameters that control the thickness distribution of thin films produced by pulsed laser deposition are investigated. It is found that highly asymmetric material distribution profiles can be obtained in vacuum when high energy densities are used and the target surface is positioned at the lens focus. The asymmetries are due to asymmetries in the spatial distribution of the beam. Under Ar gas pressure, the profile becomes symmetric and the distribution narrows as a consequence of collisions between the ejected species and the gas. In vacuum, decreasing the energy density, by decreasing the laser energy output or by moving the lens to defocus the beam, leads to symmetric distribution profiles. Nevertheless, in the first case a quite broad distribution and a low deposition rate are obtained, whereas in the second case the distribution is narrow and the deposition rate increases.     

Vacuum versus gas environment for the synthesis of nanocomposite films by pulsed-laser deposition

Nanocomposite films formed by Cu nanocrystals (NCs) with sizes <10 nm embedded in an amorphous Al₂O₃ host have been grown by alternate pulsed-laser deposition both in vacuum and in a buffer gas (Ar) up to pressures of 0.1 Torr. The dimensions, dimension distributions, and shape of the NC produced in vacuum and in Ar up to pressures of 5᎒^-3 Torr follow a similar trend as a function of the Cu areal density. This allows us to conclude that the nucleation and growth of the NC are dominated by processes occurring at the substrate surface rather than in the gas phase. For Ar pressures ̓᎒^-2 Torr, the anisotropy of the NC is enhanced, the deposition rate decreases abruptly and a significant amount of the buffer gas is incorporated into the host, thus leading to the formation of a porous material.     

Inflation,quantum fields,and CMB anisotropies

Inflationary cosmology has proved to be the most successful at predicting the properties of the anisotropies observed in the cosmic microwave background (CMB). In this essay we show that quantum field renormalization significantly influences the generation of primordial perturbations and hence the expected measurable imprint of cosmological inflation on the CMB. However, the new predictions remain in agreement with observation, and in fact favor the simplest forms of inflation. In the near future, observations of the influence of gravitational waves from the early universe on the CMB will test our new predictions.     

In‐capillary microextraction using monolithic polymers: Application to preconcentration of carbamate pesticides prior to their separation by MEKC

In the present work we report a novel procedure for in‐capillary microextraction using a monolithic polymeric sorbent. In the proposed methodology, sample treatment takes place in the CE instrument but in a different capillary from that used for the electrophoretic separation. Polymers based on butyl methacrylate and divinylbenzene formed in situ inside a capillary column were assayed. The best results were found with the divinylbenzene‐based polymers. The usefulness of the proposed procedure was checked for the determination of carbamate pesticides (Methomyl, Asulam, Carbendazim, Aldicarb, Carbetamide, Propoxur, Pirimicarb, Carbaryl, Carbofuran and Methiocarb) and three of their degradation compounds (Aldicarb sulphoxide, 2‐isopropoxyphenol and α‐naphthol) using MEKC. The optimization of the MEKC is reported, a good separation of the 13 analytes being obtained in less than 6 min. The analytical method using in‐capillary microextraction was validated in terms of linearity, repeatability, precision (RSD≤18% for 50 μg/L), and LODs (1–16 μg/L), and it revealed the usefulness of this in‐capillary preconcentration procedure for the determination of analytes of intermediate polarity.     

Electrochemical synthesis of PEDOT derivatives bearing imidazolium‐ionic liquid moieties

Novel poly(3,4‐ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium‐ionic liquid moieties were synthesized by electrochemical polymerizations. For this purpose, new functional monomers were synthesized having an 3,4‐ethylenedioxythiophene (EDOT) unit and an imidazolium‐ionic liquid with different anions such as tetrafluoroborate (BF), bis(trifluoromethane)sulfonimide ((CF₃SO₂)₂N^?), and hexafluorophosphate (PF). Next, polymer films were obtained by electrochemical synthesis in dicholoromethane solutions. Obtained polymers were characterized, revealing the characteristics of PEDOT in terms of electrochemical and spectroelectrochemical properties, FTIR, ¹H NMR, and AFM microscopy. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PF > (CF₃SO₂)₂N^? > BF > pure PEDOT as determined by water contact angle measurements. Furthermore, the polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making these polymers interesting candidates for wet processing methods. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3010–3021, 2009     

New insights into alpha-GalNAc-Ser motif: influence of hydrogen bonding versus solvent interactions on the preferred conformation

The structural features of the mucin-type simplest model, namely, the glycopeptide alpha-O-GalNAc-l-Ser diamide, have been investigated by combining NMR spectroscopy, molecular dynamics simulations, and DFT calculations. In contrast to previous reports, the study reveals that intramolecular hydrogen bonds between sugar and peptide residues are very weak and, as a consequence, not strong enough to maintain the well-defined conformation of this type of molecule. In fact, the observed conformation of this model glycopeptide can be satisfactorily explained by the presence of water pockets/bridges between the sugar and the peptide moieties. Additionally, DFT calculations reveal that not only the bridging water molecules but also the surrounding water molecules in the first hydration shell are essential to keep the existing conformation.     

Models of spherical shells as sources of Majumdar–Papapetrou type spacetimes

By starting with a seed Newtonian potential–density pair we construct relativistic thick spherical shell models for a Majumdar–Papapetrou type conformastatic spacetime. As a simple example, we considerer a family of Plummer–Hernquist type relativistic spherical shells. As a second application, these structures are then used to model a system composite by a dust disk and a halo of matter. We study the equatorial circular motion of test particles around such configurations. Also the stability of the orbits is analyzed for radial perturbation using an extension of the Rayleigh criterion. The models considered satisfying all the energy conditions.