Conformational analysis of hydrazones. 1H dynamic nuclear magnetic resonance and solvent effects in aryl- and 2-furylaldehyde ethylaminoacetylhydrazones

Aryl- and 2-furylaldehyde ethylaminoacetylhydrazones were examined in different solvents and over a wide temperature range with ¹H NMR in order to study their conformational properties. Nearly equal amounts of the E/Z isomers, relative to the C?N bond, are present, even when the solvents and the substituents on the aldimino carbon produce small changes in the isomeric mixture. The activation parameters of the thermal isomerization process were measured, and the results are in the line with a lateral-shift type mechanism, also supported by theoretical calculations on a model compound. No other internal process was noted from the low-temperature spectral behaviour, and this was interpreted in terms of a highly biased equilibrium concerning the rotation around the C(O)? N bond. Chemical shifts obtained in different solvents also enable the most stable arrangement of the whole molecule of these compounds to be postulated.     

Rabi flopping in a two-level system with a time-dependent energy renormalization: intersubband transitions in quantum wells

We obtain pulse-driven Rabi oscillations guided by a generalization of the rotating-wave approximation to include, in the optical-Bloch equations, two-level systems with a time-varying transition energy. We achieve this by using chirped pulses with the central frequency given by the time-varying transition energy. Using this approach, we predict Rabi oscillations in intersubband transitions in a two-subband n-type modulation-doped quantum well by taking into account the time-dependent intersubband energy-gap renormalization due to depolarization-shift effects. We obtain Rabi oscillations for jpi (j=0,1,2, ) pulses in the presence of dephasing.     

Palladium-catalyzed oxidative homocoupling of potassium alkenyltrifluoroborates: synthesis of symmetrical 1,3-dienes

Herein, we describe a convenient method for the synthesis of symmetrical 1,3-dienes employing an oxidative palladium-catalyzed homocoupling of potassium alkenyltrifluoroborates providing products in good yields relative to existing methodologies. This is the first report of a cross-dimerization of potassium alkenyltrifluoroborates.     

Global Equivalence for Deformable Theormoeleastic Bodies

We consider equilibria arising in a model for phase transitions which correspond to stable critical points of the constrained variational problem Here W is a double‐well potential and is a strictly convex domain. For ε small, this is closely related to the problem of partitioning Ω into two subdomains of fixed volume, where the subdomain boundaries correspond to the transitional boundary between phases. Motivated by this geometry problem, we show that in a strictly convex domain, stable critical points of the original variational problem have a connected, thin transition layer separating the two phases. This relates to work in [GM] where special geometries such as cylindrical domains were treated, and is analogous to the results in [CHo] which show that in a convex domain, stable critical points of the corresponding unconstrained problem are constant. The proof of connectivity employs tools from geometric measure theory including the co‐area formula and the isoperimetric inequality on manifolds. The thinness of the transition layer follows from a separate calculation establishing spatial decay of solutions to the pure phases. (Accepted July 15, 1996)     

Platelet Graphite Nanofibers for Electrochemical Sensing and Biosensing: The Influence of Graphene Sheet Orientation

Here, we demonstrate that platelet graphite nanofibers (PGNFs) exhibit fast heterogeneous electron‐transfer rates for a wide variety of compounds such as FeCl₃, ferrocyanide, dopamine, uric acid, ascorbic acid, and the reduced form of β‐nicotinamide adenine dinucleotide. The electrochemical properties of PGNFs are superior to those of multiwalled carbon nanotubes (MWCNTs) or graphite microparticles (GMPs). Transmission electron microscopy and Raman spectroscopy reveal that this arises from the unique graphene sheet orientation of such platelet nanofibers, which accounts for their unparalleled high ratio of graphene edge planes versus basal planes.     

Characters of Fundamental Representations of Quantum Affine Algebras

We give closed formulae for the q-characters of the fundamental representations of the quantum loop algebra of a classical Lie algebra, in terms of a family of partitions satisfying some simple properties. We also give the multiplicities of the eigenvalues of the imaginary subalgebra in terms of these partitions.     

Metabolic Profiling of Murine Macrophages Exposed to Silver Nanoparticles at Dose and Time Dependencies

The macrophage time-dependent metabolic profile changing basal metabolism triggered by nanoparticles can be obtained and used to improve wound healing treatments. Herein this study demonstrates that metabolic status responds systematically to cytotoxicity manipulation, providing an interesting way of cellular control. Nuclear magnetic resonance (NMR) based metabolomics and cytotoxic assays are used to study RAW 264.7 cells exposed to AgNPs at different concentrations and incubation times. Cytotoxicity data show a slight decrease in cellular expansion rates accompanied by morphological changes in cells. Metabolomics show that despite the glycolytic activity of treated and non-treated cells remains unchanged; however, only the treated cells present a rich Citrate environment signaling up-regulation of Tricarboxylic-Acid-Cycle (TCA). Cells choose aerobic routes instead of anaerobic ones to produce energy and self-regulate their amino acid metabolism to balance TCA. Choline metabolism is down-regulated once its sub-products, Betaine and Glycine, are reduced, thus compromising Creatine synthesis. Phospholipid metabolism is down-regulated due to the decreasing of Phosphocholine and Sn-Glycerol-3-PC, in agreement with the cytotoxicity results. Pyroglutamate decreases in treated cells, signaling different levels of oxidative stress. These analytical tools can characterize AgNPs-treatments, even distinguishing dose and time dependencies. Therefore, the fine-tuning of exposition parameters can modulate cellular activity to achieve better wound healing.     

Electrodes/Electrolyte Interfaces in the Presence of a Surface‐Modified Photopolymer Electrolyte: Application in Dye‐Sensitized Solar Cells

Since hundreds of studies on photoanodes and cathodes show that the electrode/electrolyte interfaces represent a key aspect at the base of dye‐sensitized solar cell (DSSC) performances, it is reported here that these interfaces can be managed by a smart design of the spatial composition of quasi‐solid electrolytes. By means of a cheap, rapid, and green process of photoinduced polymerization, composition‐tailored polymer electrolyte membranes (PEMs) with siloxane‐enriched surfaces are prepared, and their properties are thoroughly described. When assembled in DSSCs, the interfacial action promoted by the composition‐tailored PEMs enhances the photocurrent and fill factor values, thus increasing the global photovoltaic conversion efficiency with respect to the non‐modified PEMs. Moreover, the presence of the siloxane‐chain‐enriched surface increases the hydrophobicity and reduces the water vapor permeation into the device, thus enhancing the cell′s durability.     

Magnetic and electrokinetic manipulations on a microchip device for bead-based immunosensing applications

The combination of electrophoretic and magnetic manipulations with electrochemical detection for a versatile microfluidic and bead-based biosensing application is demonstrated. Amperometric detection is performed in an off-channel setup by means of a voltammetric cell built at the microchannel outlet and using a gold working electrode. Superparamagnetic particles are introduced and handled inside the channel by means of an external permanent magnet in combination with the electrogenerated flow which allows reproducible loading. The specific detection of phenol as electroactive alkaline phosphatase product is used in this study as proof of concept for a sensitive protein quantification. Characterizations and optimization of different parameters have been carried out in order to achieve the best detection signal. The applicability of the device has been finally demonstrated by the detection of rabbit IgG as model protein after an immunoassay performed on magnetic particles as immobilization platform. A comparison between the electrochemical detection using the developed device and the optical standard detection revealed similar performances with, however, extremely lower amount of reagent used and shorter analysis time. The developed electrophoretic- and magnetic-based chip may open the way to several other biosensing applications with interest not only for other proteins but also for DNA analysis, cell counting, and environmental control.