A computational chemist approach to gas sensors: modeling the response of SnO2 to CO, O2, and H2O gases

A general bottom-up modeling strategy for gas sensor response to CO, O(2), H(2)O, and related mixtures exposure is demonstrated. In a first stage, we present first principles calculations that aimed at giving an unprecedented review of basic chemical mechanisms taking place at the sensor surface. Then, simulations of an operating gas sensor are performed via a mesoscopic model derived from calculated density functional theory data into a set of differential equations. Significant presence of catalytic oxidation reaction is highlighted.     

Perpendicular magnetocrystalline anisotropy in tetragonally distorted Fe-Co alloys

We report on the experimental realization of tetragonal Fe-Co alloys as a constituent of Fe0.36Co0.64/Pt superlattices with huge perpendicular magnetocrystalline anisotropy energy, reaching 210 microeV/atom, and a saturation magnetization of 2.5 microB/atom at 40 K, in qualitative agreement with theoretical predictions. At room temperature the corresponding values and are achieved. This suggests that Fe-Co alloys with carefully chosen combinations of composition and distortion are good candidates for high-density perpendicular storage materials.     

Actively mode-locked optical parametric oscillator

We report on what we believe to be the first demonstration of active mode locking of an optical parametric oscillator. An acousto-optic modulator is inserted into a nearly degenerate (approximately 1064 nm) and doubly resonant optical parametric oscillator based on periodically poled LiNbO3 and pumped with the second harmonic of a quasi-continuous-wave single-frequency Nd:YAG laser. When the modulation frequency is matched to the free spectral range of the cavity (120 MHz), a pulsed regime is observed, with pulse durations as short as 700 ps.     

Solid phase synthesis of a redox delivery system with the aim of targeting peptides into the brain

A solid phase approach for the preparation of peptides attached to a redox chemical delivery system derived from stable annulated NADH models is reported. The synthesis starts with the grafting on a Merrifield resin of quinoline 4b, precursor of the redox carrier. From the resulting quinoline supported resin 4d, the stepwise SPPS of both octapeptide OP (RPGLLDLK) and octadecaneuropeptide ODN (QATVGDVNTDRPGLLDLK), two neuropeptides exhibiting anorexigenic effects, was successfully achieved by conventional methods. Quaternization of the quinoline moiety prior to cleavage of the modified OP and ODN peptides from the resin, led to the expected quinolinium salt 8a and 8b respectively linked to OP or ODN peptides. Finally, the reduction with NaBH4 monitored by UV-vis, provided the desired annulated NADH models as peptides carriers with either the OP (11a,b) or ODN (12a,b) moiety.     

Triazatriangulenium cations: Highly stable carbocations for phase-transfer catalysis

Highly stable triazatriangulenium carbocations, of pK(R+) higher than 20, can be used as novel phase-transfer catalysts for several classical organic reactions, their intrinsic stability in strongly basic and nucleophilic conditions rendering this novel use feasible.     

Loading and release of ibuprofen in multi- and monofilament surgical sutures

The preparation of mono- and multifilament sutures incorporating ibuprofen as an anti-inflammatory agent is considered. Poly(p-dioxanone) monofilament samples can be loaded by a molecular diffusion process using a swelling agent such as dichloromethane. The mechanical properties have been measured and have not shown a significant change for the ibuprofen loaded samples in knot tensile assays. The kinetics of both the loading process and the release in a S?rensen's medium at 37 degrees C have been investigated. Diffusion coefficients have also been estimated from film and slab poly(p-dioxanone) samples containing ibuprofen and their release behavior compared to that shown by monofilaments. Release from a coating copolymer based on lactide, epsilon-caprolactone and trimethylene carbonate (PLA/PCA/PTMC 10/60/30) has also been studied. This coating solubilizes ibuprofen molecules well and can be used for braided sutures or when a rapid dose of ibuprofen is preferred.     

Unexpected reaction of the unsaturated cluster host and catalyst [Pd3(mu3-CO)(dppm)3]2+ with the hydroxide ion: spectroscopic and kinetic evidence of an inner-sphere mechanism

The title cluster, [Pd(3)(mu(3)-CO)(dppm)(3)](2+) (dppm=bis(diphenylphosphino)methane), reacts with one equivalent of hydroxide anions (OH(-)), from tetrabutylammonium hydroxide (Bu(4)NOH), to give the paramagnetic [Pd(3)(mu(3)-CO)(dppm)(3)](+) species. Reaction with another equivalent of OH(-) leads to the zero-valent compound [Pd(3)(mu(3)-CO)(dppm)(3)](0). From electron paramagnetic resonance analysis of the reaction medium using the spin-trap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the 2-tetrahydrofuryl or methyl radicals, deriving from the tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) solvent, respectively, were detected. For both [Pd(3)(mu(3)-CO)(dppm)(3)](2+) and [Pd(3)(mu(3)-CO)(dppm)(3)](+), the mechanism involves, in a first equilibrated step, the formation of a hydroxide adduct, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which reacts irreversibly with the solvent. The kinetics were resolved by means of stopped-flow experiments and are consistent with the proposed mechanism. In the presence of an excess of Bu(4)NOH, an electrocatalytic process was observed with modest turnover numbers (7-8). The hydroxide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which bear important similarities to the well-known corresponding halide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(mu(3)-X)](n) (X=Cl, Br, I), have been studied by using density functional theory (DFT). Although the optimised geometry for the cluster in its +2 and 0 oxidation states (i.e., cation and anion clusters, respectively) is the anticipated mu(3)-OH form, the paramagnetic species, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)](0), shows a mu(2)-OH form; this suggests an important difference in electronic structure between these three species.     

Liquid chromatography/electrospray ionization mass spectrometric characterization of Harpagophytum in equine urine and plasma

A method has been developed for the analysis and characterization in equine urine and plasma of iridoid glycosides: harpagide, harpagoside and 8-para-coumaroyl harpagide, which are the main active principles of Harpagophytum, a plant with antiinflammatory properties. The method involves liquid chromatography coupled with positive electrospray ionization mass spectrometry. The addition of sodium or lithium chloride instead of formic acid in the eluting solvent has been studied in order to enhance the signal and to modify the ion's internal energy. Fragmentation pathways and associated patterns are proposed for each analyte. A comparison of three types of mass spectrometer: a 3D ion trap, a triple quadrupole and a linear ion trap, has been conducted. The 3D ion trap was selected for drug screening analysis whereas the linear ion trap was retained for identification and quantitation analysis.     

Growth hormone-releasing factor: structural modification or protection for more potent analogs

Growth hormone-releasing factor was discovered in 1982 by Guillemin and has been subjected to intense investigations because of its huge potential applications. The major concerns encountered with the native molecules were their short half-lives in vivo in many species including man, precluding the practical use of these peptides for medical or production purposes. Many efforts to produce analogs of shorter length, more resistant to degradation and having higher affinity to the receptors have been made during the last decades. The present paper presents a quick review of the work done to produce such analogs.     

Improved synthetic pathway for the derivatization of huprine scaffold

In the search of new huprine-like acetylcholinesterase binders, we have developed an improved, shorter, and high-scalable synthetic pathway for the huprine synthesis based on a Reformatsky reaction-one-pot fragmentation/Friedländer condensation sequence. An extension for the one-pot synthesis of huprine-like 4-chloroquinolines is also presented. This modified route is particularly interesting as it allows to yield a huprine containing a functional group at position 9 in only three steps from commercially available material.