Nanocomposite Carbon‐PDMS Material for Chip‐Based Electrochemical Detection

This paper presents an alternative approach to create low‐cost and patternable carbon electrodes suitable for microfluidic devices. The fabrication and the electrochemical performances of electrodes made of Polydimethylsiloxane doped with commercially available carbon black (C‐PDMS) are described. Conductivity and electrochemical measurements performed on various carbon to PDMS ratios showed that electrodes with suitable electrochemical properties were obtained with a ratio of 25 %.     

Purification and structure elucidation of three naturally bioactive molecules from the new terrestrial Streptomyces sp. TN17 strain

Thirty litres of fermentation broth was extracted from the newly isolated Streptomyces sp. strain TN17 and various separation and purification steps led to the isolation of three pure bioactive compounds (1-3). Compound 1: cyclo (L-Leu-L-Arg), a diketopiperazine 'DKP' derivative; 2: di-(2-ethylhexyl) phthalate, a phthalate derivative; and 3: cyclo 1-[2-(cyclopentanecarbonyl-3-phenyl-propionyl]-pyrrolidine-2-carboxylic acid (1-carbamoyl-propyl)-amide, a cyclic tetrapeptide derivative. The chemical structure of these three active compounds was established on the basis of spectroscopic studies (MS and NMR) and by comparison with data from the literature. According to our biological studies, the pure compounds (1-3) possess antibacterial and antifungal activities.     

Hole tunneling and hopping in a Ru(bpy)3(2+)-phenothiazine dyad with a bridge derived from oligo-p-phenylene

A molecular dyad was synthesized in which a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer and a phenothiazine redox partner are bridged by a sequence of tetramethoxybenzene, p-dimethoxybenzene, and p-xylene units. Hole transfer from the oxidized metal complex to the phenothiazine was triggered using a flash-quench technique and investigated by transient absorption spectroscopy. Optical spectroscopic and electrochemical experiments performed on a suitable reference molecule in addition to the above-mentioned dyad lead to the conclusion that hole transfer from Ru(bpy)(3)(3+) to phenothiazine proceeds through a sequence of hopping and tunneling steps: Initial hole hopping from Ru(bpy)(3)(3+) to the easily oxidizable tetramethoxybenzene unit is followed by tunneling through the barrier imposed by the p-dimethoxybenzene and p-xylene spacers. The overall charge transfer proceeds with a time constant of 41 ns, which compares favorably to a time constant of 1835 ns associated with equidistant hole tunneling between the same donor-acceptor couple bridged by three identical p-xylene units. The combined hopping/tunneling sequence thus leads to an acceleration of hole transfer by roughly a factor of 50 when compared to a pure tunneling mechanism.     

First identification of dimethoxycinnamic acids in human plasma after coffee intake by liquid chromatography-mass spectrometry

There is a substantial amount of published literature on the bioavailability of various coffee components including the most abundant metabolites, caffeic and ferulic acids. Surprisingly, to date, the appearance of dimethoxycinnamic acid derivatives in humans has not been reported despite the fact that methylated form of catechol-type polyphenols could help maintain, modify or even improve their biological activities. This study reports an LC-MS method for the detection of dimethoxycinnamic acid in human plasma after treatment with an esterase. Liquid chromatography, including the combination of methanol and acetonitrile as organic eluent, was optimized to resolve all interferences and enable reliable detection and identification of 3,4-dimethoxycinnamic and 3,4-dimethoxy-dihydrocinnamic acids. In addition to the good mass accuracy achieved (better than 5 ppm), tandem mass spectrometric and co-chromatography experiments further confirmed the identity of the compounds. The optimized method was applied to analyze samples obtained immediately, 1 and 10 h after coffee ingestion. The results show that in particular 3,4-dimethoxycinnamic acid appears in high abundance (～380 nM at 60 min) in plasma upon coffee intake, indicating that it is important to consider these derivatives in future bioavailability and bioefficacy studies.     

Structure resolution of Ba5Al3F19 and investigation of fluorine ion dynamics by synchrotron powder diffraction, variable-temperature solid-state NMR, and quantum computations

The room temperature structure of Ba(5)Al(3)F(19) has been solved using electron microscopy and synchrotron powder diffraction data. One-dimensional (1D) (27)Al and ultrafast magic-angle-spinning (MAS) (19)F NMR spectra have been recorded and are in agreement with the proposed structural model for Ba(5)Al(3)F(19). The (19)F isotropic chemical shift and (27)Al quadrupolar parameters have been calculated using the CASTEP code from the experimental and density functional theory geometry-optimized structures. After optimization, the calculated NMR parameters of both the (19)F and (27)Al nuclei show improved consistency with the experimental values, demonstrating that the geometry optimization step is necessary to obtain more accurate and reliable structural data. This also enables a complete and unambiguous assignment of the (19)F MAS NMR spectrum of Ba(5)Al(3)F(19). Variable-temperature 1D MAS (19)F NMR experiments have been carried out, showing the occurrence of fluorine ion mobility. Complementary insights were obtained from both two-dimensional (2D) exchange and 2D double-quantum dipolar recoupling NMR experiments, and a detailed analysis of the anionic motion in Ba(5)Al(3)F(19) is proposed, including the distinction between reorientational processes and chemical exchange involving bond breaking and re-formation.     

Tip- or electron beam-induced surface polymerization

Control on the formation of a two-dimensional polymer could be achieved in two different ways. Manipulation with the tip of a scanning tunneling microscope allowed for assigning the localization of the polymerization reaction. Additionally, electron irradiation could accelerate greatly the reaction kinetics.     

Redox strategy for reversible attachment of biomolecules using bifunctional linkers

Soft attachment of streptavidin to β-cyclodextrin-modified pegylated SAMs was efficiently performed in a reversible and repetitive way via orthogonal bifunctional linkers involving streptavidin-biotin recognition and redox-driven multivalent host-guest (β-cyclodextrin-ferrocene) interactions.     

Molecular dynamics effects on luminescence properties of oligothiophene derivatives: a molecular mechanics-response theory study based on the CHARMM force field and density functional theory

CHARMM force field parameter values for a class of oligothiophene derivatives have been derived with reference to density functional theory/B3LYP potential energy surfaces. The force field parametrization of these luminescent conjugated polyelectrolytes includes the electronic ground state as well as the strongly light absorbing first excited state. In conjunction with quantum chemical response theory calculations of transition state properties, a molecular dynamical model of the Stokes shift is obtained. The theoretical model is benchmarked against experimental data recorded at room temperature which refer to sodium salts of p-HTAA and p-FTAA with distilled water as a solvent. For p-HTAA the theoretically predicted Stokes shift of 112 nm is in good agreement with the experimental result of 124 nm, given the approximations about exciton localization that were introduced to obtain a force field for the excited state.     

Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles: X-ray structure of their charge transfer complexes with tetrathiafulvalene

Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (E(1/2)(I)) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EA(CT)) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA(CT) versus the reversible half wave potential (E(1/2)(I)) appears to be a useful tool to estimate readily the E(1/2)(I) or EA(CT) values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.