N-H···π hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ～6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.     

Quinonoid modified electrodes amplify the current from certain soluble one-electron redox reagents

Chemically modified carbon electrodes are prepared which hold polymeric layers of anthraquinone or dopamine units on the surface. In each case only those quinonoid units nearest the carbon are electroactive in neutral solution. Other units can be activated by one-electron redox shuttles dissolved in the solution phase which help propagate the redox process through the film. Cobalticinium dicarboxylic acid and methyl viologen are used to catalyze reductive reactions and ferrocene carboxylic acid catalyzes the oxidative propagation.     

45- and 70-base DNA supramolecular polymerizations on quartz crystal microbalance biosensor

Supramolecular polymerizations of 45- and 70- base DNAs on the surface of an in-situ time-resolved 27 MHz quartz crystal microbalance biosensor.     

Electrochemical detection of Arachis hypogaea (peanut) agglutinin binding to monovalent and clustered lactosyl motifs immobilized on a polypyrrole film

Direct detection of peanut agglutinin/lactose interactions was realized by an electrochemical approach based on a polypyrrole coated electrode displaying pendant carbohydrates.     

Radicals masquerading as electrophiles: a computational study of the intramolecular addition reactions of acyl radicals to imines

Ab initio calculations using 6-311G**, cc-pVDZ, and aug-cc-pVDZ, with (MP2, QCISD, CCSD(T)) and without (UHF) electron correlation, and density functional methods (BHandHLYP and B3LYP) predict that cyclization of the 5-aza-5-hexenoyl and (E)-6-aza-5-hexenoyl radicals proceed to afford the 5-exo products. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory, energy barriers (deltaE(double dagger)) of 36.1 and 47.0 kJ mol(-1) were calculated for the 5-exo and 6-endo pathways for the cyclization of the 5-aza-5-hexenoyl radical. On the other hand, at the same level of theory, deltaE(double dagger) of 38.9 and 45.4 kJ mol(-1) were obtained for the 5-exo and 6-endo cyclization modes of (E)-6-aza-5-hexenoyl radical, with exothermicities of about 27 and 110 kJ mol(-1) calculated for the exo and endo modes, respectively. Under suitable experimental conditions, the 6-endo cyclization product is likely to dominate. Analysis of the molecular orbitals involved in these ring-closure reactions indicate that both reactions at nitrogen are assisted by dual orbital interactions involving simultaneous SOMO-pi* and LP-pi* overlap in the transitions states. Interestingly, the (Z)-6-aza-5-hexenoyl radical, that cannot benefit from these dual orbital effects is predicted to ring-close exclusively in the 5-exo fashion.     

Laser processing for bio-microfluidics applications (part I)

This paper reviews applications of laser-based techniques to the fabrication of microfluidic devices for biochips and addresses some of the challenges associated with the manufacture of these devices. Special emphasis is placed on the use of lasers for the rapid prototyping and production of biochips in particular for applications in which silicon is not the preferred material base. Part I of this review addresses applications and devices using UV lasers for laser ablation and surface treatment of microchannels, in particular in polymers.     

Influence of age and sex on aortic distensibility assessed by MRI in healthy subjects

Magnetic resonance imaging (MRI) is particularly well adapted to the evaluation of aortic distensibility. The calculation of this parameter, based on the change in vessel cross-sectional area per unit change in blood pressure, requires precise delineation of the aortic wall on a series of cine-MR images. Firstly, the study consisted in validating a new automatic method to assess aortic elasticity. Secondly, aortic distensibility was studied for the ascending and descending thoracic aortas in 26 healthy subjects. Two homogeneous groups were available to evaluate the influence of sex and age (with an age limit value of 35 years). The automatic postprocessing method proved to be robust and reliable enough to automatically determine aortic distensibility, even on artefacted images. In the 26 healthy volunteers, a marked decrease in distensibility appears with age, although this decrease is only significant for the ascending aorta (8.97±2.69 10⁻³ mmHg⁻¹ vs. 5.97±2.02 10⁻³ mmHg⁻¹). Women have a higher aortic distensibility than men but only significantly at the level of the descending aorta (7.20±1.61 10⁻³ mmHg⁻¹ vs. 5.05±2.40 10⁻³ mmHg⁻¹). Through our automatic contouring method, the aortic distensibility from routine cine-MRI has been studied on a healthy subject population providing reference values of aortic stiffness. The aortic distensibility calculation shows that age and sex are causes of aortic stiffness variations in healthy subjects.