Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Optical detection of cold atoms without spontaneous emission

We have demonstrated nondestructive detection of cold atoms with a probe laser by a frequency-modulation spectroscopy technique. We were able to tune the probe laser and its sidebands far from atomic resonance to reduce the spontaneous emission to less than 0.2 photon per atom during detection.     

Photothermal heterodyne imaging of individual nonfluorescent nanoclusters and nanocrystals

We introduce a new, highly sensitive, and simple heterodyne optical method for imaging individual nonfluorescent nanoclusters and nanocrystals. A 2 order of magnitude improvement of the signal is achieved compared to previous methods. This allows for the unprecedented detection of individual small absorptive objects such as metallic clusters (of 67 atoms) or nonluminescent semiconductor nanocrystals. The measured signals are in agreement with a calculation based on the scattering field theory from a photothermal-induced modulated index of refraction profile around the nanoparticle.     

Absorption and scattering microscopy of single metal nanoparticles

Several recently developed detection techniques opened studies of individual metal nanoparticles (1-100 nm in diameter) in the optical far field. Eliminating averaging over the broad size and shape distributions produced by even the best of current synthesis methods, these studies hold great promise for gaining a deeper insight into many of the properties of metal nanoparticles, notably electronic and vibrational relaxation. All methods are based on detection of a scattered wave emitted either by the particle itself, or by its close environment. Direct absorption and interference techniques rely on the particle's scattering and have similar limits in signal-to-noise ratio. The photothermal method uses a photo-induced change in the refractive index of the environment as an additional step to scatter a wave with a different wavelength. This leads to a considerable improvement in signal-to-background ratio, and thus to a much higher sensitivity. We briefly discuss and compare these various techniques, review the new results they generated so far, and conclude on their great potential for nanoscience and for single-molecule labelling in biological assays and live cells.     

Spectroscopic and structural impact of a stem base-pair change in DNA hairpins: GTTC-ACA-GAAC versus GTAC-ACA-GTAC

Successive investigations over the last decade have revealed and confirmed a stable loop closure in a family of d-[GTAC-5Pur6N7N-GTAC] hairpins, where 5Pur6N7N is a AAA, GAG and AXC loop (X being any nucleotide). The trinucleotide loop is characterized by a well defined 5Pur-7N mispairing mode, and by upfield chemical shifts for three sugar protons of the apical nucleotide 6N. The GTTC-ACA-GAAC DNA hairpin, of interest for its likely involvement in Vibrio cholerae genome mutations, has now been investigated. The GTAC-ACA-GTAC DNA hairpin has also been studied because it is intermediate between the other structures, as it contains the loop of the hairpin under consideration and the stem of the above family. The two hairpins with the ACA loop are stable. They show the same mispairing mode and similar upfield shifts as the previous family, but GTTC-ACA-GAAC seems to be slightly less compact than any other. GTTC-ACA-GAAC is remarkable in that it exhibits a B(II) character for the phosphate-ester conformation at 8Gp9A, together with a swing of the upper hairpin into the major groove that, in particular, brings 6CH1' roughly as close to 7AH2 as to 6CH6. These unexpected structural features are qualitatively deduced from (1)H and (31)P NMR spectra, and confirmed by Raman spectroscopy. This comparative study shows that not only the loop sequence but also the stem sequence may control hairpin structures.     

Ultrasound in organic electrosynthesis

Mechanical effects induced by ultrasonication can be very helpful for the activation of electrochemical reactions. The continuous cleaning of the electrodes by ultrasound irradiation of the electrochemical cell or the enhancement of mass transfer at the electrodes are examples of such activation. Finally, ultrasonication can play an important part for the orientation of reactions whose selectivities are very sensitive to stirring. Two very different examples have been chosen to illustrate these phenomena: the indirect electrooxidation of di-ketone-L-sorbose into the corresponding ketogulonic acid and the direct electroreduction of acetophenone into pinacol.