Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules

We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.     

Vibronic interaction in the lower electronic states of benzene

Results of further calculations on the dynamic coupling between the lower B _1u and E _1u electronic states of benzene via a single e _2g mode are presented. In part I we gave the ‘pseudo-cylindrical’ solutions that result when the leading coupling term, linear in the nuclear displacements, is considered (cylindrical Born-Oppenheimer potential). Here we investigate the effect of

1. (1) the next higher terms in the expansion of the coupling hamiltonian for the free molecule (hexagonal Born-Oppenheimer potential);

2. (2) a crystal field anisotropy.

From the scanty data on the coupling constants available a priori it would follow that the refinement introduced by (1) is small for benzene. On the contrary, the effect of even a small crystal field anisotropy is predicted to be appreciable.

The results of the calculations are analysed by comparison with experimental data on the benzene crystal at low temperature. A consistent interpretation of both magnetic resonance results and the triplet ← singlet absorption spectrum is obtained.     

The Intramolecular Diels-Alder Furan Approach in Synthesis : 11-oxatricyclo|6.2.1.01,6|undec-9-en-5-one

Although the synthetic potential of the intramolecular variant of the Diels-Alder reaction has now been fully recognized³, little attention has so far been paid to this type of addition using the furan nucleus as the diene partner4–8. The presence of an oxygenated cyclohexene system in several complex natural products (e.g. gibberellic acid, morphine), the diverse possibilities of the substituted 7-oxabicyclo |2.2.1|-2-heptene system for further transformation⁹, the expected enhanced reactivity and stereoselectivity of the intramolecular cycloaddition and the availability of a wide variety of commercial furan derivatives make the sequence a → b → c particularly attractive in total synthesis.     

Determination of neutron temperature in irradiation channels of reactor

The neutron temperature is a characteristic parameter in irradiation channels of reactor. For nuclides which have resonances in the thermal neutron energy range, their Westcott g-factors are different from unity. The values of g-factors and cross-sections of (n, γ) reaction of these nuclides are temperature dependence. The standard energy for tabulation of thermal neutron cross-section (σ₀) is that of room temperature (293.59 K or 20.43 °C), corresponding to a neutron energy 0.0253 eV or to a neutron velocity of 2200 m/s. However, in the irradiation channels of reactor, the temperature is not exact at 20.43 °C. Thus, the temperature at the irradiation position must be known to convert σ₀ to σ(T). A method for determination of the neutron temperature in irradiation channels of Dalat reactor is presented by fitting the thermal neutron spectrum obtained from the calculation using MCNP code.     

A new force field for simulating phosphatidylcholine bilayers

A new force field for the simulation of dipalmitoylphosphatidylcholine (DPPC) in the liquid‐crystalline, fluid phase at zero surface tension is presented. The structure of the bilayer with the area per lipid (0.629 nm²; experiment 0.629–0.64 nm²), the volume per lipid (1.226 nm³; experiment 1.229–1.232 nm³), and the ordering of the palmitoyl chains (order parameters) are all in very good agreement with experiment. Experimental electron density profiles are well reproduced in particular with regard to the penetration of water into the bilayer. The force field was further validated by simulating the spontaneous assembly of DPPC into a bilayer in water. Notably, the timescale on which membrane sealing was observed using this model appears closer to the timescales for membrane resealing suggested by electroporation experiments than previous simulations using existing models. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

The transient EPR spectra and spin dynamics of coupled three-spin systems in photosynthetic reaction centres

The concept of introducing an additional, stable paramagnetic species into photosynthetic reaction centres to increase the information content of their spin polarized transient EPR spectra is investigated theoretically. The light-induced electron transfer in such systems generates a series of coupled three-spin states consisting of sequential photoinduced radical pairs coupled to the stable spin which acts as an “observer”. The spin polarized transient EPR spectra are investigated using the coupled three-spin system P⁺I⁻Q⁻ _A in pre-reduced bacterial reaction centres as a specific example which has been studied experimentally. The evolution of the spin system and the spin polarized EPR spectra of P⁺I⁻Q⁻ _A and Q⁻ _A following recombination of the radical pair (P = primary donor, I = primary acceptor, Q_A = quinone acceptor) are calculated numerically by solving the equations of motion for the density matrix. The net polarization of the observer spin is also calculated analytically by perturbation theory for the case of a single, short-lived, charge-separated state. The result bears a close resemblance to the chemically induced nuclear polarization (CIDNP) generated in photolysis reactions in which a nuclear spin plays the role of the observer interacting with the radical pair intermediates. However, because the Zeeman frequencies of the three electron spins involved are usually quite similar, the polarization of the electron observer spin in strong magnetic fields can reflect features of the CIDNP effect in both, high and low magnetic fields. The dependence of the quinone spin polarization on the exchange couplings in the three-spin system is investigated by numerical simulations, and it is shown that the observed emissive polarization pattern is compatible with either sign, positive or negative, for a range of exchange couplings, J_PI, in the primary pair. The microwave frequency and orientation dependence of the spectra are discussed as two of several possible criteria for determining the sign of J_PI.