Structures and electronic absorption spectra of a recently synthesised class of photodynamic therapy agents

A theoretical study was performed on a novel class of boron-containing molecules (various substituted tetraarylazadipyrromethenes), which show in vitro activity for application in photodynamic therapy. Geometric optimisation of the structures for the singlet and triplet electronic states was carried out on compounds in vacuo at the density functional level of theory, by employing the PBE0 hybrid functional and the split-valence plus polarisation basis set. The absorbance properties in the UV-visible region were examined by means of time-dependent density functional response theory, using the same functional as mentioned above. To evaluate the influence of the solvent on the excitation energies, the continuum polarisable model was applied. Calculated electronic excitations, such as those regarding the Q-like band, were found to be in good agreement (within 0.01-0.1 eV) with experimental values and experimental trends on changing both the substituents and solvent.     

Coriolis coupling and nonadiabaticity in chemical reaction dynamics

The nonadiabatic quantum dynamics and Coriolis coupling effect in chemical reaction have been reviewed, with emphasis on recent progress in using the time-dependent wave packet approach to study the Coriolis coupling and nonadiabatic effects, which was done by K. L. Han and his group. Several typical chemical reactions, for example, H+D(2), F+H(2)/D(2)/HD, D(+)+H(2), O+H(2), and He+H(2)(+), have been discussed. One can find that there is a significant role of Coriolis coupling in reaction dynamics for the ion-molecule collisions of D(+)+H(2), Ne+H(2)(+), and He+H(2)(+) in both adiabatic and nonadiabatic context.     

Structure, conformation and hydrogen bonding of two amino-cycloalkanespiro-5-hydantoins

The crystal structures of 3-amino-cycloheptanespiro-4′-imidazolidine-2′,5′-dione (I) {systematic name: 3-amino-1,3-diazaspiro[4.6] undecane-2,4-dione} and 3-amino-cyclooctanespiro-4′-imidazolidine-2′,5′-dione (II) {systematic name: 3-amino-1,3-diazaspiro[4.7] dodecane-2,4-dione}, have been determined. In both compounds the polar hydantoin groups cause molecules to aggregate via N-H...O and N-H...N interactions, forming a layer structure, in which the cycloalkane rings project outwards from the central, more polar, region. The observed molecular structure is compared with that calculated by density functional theory methods.      

Synthesis of phosphorus‐containing dipeptide mimetics via the Kabachnik–Fields reaction

The synthesis of three novel dimethyl (2‐(4,4‐dimethyl‐2,5‐dioxoimidazolidin‐1‐ylamino)‐ 2‐oxoethylamino)methylphosphonate, dimethyl (1‐ (4,4‐dimethyl‐2,5‐dioxoimidazolidin‐1‐ylamino)‐4‐ methyl‐1‐oxopentan‐2‐ylamino)methylphosphonate, and dimethyl (1‐(4,4‐dimethyl‐2,5‐dioxoimidazolidin‐ 1‐ylamino)‐1‐oxo‐3‐phenylpropan‐2‐ylamino)methylphosphonate, respectively, is reported. The newly synthesized compounds were prepared via the Kabachnik–Fields reaction. Their structures have been characterized by elemental analysis, IR, and NMR (¹H, ¹³C, and ³¹P) spectra. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:669–672, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20731     

Potentiometric characterisation of cyclodextrin inclusion complexes of local anaesthetics

The complexation of several local anaesthetics by β and γ-cyclodextrins was studied by potentiometry with glass electrode. Tetracaine and dibucaine complexation constants were determined at 25°C in the presence of 0.1 M of NaCl. It was found that prilocaine and lidocaine complexes cannot be detected.     

A glucose biosensor using methyl viologen redox mediator on carbon film electrodes

A new methyl viologen-mediated amperometric enzyme electrode sensitive to glucose has been developed using carbon film electrode substrates. Carbon film electrodes from resistors fabricated by pyrolytic deposition of carbon were modified by immobilization of glucose oxidase through cross-linking with glutaraldehyde in the presence of bovine serum albumin. The mediator, methyl viologen, was directly immobilised with the enzyme together with Nafion cation-exchange polymer. The electrochemistry of the glucose oxidase/methyl viologen modified electrode was investigated by cyclic voltammetry and by electrochemical impedance spectroscopy. The biosensor response to glucose was evaluated amperometrically; the detection limit was 20 μM, the linear range extended to 1.2 mM and the reproducibility of around 3%. When stored in phosphate buffer at 4 °C and used every day, the sensor showed good stability over more several weeks.     

Exact solution for the fractional cable equation with nonlocal boundary conditions

The fractional cable equation is studied on a bounded space domain. One of the prescribed boundary conditions is of Dirichlet type, the other is of a general form, which includes the case of nonlocal boundary conditions. In real problems nonlocal boundary conditions are prescribed when the data on the boundary can not be measured directly. We apply spectral projection operators to convert the problem to a system of integral equations in any generalized eigenspace. In this way we prove uniqueness of the solution and give an algorithm for constructing the solution in the form of an expansion in terms of the generalized eigenfunctions and three-parameter Mittag-Leffler functions. Explicit representation of the solution is given for the case of double eigenvalues. We consider some examples and as a particular case we recover a recent result. The asymptotic behavior of the solution is also studied.     

The emergence of kinship behavior in structured populations of unrelated individuals

The paper provides an explanation for altruistic behavior based on the matching and learning technology in the population. In a infinite structured population, in which individuals meet and interact with their neighbors, individuals learn by imitating their more successful neighbors. We ask which strategies are robust against invasion of mutants: A strategy is unbeatable if when all play it and a finite group of identical mutants enters then the learning process eliminates the mutants with probability 1. We find that such an unbeatable strategy is necessarily one in which each individual behaves as if he is related to his neighbors and takes into account their welfare as well as his. The degree to which he cares depends on the radii of his neighborhoods. Received June 1996/Revised version October 1998     

The Influence of Carbon Nature on the Catalytic Performance of Ru/C in Levulinic Acid Hydrogenation with Internal Hydrogen Source

The influence of the nature of carbon materials used as a support for Ru/C catalysts on levulinic acid hydrogenation with formic acid as a hydrogen source toward gamma-valerolactone was investigated. It has been shown that the physicochemical properties of carbon strongly affect the catalytic activity of Ru catalysts. The relationship between the hydrogen mobility, strength of hydrogen adsorption, and catalytic performance was established. The catalyst possessing the highest number of defects, stimulating metal support interaction, exhibited the highest activity. The effect of the catalyst grain size was also studied. It was shown that the decrease in the grain size resulted in the formation of smaller Ru crystallites on the catalyst surface, which facilitates the activity.