Lasing of iodine in the fullerene-oxygen-iodine system

The possibility of lasing in the fullerene-oxygen-iodine system with optical excitation of fullerene is studied. Laser radiation with an energy of 25 mJ and a pulse duration of 5–10 ms is obtained.     

Synthesis and characterization of polymers produced by horseradish peroxidase in dioxane

Polymers were synthesized from substituted phenolic and aromatic amine compounds with hydrogen peroxide as the source of an oxidizing agent and horseradish peroxidase enzyme as the catalyst. The polymerization reaction was carried out in a monophasic organic solvent with small amounts of water at room temperature. Conditions for the synthesis of polymers with respect to reaction time and yield were studied with a number of monomers at different concentrations and in solvents with different buffers with pH range of 5.0–7.5. Physical and chemical properties of these homo-and copolymers were determined with respect to melting point, solubility, elemental analysis, molecular weight distribution, infrared absorption (including FTIR), solid-state ¹³C nuclear magnetic resonance, thermal gravimetric analysis, and differential scanning calorimetry. The enzyme catalyzed reactions produced polymers of molecular weight greater than 400,000 which were further fractionated by differential solubility in solvent mixtures and the molecular weight distribution of the polymer fractions were determined. In general, the polymers synthesized have low solubilities, high melting points, and some degree of branching.     

Evaluation of automated nano-electrospray mass spectrometry in the determination of non-covalent protein-ligand complexes

The use of electrospray ionization mass spectrometry (ESI-MS) for studying non-covalent interactions between macromolecules and ligands is well established. ESI-MS can be a useful tool for the determination of dissociation constants between molecules in the gas phase. We validate this method by studying the binding of the catalytic domain of cellobiohydrolase I (CBH I) from Trichoderma reesei to the disaccharide inhibitor cellobiose. The method was further applied to study two newly synthesized cellobiose derivatives (m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside and p-benzyloxybenzyl beta-cellobioside). In a titration experiment, peak areas of different charge states of the free enzyme and the complex were summed in order to determine the dissociation constant. For cellobiose and m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside, the calculated values are in good agreement with those reported from either displacement titration or equilibrium binding experiments in solution. Due to non-specific binding, the dissociation constant of p-benzyloxybenzyl beta-cellobioside does not correspond with the solution-based value. Our results indicate the need for careful interpretation of data sets when using nanoESI to study non-covalent interactions.     

Hydrogen bond studies: 80. A deuteron magnetic resonance and infrared spectroscopic study of the water molecule in lithium formate monohydrate,LiHCOO · H2O

A deuteron magnetic resonance and infrared study of the water molecules in lithium formate monohydrate, LiHCOO · H₂O, has been made. The quadrupole coupling constants (e²qQ/h) and asymmetry parameters (η) were found to be 198.7±0.4 and 231.3±0.6 kHz, and 0.060±0.005 and 0.097±0.003, respectively, at 25 ° C.An interpretation is given of the infrared spectra in the OH-stretching region in terms of intra- and intermolecular couplings of the water molecules. It is found that the water molecules are vibrationally distorted by their environments such that the OH-stretching modes consist of independent stretchings of the two O-H bonds.     

Comparison of a pump-around, a diffusion-driven, and a shear-driven system for the hybridization of mouse lung and testis total RNA on microarrays

In the present study, we demonstrate the benefits of a shear-driven rotating microchamber system for the enhancement of microarray hybridizations, by comparing the system with two commonly used hybridization techniques: purely diffusion-driven hybridization under coverslip and hybridization using a fully automated hybridization station, in which the sample is pumped in an oscillating manner. Starting from the same amount of DNA for the three different methods, a series of hybridization experiments using mouse lung and testis DNA is presented to demonstrate these benefits. The gain observed using the rotating microchamber is large: both in terms of analysis speed (up to tenfold increase) and in final spot intensity (up to sixfold increase). The gain is due to the combined effect of the hybridization chamber miniaturization (leading to a sample concentration increase if comparing iso-mass conditions) and the transport enhancement originating from the rotational shear-driven flow induced by the rotation of the chamber bottom wall.     

Integrability and ergodicity of classical billiards in a magnetic field

We consider classical billiards in plane, connected, but not necessarily bounded domains. The charged billiard ball is immersed in a homogeneous, stationary magnetic field perpendicular to the plane. The part of dynamics which is not trivially integrable can be described by a bouncing map. We compute a general expression for the Jacobian matrix of this map, which allows us to determine stability and bifurcation values of specific periodic orbits. In some cases, the bouncing map is a twist map and admits a generating function. We give a general form for this function which is useful to do perturbative calculations and to classify periodic orbits. We prove that billiards in convex domains with sufficiently smooth boundaries possess invariant tori corresponding to skipping trajectories. Moreover, in strong field we construct adiabatic invariants over exponentially large times. To some extent, these results remain true for a class of nonconvex billiards. On the other hand, we present evidence that the billiard in a square is ergodic for some large enough values of the magnetic field. A numerical study reveals that the scattering on two circles is essentially chaotic.     

Can magnetic circular dichroism tackle the problem of site symmetry in solutions?

A new approach to unravel the site symmetry of lanthanides in solutions is presented. The magnetic circular dichroism spectra of Eu³⁺ in the symmetries D_3h, C_4v and D_2d are simulated. In these simulations, the main idea is to introduce the magnetic field along a 3-fold axis, being the resultant of the three equivalent X-, Y- and Z-direction of a cube. This implies that the parallel and perpendicular Zeeman effects are taken into account simultaneously.     

Structure and dynamic stability of cyclodextrin inclusion complexes with 1,4-disubstituted bicyclo[2.2.2]octanes

The properties of inclusion complexes of 1,4-di-R-bicyclo[2.2.2]octaves (R = H (1), Me (2), Cl (3), Br (4), and OH (5)) with cyclodextrins have been studied by NMR, microcalorimetry, and force-field computations. The compounds2 and3 (but not the other compounds) give dynamically stable 1:2 guest-host complexes with -cyclodextrin. Microcalorimetry of5 in water indicates a moderately strong 1:1 complex with - but weak complexes with - or -cyclodextrin. The behaviour depends on the subtle interplay size, polarity, hydrophobicity and type of solvent.     

Critical factors for high-performance physically adsorbed (dynamic) polymeric wall coatings for capillary electrophoresis of DNA

Physically adsorbed (dynamic) polymeric wall coatings for microchannel electrophoresis have distinct advantages over covalently linked coatings. In order to determine the critical factors that control the formation of dynamic wall coatings, we have created a set of model polymers and copolymers based on N,N-dimethylacrylamide (DMA) and N,N-diethylacrylamide (DEA), and studied their adsorption behavior from aqueous solution as well as their performance for microchannel electrophoresis of DNA. This study is revealing in terms of the polymer properties that help create an "ideal" wall coating. Our measurements indicate that the chemical nature of the coating polymer strongly impacts its electroosmotic flow (EOF) suppression capabilities. Additionally, we find that a critical polymer chain length is required for polymers of this type to perform effectively as microchannel wall coatings. The effective mobilities of double-stranded (dsDNA) fragments within dynamically coated capillaries were determined in order to correlate polymer hydrophobicity with separation performance. Even for dsDNA, which is not expected to be a strongly adsorbing analyte, wall coating hydrophobicity has a deleterious influence on separation performance.     

Hydrogen bond studies: Part 118. A deuteron magnetic resonance study of BeSO4· 4D2O and Li2SO4· D2O

The electric field gradient (EFG) tensors at the deuterons in the water molecules in BeSO₄ · 4D₂O at 25°C are reported. The quadrupole coupling constants (e²Q/h) and asymmetry parameters (η) for the two independent deuterons are 181.1(4) and 194.8(3) kHz, and 0.226(4) and 0.123(3), respectively. The EFG tensor corresponding to the smallest e²qQ/h is considerably distorted by the beryllium ion, which causes a high η value as well as a deviation of the y-principal axis by 21.8(6)° from the normal to the water molecule plane. A redetermination of the EFG tensors at the deuterons in the water molecule in Li₂SO₄ · D₂O at 25°C and ?110°C is also reported. The e²Q/h and η values for the two deuterons are 236.6(1.2) and 239.8(1.1) kHz, and 0.091(8) and 0.126(7), respectively, at ?110°C. The corresponding e²qQ/h and η values for the averaged EFG tensor at 25°C are 125.8(1.1) kHz and 0.813(13), respectively. The results are in good agreement with those from the pioneer work by Ketudat and Pound, 20 years ago on the same compound.