Coordination of methanol clusters to benzene: a computational study

Benzene-methanol cluster structures were investigated with theoretical chemistry methods to describe the microsolvation of benzene and the benzene-methanol azeotrope. Benzene-methanol (MeOH) clusters containing up to six methanol molecules have been calculated by ab initio [MP2/6-311++G(d,p)//MP2/6-31+G(d,p) + BSSE correction] method. The BSSE was found quite large with this basis set, hence, different extrapolation schemes in combination with the aug-cc-pVxZ basis sets have been used to estimate the complete basis set limit of the MP2 interaction energy [ΔE(MP2/CBS)]. For smaller clusters, n ≤ 3, DFT procedures (DFTB+, MPWB1K, M06-2X) have also been applied. Geometries obtained for these clusters by M06-2X and MP2 calculations are quite similar. Based on the MP2/CBS results, the most stable C(6)H(6)(MeOH)(3) cluster is characterized by a hydrogen bonded MeOH trimer chain interacting with benzene via π···H-O and O···H-C(benzene) hydrogen bonds. Larger benzene-MeOH clusters with n ≥ 4 consist of cyclic (MeOH)(n) subclusters interacting with benzene by dispersive forces, to be denoted by C(6)H(6) + (MeOH)(n). Interaction energies and cooperativity effects are discussed in comparison with methanol clusters. Besides MP2/CBS calculations, for selected larger clusters the M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d,p) procedure including the BSSE correction was also used. Interaction energies obtained thereby are usually close to the MP2/CBS limit. To model the benzene-MeOH azeotrope, several structures for (C(6)H(6))(2)(MeOH)(3) clusters have been calculated. The most stable structures contain a tilted T-shaped benzene dimer interacting by π···H-O and O···H-C (benzene) hydrogen bonds with a (MeOH)(3) chain. A slightly less negative interaction energy results for a parallel displaced benzene sandwich dimer with a (MeOH)(3) chain atop of one of the benzene molecules.     

Radiation induced degradation of pharmaceutical residues in water: Chloramphenicol

The γ-radiolytic degradation of chloramphenicol (CPL) was investigated in 0.1–1 mmol dm^?3 aqueous solutions at various radiation conditions. The destruction of CPL was monitored by UV–vis spectrophotometric method through the decrease in the intensity of the absorbance band at 276 nm. LC-MS/MS was used to identify the degradation products. Results indicate that ^?OH can add onto the CPL aromatic ring or can abstract H-atom from the side chain. The reductive dechlorination of CPL was also studied based on the reaction of e_aq^? with CPL. In 0.1 mmol dm^?3 solution above 2.5 kGy dose complete CPL degradation was achieved. In the presence of dissolved oxygen at relatively low dose, various oxidation products were observed. In the presence of tertiary butanol radical scavenger tertiary butanol group containing products were also detected. The toxicity increased as a function of dose to 1.0 kGy. At doses higher than 1.0 kGy the toxicity decreased continuously due to further degradation. It was also demonstrated that the O₂^??/HO₂^? pair has low reactivity in CPL solution.     

Horseradish Peroxidase as a Catalyst for Atom Transfer Radical Polymerization

The hemoprotein horseradish peroxidase (HRP) catalyzes the polymerization of N‐isopropylacrylamide with an alkyl bromide initiator under conditions of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) in the absence of any peroxide. This is a novel activity of HRP, which we propose to name ATRPase activity. Bromine‐terminated polymers with polydispersity indices (PDIs) as low as 1.44 are obtained. The polymerization follows first order kinetics, but the evolution of molecular weight and the PDI upon increasing conversion deviate from the results expected for an ATRP mechanism. Conversion, and PDI depend on the pH and on the concentration of the reducing agent, sodium ascorbate. HRP is stable during the polymerization and does not unfold or form conjugates.

     

External field induced tricritical phenomenon in the isotropicnematic phase transition of hard non-spherical particle systems

The effect of static external field is studied on the isotropic–nematic phase transition of a system of hard non-spherical particles (rods or platelets) with negative anisotropic polarizability (susceptabilities). On the basis of Onsager theory, the phase coexistence curve is calculated numerically without any approximation. It is found that a weakly ordered nematic phase (uniaxial planar) is in coexistence with a highly ordered biaxial nematic phase which ends at a tricritical point. In the limit of infinite field strength, the orientations of the particles are confined in a plane perpendicular to the field and continuous isotropic–nematic phase transition takes place.     

Special Relativity over the Field of Rational Numbers

We investigate the question: what structures of numbers (as physical quantities) are suitable to be used in special relativity? The answer to this question depends strongly on the auxiliary assumptions we add to the basic assumptions of special relativity. We show that there is a natural axiom system of special relativity which can be modeled even over the field of rational numbers.     

Bi-exponential diffusion signal decay in normal appearing white matter of multiple sclerosis

Purpose

Our aim was to characterize bi-exponential diffusion signal changes in normal appearing white matter of multiple sclerosis (MS) patients.

Methods

Diffusion parameters were measured using mono-exponential (0–1000 s/mm²) and bi-exponential (0–5000 s/mm²) approaches from 14 relapsing-remitting subtype of MS patients and 14 age- and sex-matched controls after acquiring diffusion-weighted images on a 3T MRI system. The results were analyzed using parametric or nonparametric tests and multiple linear regression models.

Results

Mono-exponential apparent diffusion coefficient (ADC) slightly increased in controls (P=.09), but decreased significantly in MS as a function of age, nonetheless an elevated ADC was observed with increasing lesion number in patients. Bi-exponential analyses showed that the increased ADC is the result of decreased relative volume fraction of slow diffusing component (f_s). However, the fast and slow diffusion components (ADC_f, ADC_s) did not change as a function of either age in controls or lesion number and age in MS patients.

Conclusions

These data demonstrated that the myelin content of the white matter affects diffusion in relapsing-remitting subtype of multiple sclerosis that is possibly a consequence of the shift between different water fractions.     

On the sup-norm of Maass cusp forms of large level. III

Let $f$ be a Hecke–Maass cuspidal newform of square-free level $N$ and Laplacian eigenvalue $\lambda $ . It is shown that $\left||f \right||_\infty \ll _{\lambda ,\epsilon } N^{-\frac{1}{6}+\epsilon } \left||f \right||_2$ for any $\epsilon >0$ .     

Generalized Robba rings

We prove that any projective coadmissible module over the locally analytic distribution algebra of a compact p-adic Lie group is finitely generated. In particular, the category of coadmissible modules does not have enough projectives. In the Appendix a “generalized Robba ring” for uniform pro-p groups is constructed which naturally contains the locally analytic distribution algebra as a subring. The construction uses the theory of generalized microlocalization of quasi-abelian normed algebras that is also developed there. We equip this generalized Robba ring with a selfdual locally convex topology extending the topology on the distribution algebra. This is used to show some results on coadmissible modules.     

Auger spectrometric studies on fracture surfaces of tool steel

The fracture surfaces of tool steel K-13 (Hungarian Standard) were studied by Auger electron spectroscopy. Notched specimens of 3 × 3 mm² were fractured in UHV (6 × 10⁻⁸ Pa) with a fracturer (Riber FR 100) and studied with a CMA analyser (Riber OPC 103). With our modification the fracturer was operated within the −150°C −+230°C temperature range. The fracture surfaces were tested with a scanning electron microscope (JEOL JSM 35). The evaluation of Auger spectra was based on the PHI (PALMBERG et al.). Handbook, however the backscattering correction of Jablonski was applied in some cases. The choice of adequate fracturing temperature proved to be very important. Low temperature fracture of this steel alloy is producing very rigid transgranular fracture. The effects of sample heat treatment and of fracturing temperature as well were studied in details. The Auger spectra of fracture surfaces are strongly affected by the heat treatment of the samples. The grain boundary fracture surface of a sample austenitized at 1100°C quenched and tempered at 600°C exhibited a strong enrichment of P, correlating with the enrichment of Cr, V and Mo. The transgranular fracture surface of the same sample but without tempering corresponded to the bulk composition. In some cases and spots on the fracture surfaces, giant S or P peaks were associated with secondary phases (inclusions) on the SEM pictures.     

Development and characterization of ultra-porous silica films made by the sol–gel method. Application to biosensing

The aim of this work is to demonstrate the sensing ability of reverse-symmetry waveguides to investigate adsorption of casein and build-up of poly-L-lysine mediated casein multilayers. A first part of this study is dedicated to the elaboration and characterization of ultra-porous thin films with very low refractive indices by an appropriate sol–gel method. This will form the basis of our planar optical sensors. Optical waveguide light mode spectroscopy is a real-time and sensitive method to study protein adsorption kinetics and lipid bilayers. We used it to test the obtained waveguides for in-situ monitoring of biomolecule adsorption. As a result, significant changes in the incoupling peak position were observed during the layer-by-layer adsorption. Finally, refractive index and thickness of the adsorbed layers were established.