Nucleophilic substitution of chlorobis(4-methoxyphenyl)methane: reactivity of carbenium ions in ILs-trifluoroethanol mixtures

The ionization of chlorobis(4-methoxyphenyl)methane (1-Cl) was performed in 1:1 mixtures of TFE/ILs (ILs = [emim][Tf₂N], [bmim][Tf₂N], [bpy][Tf₂N]), and TFE/CH₃CN. The decay of the immediately formed carbenium ion 1⁺ was followed by stopped flow, showing that the lifetime of this intermediate significantly decreases on going from CH₃CN to [emim][Tf₂N]. Ab initio calculations suggest an increase in the electrophilicity of the carbenium ion in ILs.     

Numerical computation of polynomial zeros by means of Aberth's method

An algorithm for computing polynomial zeros, based on Aberth's method, is presented. The starting approximations are chosen by means of a suitable application of Rouché's theorem. More precisely, an integerq 1 and a set of annuliA _i,i=1,...,q, in the complex plane, are determined together with the numberk _i of zeros of the polynomial contained in each annulusA _i. As starting approximations we choosek _i complex numbers lying on a suitable circle contained in the annulusA _i, fori=1,...,q. The computation of Newton's correction is performed in such a way that overflow situations are removed. A suitable stop condition, based on a rigorous backward rounding error analysis, guarantees that the computed approximations are the exact zeros of a nearby polynomial. This implies the backward stability of our algorithm. We provide a Fortran 77 implementation of the algorithm which is robust against overflow and allows us to deal with polynomials of any degree, not necessarily monic, whose zeros and coefficients are representable as floating point numbers. In all the tests performed with more than 1000 polynomials having degrees from 10 up to 25,600 and randomly generated coefficients, the Fortran 77 implementation of our algorithm computed approximations to all the zeros within the relative precision allowed by the classical conditioning theorems with 11.1 average iterations. In the worst case the number of iterations needed has been at most 17. Comparisons with available public domain software and with the algorithm PA16AD of Harwell are performed and show the effectiveness of our approach. A multiprecision implementation in MATHEMATICA is presented together with the results of the numerical tests performed.Work performed under the support of the ESPRIT BRA project 6846 POSSO (POlynomial System SOlving).     

Inside the failure mechanism of tin oxide as anode for sodium ion batteries

Journal of Solid State Electrochemistry - The conversion-alloying compounds have been identified as promising anode materials for sodium ion batteries (SIBs). One of them, SnO2, with an enormous...     

Constraining molecules at the closest approach: chemistry at high pressure

The purpose of this tutorial review is to illustrate the effects that the application of high pressures can have on chemical reactions involving highly compressible molecular materials. The essentials of the high-pressure technology (generation and in situ control of high pressures) are described with particular attention to the versatile diamond anvil cell (DAC) apparatus. The general effects of pressure on chemical equilibrium, reaction rate and reaction mechanism are discussed. The motivation for application of high-pressure methods (in the 1-300 MPa range) to chemical synthesis and in biochemistry are illustrated focusing the attention on environmental effects and with an excursus on developing biotechnological applications. The peculiarities and the unexpected outcomes of chemical reactions occurring at very high pressures (>or=300 MPa) are discussed considering the extraordinary results obtained in polymerization and amorphization of simple molecules and of unsaturated hydrocarbons. The possible connection of the high temperature-high pressure thresholds for chemical reactions with microscopic counterparts (intermolecular distances, molecular orientations) is also discussed.     

Identification of immunoreactive proteins of Chlamydia trachomatis by Western blot analysis of a two-dimensional electrophoresis map with patient sera.

Western blots of two-dimensional electrophoretic maps of proteins from Chlamydia trachomatis were probed with sera from 17 seropositive patients with genital inflammatory disease. Immunoblot patterns (comprising 28 to 2 spots, average 14.8) were different for each patient; however, antibodies against a spot-cluster due to the chlamydia-specific antigen outer membrane protein-2 (OMP2) were observed in all sera. The next most frequent group of antibodies (15/17; 88%) recognized the hsp60 GroEL-like protein, described as immunopathogenic in chlamydial infections. Reactivity to the major surface-exposed and variable antigen major outer membrane protein (MOMP) was observed at a relatively lower frequency (13/17; 76%). The hsp70 DnaK-like protein was also frequently recognized (11/17; 64.7%) in this patient group. Besides the above confirmatory findings, the study detected several new immunoreactive proteins, with frequencies ranging from 11/17 to 1/17. Some were characterized also by N-terminal amino acid sequencing and homology searches. Amongst these were a novel outer membrane protein (OmpB) and, interestingly, five conserved bacterial proteins: four (23%) sera reacted with the RNA polymerase alpha-subunit, five (29%) recognized the ribosomal protein S1, eight (47%) the protein elongation factor EF-Tu, seven (41%) a putative stress-induced protease of the HtrA family, and seven sera (41%) the ribosomal protein L7/L12. Homologs of the last two proteins were shown to confer protective immunity in other bacterial infections. The data show that immunological sensitization processes commonly thought to play a role in chlamydial pathogenicity may be sustained not only by the hsp60 GroEl-like protein, but also by other conserved bacterial antigens, some of which may be also considered as potential vaccine candidates.     

Effects of Group III Cation Substitution in the Raman Spectra of Some Defective Chalcopyrites

We report on the Raman spectra of CdIn₂Se₄ and ZnIn₂Se₄ obtained in a transparency region. These spectra have a disordered-like appearance at high frequencies. A comparison is made with the Raman and IR spectra of the similar compounds CdGa₂Se₄ and ZnGa₂Se₄. The overall vibrational behaviour is mainly determined by the anion and a correspondence may be observed between the frequencies of some high energy polar modes. A strong non-polar breathing mode is observed at nearly the same frequency in all these compounds. The observed similarities between the spectra are discussed within the frame of the existing simplified models.     

On the parallel evaluation of a sparse polynomial at a point

A new version of the Ruffini–Horner rule is presented for the evaluation of a polynomial of degree n at a point. In the PRAM model of parallel computation the new algorithm requires log n parallel steps with n/2+1 processors and the total number of arithmetic operations is n+⌈log₂(n+1)⌉ -1 multiplications and n additions. If the polynomial is sparse, i.e., the number of nonzero coefficients is k≪ n, then the total number of operations is at most k(⌈log n⌉- ⌊log k⌋)+2k+⌈log n⌉. Moreover, similarly to the customary Ruffini–Horner rule, the algorithm is backward numerically stable. In other words, the value provided by applying the algorithm in floating point arithmetic with machine precision μ coincides with the value taken on at the same point by a slightly perturbed polynomial. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effect of Cathode Nozzle Geometry and Process Parameters on the Energy Distribution for an Argon Transferred Arc

The influence of two nozzle geometries and three process parameters (arc current, arc length and plasma sheath gas flow rate) on the energy distribution for an argon transferred arc is investigated. Measurements are reported for a straight bore cylindrical and for a convergent nozzle, with arc currents of 100 A and 200 A and electrode gaps of 10 mm and 20 mm. These correspond to typical operating parameters generally used in plasma transferred arc cutting and welding operations. The experimental set up consisted of three principal components: the cathode-torch assembly, the external, water-cooled anode, and the reactor chamber. For each set of measurements the power delivered to each system component was measured through calorimetric means, as function of the arc’s operating conditions. The results obtained from this study show that the shape of the cathode torch nozzle has an important influence on arc behaviour and on the energy distribution between the different system components. A convergent nozzle results in higher arc voltages, and consequently, in higher powers being generated in the discharge for the same applied arc current, when compared to the case of a straight bore nozzle. This effect is attributed to the fluidynamic constriction of the arc root attachment, and the consequential increase in the arc voltage and thus, in the Joule heating. The experimental data so obtained is compared with the predictions of a numerical model for the electric arc, based on the solution of the Navier–Stokes and Maxwell equations, using the commercial code FLUENT©. The original code was enhanced with dedicated subroutines to account for the strong temperature dependence of the thermodynamic and transport properties under plasma conditions. The computational domain includes the heat conduction within the solid electrodes and the arc-electrode interactions, in order to be able to calculate the heat distribution in the overall system. The level of agreement achieved between the experimental data and the model predictions confirms the suitability of the proposed, “relatively simple” model as a tool to use for the design and optimization of transferred arc processes and related devices. This conclusion was further supported by spectroscopic measurements of the temperature profiles present in the arc column and image analysis of the intensity distribution within the arc, under the same operating conditions.     

Quasi-Toeplitz matrix arithmetic: a MATLAB toolbox

Numerical Algorithms - A quasi-Toeplitz (QT) matrix is a semi-infinite matrix of the kind $A=T(a)+E$ where $T(a)=(a_{j-i})_{i,j\in \mathbb Z^{+}}$ , $E=(e_{i,j})_{i,j\in \mathbb Z^{+}}$ is compact...