A note on nonassociated plastic flow rules

The analytical properties of the constitutive equations in plasticity with a nonassociated flow rule are investigated. Under the assumption of small deformations the directional stiffness (and compliance) rule is considered and the relevant spectral properties of the tangent stiffness tensor are assessed. It is shown that the directional stiffness may be larger than the elastic. It may also be negative in the case of a formally perfectly plastic material and so the nonassociative flow rule represents (spurious) softening in terms of an associated flow rule. The issue of uniqueness at finite strains is briefly addressed, whereby use is made of the tangent stiffness tensor relating the velocity gradient to the first Piola-Kirchhoff stress rate. The relevant spectral properties, which generalise those from the small deformation case, are found explicit. A sufficient condition for uniqueness is given in terms of a critical (upper bound) value of the hardening modulus.     

Moment problem with contractive solutions: the regular case

An operator multivariate moment problem with contractive solutions having regular unitary dilation is characterized in terms of the initial data. This extends a recent result of Sebestyén and Popovici, but the ideas of our proof differ from those used by them. The connection between the operator multivariate moment problem and harmonizable multivariate discrete processes is mentioned.

     

Conductance of tetraalkylammonium salts in propylene carbonate at 25°C

Conductance measurements of 12 quaternary ammonium salts in propylene carbonate (PC) have been made at 25°C. The cations were either tetramethylammonium, tetraethylammonium, or tetra-n-butylammonium, and the concentrations of salt varied from about 2×10^–4 to 5×10^–3 M. The data were analyzed by the equation of Pitts. The results showed that the benzoate, nitrobenzoate, and pentachlorophenolate salts are completely dissociated. The nitrophenolate, chlorophenolate, methylsulfonate, and nitrate salts are only slightly associated (K _A from 2.5 to 6.5), while the acetate, phenylacetate, and nitrophenolate salts display somewhat more extensive association, with ionpair association constants from 17 to 45. Limiting molar conductances for the anions were derived. The factors affecting ionic mobilities in this dipolar aprotic solvent are discussed.On leave 1973–1975 from the University of Gdask, Poland.     

Conformation of solvent N,N-dimethylpropionamide in the coordination sphere of the zinc(II) ion studied by Raman spectroscopy and DFT calculations

Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion.     

A Review of Infrared Spectra from Wood and Wood Components Following Treatment with Liquid Ammonia and Solvated Electrons in Liquid Ammonia

ABSTRACT

The chemical changes that occur in wood and wood components (cellulose, holocellulose and lignin) following treatment with liquid ammonia and solvated electrons (e^? _s,) in liquid ammonia have been investigated using FTIR spectroscopy.

When ammonia penetrates into a wood structure, all carboxylate groups will react with ammonia to form ammonium salts, aldehydic and ketonic groups will follow a similar reaction to produce imines, and ester groups will react to forni amides.

After treatment with (e^? _s) in liquid ammonia, wood samples show diminished absorption around 15 13 cm^?1, a position corresponding to aromatic groups, and diminished absorption peaks associated with aldehydic, ketonic, and ester groups.

The overall changes in the IR spectra of cellulose in liquid ammonia and (e^? _s) in liquid ammonia are not dramatic. The IR spectra of the isolated holocellulose after treatment with (e^? _s) in liquid ammonia have intensities and band shape similar to those of cellulose. The isolated lignin behaves in a manner similar to wood, in that the liquid ammonia causes some decrease in the intensities of absorptions associated with C-O and C=O bands, and increase in strength of the amide functional group at 1600 cm^?1. The resulting extracts of wood, following treatment with (e^? _s) in liquid ammonia, appear to loose their “aromaticity”.

Because wood has long been used, and still is used extensively as an important constructional material, the changes in mechanical characteristics caused by the action of various reducing agents appears to have been an important area of scientific interest. The following review focuses on the chemical changes in the functional groups of the surface moieties of wood when treated with a reducing agent, such as (e^? _s + NH_3liq), using infrared spectroscopy.     

Diffraction methods analysis of the approximation of the real glass structure

X-ray and electron diffraction methods are discussed and the results of an analysis of glass structure are reported.Experimental methods were employed to analyse the structures of a series of complex oxide glasses of the type:

$\text{SiO}{}_2\text{(～72\%)+}\text{Na}{}_2\text{O}\text{(～14\%)+}\text{CaO}\text{(～8\%) +}\text{MgO}\text{(～4\%)+R}{}_2\text{O}{}_3\text{(～2\%)}$

.In calculating the structural parameters of the real glass structure the assumed effective molecule was approximated which included from two (SiO₂) to five (SiO₂Na₂OCaOMgO) groups of various atoms. The structural parameters obtained allowed the real internal structure to be established and were employed in the construction of a space model of the glass.The most probable structural models are presented, obtained by successive approximation with individual oxide groups added one after another. The models' structural and physicochemical parameters were chosen to be consistent with those of the nodal model which is near to the real glass structure. The parameters required to construct the nodal model in question were established by analysing radial distribution functions and by the differentiation of the adequate radial distribution functions by subtraction and successively approximating the effective molecule including the oxide groups (SiO₂, Na₂O, CaO and MgO) added one after another.An aperiodic model of a nodal lattice is presented in a scheme, stressing the structural parameters and local orderings in groups describing the internal structure of complex oxide glasses. Also, an approximate nodal space model of great importance for the construction of a structural model of glass is presented and discussed with regard to its utility and accuracy in the determination of its parameters.     

Photophysical characterization of imidazolium-substituted Pd(II), In(III), and Zn(II) porphyrins as photosensitizers for photodynamic therapy

The photophysical properties of four imidazolium-substituted metalloporphyrins have been assessed to gain insights into the relative efficacy of the compounds for photodynamic therapy (PDT). A set of zinc(II), palladium(II), and chloro-indium(III) porphyrins all bear a net positive charge owing to the diethylimidazolium unit; one zinc chelate bears a negative charge owing to a bis(sulfobutyl)imidazolium unit. The photophysical properties of the cationic and anionic zinc porphyrins are very similar to one another in organic solvents, phosphate-buffered saline, and in the presence of bovine serum albumin. The properties of the zinc and palladium porphyrins bearing charged peripheral groups are generally similar to those of neutral analogs in organic solvents. The palladium porphyrin shows an essentially quantitative yield (≥0.99) of the triplet excited state compared to the zinc porphyrins (0.9), and all are quantitatively quenched (at the diffusion limit) by molecular oxygen in air-saturated fluid solution. If the rate constant and yield of quenching of the triplet excited state by energy or electron transfer to molecular oxygen is the same in the cellular environment as in solution, then these processes combined with the triplet yield contribute only a factor of 1.3 to the higher PDT activity of analogous palladium versus zinc porphyrins, which is much smaller than what is observed. Therefore, other factors such as transient reduction of the excited porphyrin or delivery to the target site must predominantly underlie the difference in PDT efficacy of these sensitizers.     

Dynamics and control of underactuated mechanical systems: analysis and simple experimental verification

Underactuated mechanical systems are systems with fewer control inputs than the degrees of freedom, m < n, the relevant technical examples being e.g. cranes, aircrafts and flexible manipulators. The determination of an input control strategy that forces an underactuated system to complete a set of m specified motion tasks (servo-constraints) is a demanding problem. The solution is conditioned to differential flatness of the problem, denoted that all 2n state variables and m control inputs can algebraically be expressed, at least theoretically, in terms of the desired m outputs and their time derivatives up to a certain order. A more practical formulation, motivated hereafter, is to pose the problem as a set of differential-algebraic equations, and then obtain the solution numerically. The theoretical considerations are illustrated by a simple two-degree-of-freedom underactuated system composed of two rotating discs connected by a flexible rod (torsional spring), in which the pre-specified motion of the first disc is actuated by the torque applied to the second disc, n = 2 and m = 1. The determined control strategy is then verified experimentally on a laboratory stand representing the two-disc system. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simultaneous Determination of Major Constituents of Honeybee Venom by LC-DAD

The aim of the study was to develop an LC method for honeybee venom analysis, using cytochrome c as an internal standard. The SynChropack C8 6.5 μm, 4.6 × 100 mm column was applied. The bee venom was separated by linear gradient 5–80% B at 30 min (eluent A—0.1% TFA in water, eluent B—0.1% TFA in acetonitrile:water (80:20)). The flow rate of mobile phase was maintained at 1 mL min^?1, injection volume: 40 μL, separation temperature: 25 °C. The analysis was monitored at 220 nm. Several honeybee venom constituents were separated and the content of four of them (apamine, mast cell degranulating peptide, phospholipase A₂ and melittin) were determined. By applying this methodology differences in chemical composition of honeybee venom were evaluated. In order to confirm the data obtained, the following steps and parameters were taken into account for the validation of the method: selectivity, precision (injection repeatability, analysis repeatability), accuracy (recovery), linearity and operating range, limit of detection and limit of quantitation. All steps of validation proved that the developed analytical procedure was suitable for its intended purpose (standardization). Due to its simplicity, the developed method can be easily automated and incorporated into routine operations both in the bee venom identification, quality control and assay tests.     

The precision of DCE-MRI using the tissue homogeneity model with continuous formulation of the perfusion parameters

The present trend in dynamic contrast-enhanced MRI is to increase the number of estimated perfusion parameters using complex pharmacokinetic models. However, less attention is given to the precision analysis of the parameter estimates. In this paper, the distributed capillary adiabatic tissue homogeneity pharmacokinetic model is extended by the bolus arrival time formulated as a free continuous parameter. With the continuous formulation of all perfusion parameters, it is possible to use standard gradient-based optimization algorithms in the approximation of the tissue concentration time sequences. This new six-parameter model is investigated by comparing Monte-Carlo simulations with theoretically derived covariance matrices. The covariance-matrix approach is extended from the usual analysis of the primary perfusion parameters of the pharmacokinetic model to the analysis of the perfusion parameters derived from the primary ones. The results indicate that the precision of the estimated perfusion parameters can be described by the covariance matrix for signal-to-noise ratio higher than ~ 20 dB. The application of the new analysis model on a real DCE-MRI data set is also presented.