Transition theories of elastic-plastic deformation of metallic polycrystals

Summary A general approach to the problem of determination of elastoplastic behavior of metallic polycrystals at finite deformation is presented. The relation between moving dislocation density and global slip rate for grains is developed. Transition to grain response is obtained by introducing the hardening matrix. Field equations for heterogeneous elastoplastic metals are transformed into an integral equation, using Green functions technique. This allows to find the spin of the lattice related to texture formation.Scale transition is achieved by a self-consistent approximation of the integral equation. New results concerning BCC metals (sheet steel) are presented. They apply to tensile test, Lankford coefficient, initial and subsequent yield surfaces, and evolution of the internal state of the polycrystal: second-order residual stress, stored energy and texture evolution.     

Automated multiple solid phase micro extraction. An approach to enhance the limit of detection for the determination of pesticides in water

A method was developed to decrease the limit of detection (LOD) for pesticide residue analysis in water using multiple SPME. To enhance the absolute amount transferred to the GC column an enrichment step is integrated in the SPME/GC-analysis. A series of several extraction and desorption steps are performed and the analytes are trapped at the front of the cold GC column before the GC analysis is started. The parameters mainly influencing this enrichment are the equilibrium time, the slope of the adsorption time/peak area profile at its start, the number and the duration of the extraction steps. The role of these parameters was investigated.     

Automated solid phase dynamic extraction – Extraction of organics using a wall coated syringe needle

Extractions of liquid samples were carried out using wall coated needles prepared from stainless steel capillary columns instead of syringe needles. This micro extraction technique was applied to the analysis of pesticides in water. Important parameters influencing the extraction such as sample velocity, extraction time and also the desorption parameters were investigated and optimized. Automation of this technique was realized using a conventional automatic sampler. Limits of detection were improved using the multiple extraction / desorption technique. Chromatographic data and limits of detection were compared with those obtained by solid phase micro extraction (SPME). Using a needle with a 7 μm film yielded limits of detection varying from 0.001–0.1 μg/L and were in the same range as those resulting from the extraction using a 100 μm polydimethylsiloxane (PDMS) SPME fiber. The main advantages of the needle extraction technique were the significantly higher extraction speed and the practical aspects of a stable steel needle compared to those of a fragile fiber. The extraction speed using a needle with a ¶7 μm film was up to five times higher than the speed of SPME using a 100 μm PDMS fiber. The steel needle could be stressed mechanically in a higher extent than a SPME fiber. Sample volumes and aliquots of liquid media could be handled and moved from one bottle to another using the automatic sampler.     

Polarization of Molecular ions in NaTCNQ and TTF. TCNQ Crtstals

Self-consistent electrostatic intersite potentials and atomic charges have been calculated. Lattice cohesion energy for NaTCNQ has been reproduced when polarization of TCNQ- anion in the lattice was taken into account.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

Multiple Binding Sites Contribute to the Mechanism of Mixed Agonistic and Positive Allosteric Modulators of the Cannabinoid CB1 Receptor

The cannabinoid CB1 receptor (CB1R) is an abundant metabotropic G‐protein‐coupled receptor that has been difficult to address therapeutically because of CNS side effects exerted by orthosteric drug candidates. Recent efforts have focused on developing allosteric modulators that target CB1R. Compounds from the recently discovered class of mixed agonistic and positive allosteric modulators (Ago‐PAMs) based on 2‐phenylindoles have shown promising functional and binding properties as CB1R ligands. Here, we identify binding modes of both the CP 55,940 agonist and GAT228, a 2‐phenylindole allosteric modulator, by using our metadynamics simulation protocol, and quantify their affinity and cooperativity by atomistic simulations. We demonstrate the involvement of multiple adjunct binding sites in the Ago‐PAM characteristics of the 2‐phenylindole modulators and explain their ability to compete with orthosteric agonists at higher concentrations. We validate these results experimentally by showing the contribution of multiple sites on the allosteric binding of ZCZ011, another homologous member of the class, together with the orthosteric agonist.     

Automated solid phase dynamic extraction--extraction of organics using a wall coated syringe needle

Extractions of liquid samples were carried out using wall coated needles prepared from stainless steel capillary columns instead of syringe needles. This micro extraction technique was applied to the analysis of pesticides in water. Important parameters influencing the extraction such as sample velocity, extraction time and also the desorption parameters were investigated and optimized. Automation of this technique was realized using a conventional automatic sampler. Limits of detection were improved using the multiple extraction/desorption technique. Chromatographic data and limits of detection were compared with those obtained by solid phase micro extraction (SPME). Using a needle with a 7 microns film yielded limits of detection varying from 0.001-0.1 microgram/L and were in the same range as those resulting from the extraction using a 100 microns polydimethylsiloxane (PDMS) SPME fiber. The main advantages of the needle extraction technique were the significantly higher extraction speed and the practical aspects of a stable steel needle compared to those of a fragile fiber. The extraction speed using a needle with a 7 microns film was up to five times higher than the speed of SPME using a 100 microns PDMS fiber. The steel needle could be stressed mechanically in a higher extent than a SPME fiber. Sample volumes and aliquots of liquid media could be handled and moved from one bottle to another using the automatic sampler.     

In situ Crystallization Technique – an Approach to Circumvent Crystal Structures with high Z′‐Crystallization Behavior of (CF3)2C–OH

In situ crystallization on the diffractometer of 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) with and without pyridine allows to obtain the new polymorphic form II of HFIP and the cocrystal HFIP‐pyridine. In contrast of the known HFIP form I, single‐crystal X‐ray diffraction analysis of HFIP form II shows a reduced number of molecules in the asymmetric unit (form I: Z′ = 8, form II: Z′ = 4) Furthermore, UNI Force Field calculations were used to gain a deeper understanding of the intermolecular potentials of the main interactions of the described crystal structures.     

Transverse oscillations of a long-pulse electron beam on alaser-formed channel

An intense relativistic electron beam may be transported in low-pressure gas using an ion channel which focuses and guides the beam. The beam can be unstable to the growth of transverse oscillations caused by the electric force between the beam and channel-the ion hose instability. Beam propagation on channels created by photoionization of gas with an excimer laser is discussed. Ion hose oscillations have been recorded which have a betatron wavelength of approximately 1.5 m. The growth rate of the ion hose instability in the linear regime was measured as 1.67±0.45. At this level of growth, the amplitude of beam oscillations equals the channel radius after a period of one-third of an ion oscillation time     

Charge density flow as a driving force of distortion in excited protonated azaaromatics

The INDO method was used to calculate electronic charge densities in the ground and lowest excited singlet and triplet states of neutral and protonated 2,3- and 1,4-diaza derivatives of naphthalene and phenanthrene, and benzo (a) phenazine. Experiniental changes of pK_a upon excitation can be correlated with the values of electron density flow into the heterocy- clic ring. Electron-density increase turns out to be a major factor which causes distortion in some excited protonated species.