Towards Diastereomeric Pure Salts with Antisolvent Methods

Chiral molecules, especially enantiomers and diastereomers of purity > 99 %, present a significant market share within the chemical, pharmaceutical, and flavor industries. Antisolvent precipitations, both batch and semicontinuous operations to serve the current trends in flow chemistry were demonstrated to be environmentally benign and efficient tools in achieving high optical purities. Although salts are known to be insoluble in supercritical CO₂, instabilities of the nascent salts were detected and applied for increasing efficiency. Diastereomeric excess values of the crystalline products exceeded 99 % in maximum of three consecutive steps both by repeated resolution with half molar equivalent of the amine to the acid and by direct recrystallization of the salts.     

On the effects of the packet size distribution on the packet loss process

Real-time multimedia applications have to use forward error correction (FEC) anderror concealment techniques to cope with losses in today’s best-effort Internet. The efficiency of these solutions is known however to depend on the correlation between losses in the media stream. In this paper we investigate how the packet size distribution affects the packet loss process, that is, the distribution of the number of lost packets in a block, the related FEC performance and the average loss run length. We present mathematical models for the loss process of the MMPP+M/D/1/K and the MMPP+M/M/1/K queues; we validate the models via simulations, and compare the results to simulation results with an MPEG-4 coded video trace. We conclude that the deterministic packet size distribution (PSD) not only results in lower stationary loss probability than the exponential one, but also gives a less correlated loss process, both at a particular average link load and at a particular stationary loss probability as seen by the media stream.Our results show that for applications that can only measure the packet loss probability, the effects of the PSD on FEC performance are higher in access networks, where a single multimedia stream might affect the multiplexing behavior. Our results show that the effects of the PSD on FEC performance are higher in access networks, where a single multimedia stream might affect the multiplexing behavior and thus can improve the queuing performance by decreasing the variance of its PSD.     

Upgrading of gas oils: the HDS kinetics of dibenzothiophene and its derivatives in real gas oil

The hydrodesulphurization (HDS) of dibenzothiophene (DBT), 4-methyl dibenzothiophene (4 M-DBT), 4,6-dimethyl dibenzothiophene (4,6 DM-DBT) and 4,6-diethyl dibenzothiophene (4,6 DE-DBT) as real gas oil components on NiMo/Al₂O₃ catalyst was investigated. On the basis of the first order rate constants of HDS of the individual sulphur compounds reactivities of the investigated compounds decreased in the order DBT ≫ 4 M-DBT > 4,6 DE-DBT ≈ 4,6 DM-DBT. Apparent activation energies of HDS of above sulphur compounds increased from 80.0 to 120.5 kJ/mol.     

Equilibrium and dynamics of acetylene sorption in multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWCNT) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and by adsorption of N₂ and acetylene. The dynamics of acetylene sorption was studied by frequency response spectroscopy. The average tube dimension and the shell number were determined from a statistical evaluation of the TEM images. This value agreed with that obtained from XRD via the Scherrer equation only if a shape factor of 0.49 was used. The diffusion of acetylene in the nanotubes of the MWCNT sample was found to be the rate-controlling step of the sorption process. Relationships between the tube dimensions and the equilibrium and dynamic sorption properties were demonstrated.     

Some new aspects of the phase diagram of the NH 4 + /H+-W-O system

The phase composition of partially-reduced products of ammonium paratungstate (APT) was investigated. The samples were prepared by reducing the APT in a H₂ + N₂/129 volume ratio/atomosphere in the temperature range 610 to 860 K, and studied by means of chemical analysis, by X-ray diffraction analysis and by thermoanalytical methods. The reduction products can be described by the general formula of M _xWO_3–y+x/2 where M can be either H⁺ and/or NH ₄ ⁺ . Products considered as tungsten bronzes (TB) can be formed in a fairly narrow temperature range. Another product, the so-called decomposed APT (DAPT) is a mixture of bronzes and of some other compounds characterized by y/2 and considered as some intermediate phases between TB and tungstates.     

Stimulatory effect of ascorbate,the alternative electron donor of photosystem II,on the hydrogen production of sulphur-deprived Chlamydomonas reinhardtii

The green alga Chlamydomonas reinhardtii is capable of photoproducing molecular hydrogen following sulphur deprivation, which results in anaerobiosis and a suppression of oxygen evolution and thus an alleviation of the inhibitory effect of oxygen on the hydrogenase. At the same time it transiently maintains a limited supply of electrons arising from photosystem II (PSII) to the hydrogenase (Melis and Happe Plant Physiol 2001; 127:740–748). In this work, using fast chl a fluorescence and P700 measurements, we show that ascorbate (Asc), a naturally occurring PSII alternative electron donor, is capable of donating electrons to PSII in heat-treated and sulphur-deprived cells and this can be significantly accelerated by supplementing the culture with 10 mM Asc. It also enhances, about three-fold, the photoproduction of hydrogen in cells subjected to sulphur deprivation as shown by gas chromatography. Similar stimulation was obtained in the presence of diphenylcarbazide (DPC), an artificial PSII electron donor. Asc and DPC also facilitated the anaerobiosis of cells, probably via super reducing the oxygen evolving complex while feeding electrons to PSII reaction centres and the linear electron transport chain, and ultimately to the hydrogenase – as shown by the significant DCMU-sensitivity of the light-induced Asc- and DPC-dependent re-reduction of P700⁺ and hydrogen evolution.     

Genetic Variation of the Endangered Gentiana lutea L. var. aurantiaca (Gentianaceae) in Populations from the Northwest Iberian Peninsula

Gentiana lutea L. (G. lutea L.) is an endangered plant, patchily distributed along the mountains of Central and Southern Europe. In this study, inter-simple sequence repeat (ISSR) markers were used to investigate the genetic variation in this species within and among populations of G. lutea L. var. aurantiaca of the Cantabrian Mountains (Northwest Iberian Peninsula). Samples of G. lutea L. collected at different locations of the Pyrenees and samples of G. lutea L. subsp. vardjanii of the Dolomites Alps were also analyzed for comparison. Using nine ISSR primers, 106 bands were generated, and 89.6% of those were polymorphic. The populations from the Northwest Iberian Peninsula were clustered in three different groups, with a significant correlation between genetic and geographic distances. Gentiana lutea L. var. aurantiaca showed 19.8% private loci and demonstrated a remarkable level of genetic variation, both among populations and within populations; those populations with the highest level of isolation show the lowest genetic variation within populations. The low number of individuals, as well as the observed genetic structure of the analyzed populations makes it necessary to protect them to ensure their survival before they are too small to persist naturally.     

Comparison of Two Analytical Methods for Assessing Antioxidant Capacity of Rapeseed and Olive Oils

The oxygen radical absorbance capacity (ORAC) and the ferric reducing antioxidant power (FRAP) methods were used for the determination of antioxidant capacities (AC) of rapeseed oils at different steps of technological process and olive oils. The mean ORAC and FRAP results obtained for rapeseed oils (1,106–160 and 552–95.6 μmol TE/100 g) were higher than for olive oils (949–123 and 167–32.1 μmol TE/100 g). Although, FRAP values were lower than ORAC values for all studied oils, there is a linear and significant correlation between these two analytical methods (r = 0.9665 and 0.9298, P < 0.0005) for rapeseed and olive oils, respectively). Also, total phenolic compounds in rapeseed oils and olives correlated with antioxidant capacities (correlation coefficient ranged between 0.9470 and 0.8049). The refining process of rapeseed oils decreased the total phenolics content and antioxidant capacities by about 80%.     

Investigation of impact materials around Barringer Meteor Crater by SEM-EDX and micro-PIXE techniques

Impact materials collected at the Barringer Meteor Crater have been characterized by SEM-EDX and micro-PIXE techniques. Fine textural and true elemental images were created. As a main feature silica-bearing shell and an S–Fe–Ni–Cu core could be distinguished. Three different types of S–Fe–Ni–Cu systems were identified such as chalcopyrite, pentlandite and pyrrhotite.