Aplicación del método de series de Uranio al grafismo rupestre de estilo paleolítico: el caso de la cavidad de Covalanas (Ramales de la Victoria, Cantabria)

[EN] Se ensaya la aplicación del procedimiento analítico de series de Uranio para el conocimiento de la seriación artística de obras parietales de estilo paleolítico. El resultado obtenido muestra la validez del método y abre nuevas vías para la obtención de fechas absolutas "ante quem" y "post quem" que sirvan para enmarcar momentos de ejecución de obras rupestres.

En torno al llamado «arte esquemático-abstracto»: a propósito de unas fechas de Covalanas (Ramales de la Victoria, Cantabria)

[ES] La introducción de técnicas físico-químicas al estudio del grafismo rupestre paleolítico está abriendo nuevos campos de conocimiento sobre los procedimientos técnicos, la cronología y la conservación de los motivos. La utilización de la técnica radiométrica de C14 A.M.S. ha sido aplicada en Covalanas. Las dataciones de época histórica de dos pequeños fragmentos de carbón procedentes de marcas negras sirven para reflexionar en torno al llamado «arte esquemático-abstracto».

Pollen profiles from a Late Palaeolithic site in the community of Bad Buchau-Kappel, Baden-Wuerttemberg, Germany

Excavations were carried out in a Late Palaeolithic site in the community of Bad Buchau-Kappel between 2003 and 2007. Archaeological investigations covered a total of more than 200 m**2. This site is the product of what likely were multiple occupations that occurred during the Late Glacial on the Federsee shore in this location. The site is situated on a mineral ridge that projected into the former Late Glacial lake Federsee. This beach ridge consists of deposits of fine to coarse gravel and sand and was surrounded by open water, except for a connection to the solid shore on the south. A lagoon lay between the hook-shaped ridge and the shore of the Federsee. This exposed location provided optimal access to the water of the lake. In addition, the small lagoon may have served as a natural harbor for landing boats or canoes. Sedimentological and palynological investigations document the dynamic history of the location between 14,500 and 11,600 years before present (cal BP). Evidence of the deposition of sands, gravels and muds since the Bølling Interstadial is provided by stratigraphic and palynological analyses. The major occupation occurred in the second half of the Younger Dryas period. Most of the finds were located on or in the sediments of the ridge; fewer finds occurred in the surrounding mud, which was also deposited during the Younger Dryas. Direct dates on some bone fragments, however, demonstrate that intermittent sporadic occupations also took place during the two millennia of the Meiendorf, Bølling, and Allerød Interstadials. These bones were reworked during the Younger Dryas and redeposited in the mud. A 14C date from one bone of 11,600 years ago (cal BP) places the Late Palaeolithic occupation of the ridge at the very end of the Younger Dryas, which is in agreement with stratigraphic observations. Stone artifacts, numbering 3,281, comprise the majority of finds from the site. These include typical artifacts of the Late Palaeolithic, such as backed points, short scrapers, and small burins. There are no bipointes or Malaurie-Points, which is in accord with the absolute date of the occupation. A majority of the artifacts are made from a brown chert that is obtainable a few kilometers north of the site in sediments of the Graupensandrinne. Other raw materials include red and green radiolarite that occur in the fluvioglacial gravels of Oberschwaben, as well as quartzite and lydite. The only non-local material present is a few artifacts of tabular chert from the region near Kelheim in Bavaria. A unique find consists of two fragments of a double-barbed harpoon made of red deer antler, which was found in the Younger Dryas mud. It is likely, but not certain, that this find belongs to the same assemblage as the numerous stone artifacts. Although not numerous, animal bones were also found in the excavations. Most of them lay in sediments of the Younger Dryas, but several 14C dates place some of these bones in earlier periods, including the Meiendorf, Bølling, and Allerød Interstadials. These bones were reworked by water and redeposited in mud sediments during the Younger Dryas. As a result, it is difficult to attribute individual bones to particular chronological positions without exact dates. Species that could be identified include wild horse (Equus spec.), moose or elk (Alces alces), red deer (Cervus elaphus), roe deer (Capreolus capreolus), aurochs or bison (Bos spec.), wild boar (Sus scrofa), as well as birds and fish, including pike (Esox Lucius).

Crime, Punishment and Article 3 ECHR: Puzzles and Prospects of Applying an Absolute Right in a Penal Context

Article 3 of the European Convention on Human Rights (ECHR), which provides that ‘No one shall be subjected to torture or to inhuman or degrading treatment or punishment’, is considered to enshrine an absolute right. Yet it contains an under-explored element: inhuman and degrading punishment. While torture has been the subject of extensive academic commentary, and inhuman and degrading treatment has been examined to some extent, the prohibition of inhuman and degrading punishment has not been explored in significant depth, in spite of its considerable potential to alter the penal landscape.

This paper elucidates the key doctrinal elements of inhuman and degrading punishment ‘and treatment associated with it’, in the words of the European Court of Human Rights (ECtHR). It addresses a number of ‘puzzles’ or problems which arise in applying the absolute right enshrined in Article 3 of the ECHR to sentencing and imprisonment, clarifies ECtHR doctrine and highlights some of its key implications. Bringing a theoretically informed understanding to bear on the application of Article 3 of the ECHR in a penal context, the paper provides clarity and coherence to a complex and crucial intersection between human rights and penology.

Interactions between pyrazole derived enantiomers and Chiralcel OJ: Prediction of enantiomer absolute configurations and elution order by molecular dynamics simulations

The separation of enantiomers and confirmation of their absolute configurations is significant in the development of chiral drugs. The interactions between the enantiomers of chiral pyrazole derivative and polysaccharide-based chiral stationary phase cellulose tris(4-methylbenzoate) (Chiralcel OJ) in seven solvents and under different temperature were studied using molecular dynamics simulations. The results show that solvent effect has remarkable influence on the interactions. Structure analysis discloses that the different interactions between two isomers and chiral stationary phase are dependent on the nature of solvents, which may invert the elution order. The computational method in the present study can be used to predict the elution order and the absolute configurations of enantiomers in HPLC separations and therefore would be valuable in development of chiral drugs.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Heuristic methods for the single machine scheduling problem with different ready times and a common due date

The single machine scheduling problem with a common due date and non-identical ready times for the jobs is examined in this work. Performance is measured by the minimization of the weighted sum of earliness and tardiness penalties of the jobs. Since this problem is NP-hard, the application of constructive heuristics that exploit specific characteristics of the problem to improve their performance is investigated. The proposed approaches are examined through a computational comparative study on a set of 280 benchmark test problems with up to 1000 jobs.

Atropisomeric xanthines: Synthesis, stereodynamics and absolute configuration

During the thesis period a new class of atropisomeric xanthine derivatives has been studied. We decided to focus our attention on these purine bases because of their various biological activities, that could play an important role in the discovery of new bioactive atropisomers. The synthesized compounds bear an Aryl-N chiral axis in position 1 of the xanthine scaffold, around which the rotation is prevented by the presence of bulky ortho substituents. Through a retro synthetic analysis we synthesized three atropisomeric structures bearing in position 1 of the purine scaffold respectively an o-tolyl, o-nitrophenyl and a 1-naphthyl group. The conformational studies by DFT simulations showed that the interconversion energy barrier between the two available skewed conformations is higher enough to obtain thermally stable atropisomers. After the separation of the atropisomers, the experimental energy of interconversion was investigated by means of kinetic studies following the thermal racemization process using an enantioselective HPLC column. The absolute configuration of each atropisomer was assigned by experimental ECD analysis and TD-DFT simulations of the ECD spectra.