First chemical evidence of royal purple as a material used for funeral treatment discovered in a Gallo�CRoman burial (Naintr��, France, third century AD)

Violet-purple residues collected from a Gallo-Roman burial dated back to the second half of the third century A.D. and excavated at Naintré (France) were chemically investigated by multi-analytical methodology involving the use of Raman spectroscopy, direct exposure-mass spectrometry (DE-MS) and high-performance liquid chromatography (HPLC-UV-visible). Little is known about funeral treatment and rituals during Roman times. Retrieving valuable information on these by chemical analysis of organic residues was thus a key aspect of this work. Analyses demonstrated the presence of the very precious purple colorant obtained from shellfish glands commonly known as Tyrian or royal purple and its exceptional preservation. Chemical investigation and archaeological evidence have shown that purple was widely spread after the deposition of the body for burial. These results are the earliest chemical evidence of purple colorant used during funeral rituals (not as textile dye) and enabled us to highlight new aspects of funeral practices in Roman times.     

Analytical pyrolysis with in situ thermally assisted derivatisation, Py(HMDS)-GC/MS, for the chemical characterization of archaeological birch bark tar

An analytical method based on pyrolysis in the presence of hexamethyldisilazane followed by gas chromatographic/mass spectrometric analysis, Py(HMDS)-GC/MS, was used for the first time to study birch bark tar, an adhesive that has been used since the Palaeolithic period. Py(HMDS)-GC/MS enabled us to obtain information simultaneously both on polymerised and solvent soluble fractions of birch bark tar. A very particular chromatographic pattern was obtained, which was mainly characterised by the presence of homologous series of linear saturated and unsaturated monocaboxylic fatty acids, and homologous series of straight-chain alkenes and alkanes. The pattern can be linked to suberin and suberan, which are known to be present in birch barks. In addition, lupane-type triterpenoids were also revealed. Py(HMDS)-GC/MS was initially applied to a reference material, and was then used to study the archaeological adhesives from a wooden spindle recovered in a Gallo-Roman burial (3rd century AD) and from the golden sheath of a Thracian dagger (8th-7th centuries BC) recovered in Belogradets (Bulgaria).     

Sub-Poissonian fluctuations in a 1D Bose gas: from the quantum quasicondensate to the strongly interacting regime

We report on local, in situ measurements of atom number fluctuations in slices of a one-dimensional Bose gas on an atom chip setup. By using current modulation techniques to prevent cloud fragmentation, we are able to probe the crossover from weak to strong interactions. For weak interactions, fluctuations go continuously from super- to sub-Poissonian as the density is increased, which is a signature of the transition between the subregimes where the two-body correlation function is dominated, respectively, by thermal and quantum contributions. At stronger interactions, the super-Poissonian region disappears, and the fluctuations go directly from Poissonian to sub-Poissonian, as expected for a "fermionized" gas.     

Approaches to open fullerenes: synthesis and kinetic stability of diels-alder adducts of substituted isobenzofurans and C60

We have examined the reactions of 1,3-disubstituted isobenzofurans with the fullerene C60 in the context of an approach to open a large orifice on the fullerene framework. A variety of substituted isobenzofurans (6a-h), generated from the reaction of 1,4-substituted 1,4-epoxynaphthalenes 3a-h with 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (4a) or 1,2,4,5-tetrazine (4b), were added to C60 to afford the Diels-Alder adducts 7a-h. The thermal stability of these adducts toward retro-Diels-Alder fragmentation differs greatly in solution from that in the solid state. In solution, the relatively facile retro-Diels-Alder fragmentation of monoadducts 7a and 7c, to give C60 and the free isobenzofurans 6a and 6c, have rate constants (and activation barriers) of k=9.29x10(-5) s-1 at 70 degrees C (Ea=32.6 kcal mol-1) and k=1.36x10(-4) s-1 at 40 degrees C (Ea=33.7 kcal mol-1), respectively, indicating that the addition of isobenzofurans to C60 is readily reversible at those temperatures. In the solid state, thermogravimetric analysis of adduct 7a indicates that its decomposition occurs only within the temperature range of 220-300 degrees C. As a result, these compounds can be stored at room temperature in the solid state for several weeks without significant decomposition but have to be handled within several hours in solution.     

Efficient preparation of enantiomerically pure α-aryl-α-trifluoromethylglycines via Auto Seeded Programmed Polythermic Preferential Crystallization of 5-aryl-5-trifluoromethylhydantoins

Both pure enantiomers of α-phenyl- (or α-(p-methoxyphenyl))-α-trifluoromethyl-glycine and their corresponding methyl esters were obtained on a preparative scale using the following four-step sequence: the preparation of 5-aryl-5-trifluoromethylhydantoins by a Bücherer-Bergs reaction starting from trifluoromethyl aryl ketones, optical resolution by Auto Seeded Programmed Polythermic Preferential Crystallization (AS3PC), basic hydrolysis of the enantiopure hydantoins by means of aqueous barium hydroxide, and esterification of the amino acids with trimethylsilyldiazomethane. Hydantoins 5 and 6 were proven to crystallize as conglomerates using first second harmonic generation and then X-ray powder diffraction. The absolute stereochemistry of (+)-5-phenyl-5-trifluoromethylhydantoin 5b was established to be (S) by X-ray diffraction analysis on a single-crystal.     

Classification of periodic orbits of two-dimensional homogeneous granular crystals with no pre-compression

In the present study we classify the periodic orbits of a squarely packed, uncompressed and undamped, homogeneous granular crystal, assuming that all elastic granules oscillate with the same frequency (i.e., under condition of 1:1 resonance); this type of Hamiltonian periodic orbits have been labeled as nonlinear normal modes. To this end we formulate an auxiliary system which consists of a two-dimensional, vibro-impact lattice composed of non-uniform “effective particles” oscillating in an anti-phase fashion. The analysis is based on the idea of balancing linear momentum in both horizontal and vertical directions for separate, groups of particles, whereby each such a group is represented by the single effective particle of the auxiliary system. It is important to emphasize that the auxiliary model can be defined for general finite, squarely packed granular crystals composed of n rows and m columns. The auxiliary model is successful in predicting the total number of such periodic orbits, as well as the amplitude ratios for different periodic regimes including strongly localized ones. In fact this methodology enables one to systematically study the generation of mode localization in these strongly nonlinear, highly degenerate dynamical systems. Good correspondence between the results of the theoretical model and direct numerical simulations is observed. The results presented herein can be further extended to study the intrinsic dynamics of the more complex granular materials, such as heterogeneous two-dimensional and three-dimensional granular crystals and multi-layered structures.     

Effects of mutations on the absorption spectra of copper proteins: a QM/MM study

The ground and excited state properties of copper proteins are studied and analyzed using hybrid quantum mechanics/molecular mechanics technique. Wild-type plastocyanin, characterized by an intense blue color, and wild-type nitrosocyanin, a red protein, are considered. These proteins differ from some ligands of the copper containing chromophore; we also studied the effects of selective mutations of one of the active site residue in plastocyanin. It is shown that this mutation is able to strongly modify the UV/VIS spectrum continuously modifying the absorption spectrum of the protein that from blue becomes red. Electrostatic and polarization effects of the macromolecular environment on the chromophore are taken into account using original techniques. Principal transitions are analyzed by mean of natural transition orbitals.     

A unified solution framework for multi-attribute vehicle routing problems

Vehicle routing attributes are extra characteristics and decisions that complement the academic problem formulations and aim to properly account for real-life application needs. Hundreds of methods have been introduced in recent years for specific attributes, but the development of a single, general-purpose algorithm, which is both efficient and applicable to a wide family of variants remains a considerable challenge. Yet, such a development is critical for understanding the proper impact of attributes on resolution approaches, and to answer the needs of actual applications. This paper contributes towards addressing these challenges with a component-based design for heuristics, targeting multi-attribute vehicle routing problems, and an efficient general-purpose solver. The proposed Unified Hybrid Genetic Search metaheuristic relies on problem-independent unified local search, genetic operators, and advanced diversity management methods. Problem specifics are confined to a limited part of the method and are addressed by means of assignment, sequencing, and route-evaluation components, which are automatically selected and adapted and provide the fundamental operators to manage attribute specificities. Extensive computational experiments on 29 prominent vehicle routing variants, 42 benchmark instance sets and overall 1099 instances, demonstrate the remarkable performance of the method which matches or outperforms the current state-of-the-art problem-tailored algorithms. Thus, generality does not necessarily go against efficiency for these problem classes.     

Bonding a linearly piezoelectric patch on a linearly elastic body

A rigorous study of the asymptotic behavior of the system constituted by a very thin linearly piezoelectric plate bonded on a linearly elastic body supplies various models for an elastic body monitored by a piezoelectric patch.