Identification of ritual blood in African artifacts using TOF-SIMS and synchrotron radiation microspectroscopies

A new protocol is implemented to demonstrate the presence of blood in the patina of African art objects from Mali. Divided into three steps, the protocol first consists in demonstrating the presence of proteins and localizing them in the sample's cross sections using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and synchrotron-based infrared microspectrometry (microFT-IR). In a second time, TOF-SIMS is used to investigate heme, which is a blood marker. If heme is missing, which could mean that it is too degraded to be detected, X-ray microfluorescence (microXRF) and X-ray absorption near-edge microspectroscopy (microXANES) are used to prove the presence of iron in the protein area and to get a fingerprint of its chemical environment. This permits us thus to demonstrate that iron is indeed linked with proteins and not with mineral phases of the sample. Coupled with the ritual context of the objects, this constitutes a proof of the use of blood. Thanks to this protocol, which has the major advantage of avoiding false positive results, the presence of blood has been demonstrated in seven out of the eight studied samples.     

Experimental and calculated liquid-liquid interfacial tension in demixing metal alloys

Liquid-liquid interracial tension in binary and temary Al-based monotectic systems has been determined experimentally with a tensiometric method in a wide temperature interval. The temperature dependence of the interfacial tension is well described by a power law function of the type σαβ - （1 - T/Tc）δ with the critical exponent δ= 1.3 and a critical temperature Tc. Theoretical models describing the liquid-liquid interface in monotectic alloys and their applicability for calculation of the interfacial tension and its temperature dependence in binary systems are considered.     

Reaktionen mit Cyclobutendionen. LII. Reaktionen von 4-Hydroxy-3-phenyl-cyclobut-(3)-en-onen-(1) mit Arylhydrazinen

Reactions of Cyclobutendiones. LII. Reaction of 4-Hydroxy-3-phenyl-3-cyclobuten-1-ones with Arylhydrazines In the reaction of hydroxycyclobutenones of the typ 1 – 4 with arylhydrazines 5 an unexpected reaction behaviour is found. The major products are hydrazones of different structure, the well known hydroxy-cyclopropane-carboxylicacid hydrazines 6 [1] are byproducts. The direction of the reaction depends on the substituents X, on the different substituted arylhydrazines and the solvents.     

NMR structure of the (+)-CPI-indole/d(GACTAATTGAC)-d(GTCAATTAGTC) covalent complex

We report the NMR solution structure of (+)-CPI-indole (CPI, 1,2,8,8a-tetrahydrocyclopropa[c]pyrrolo[3,2-e]indol-4(5H)-one), an agent belonging to the CC-1065/duocarmycin family of antitumor compounds. This (+)-CPI-indole structure is covalently bound to d(G(1)ACTAATTGTC(11))-d(G(12)TCAATTAGTC(22)), a synthetic DNA duplex containing a high-affinity binding site. The three-dimensional structure has been determined by several cycles of restrained molecular dynamics calculations with a total of 563 NMR-derived constraints, both in vacuo and by using the generalized Born solvent continuum model. In-depth analysis of the structure of this ligand-DNA complex led to a detailed knowledge of the bound state conformation of the CPI-indole, the most simplified agent related to CC-1065 and duocarmycins, the parent members of a family of extremely potent antitumor compounds. Comparison of the CPI-indole bound conformation with those previously found for (+)-duocarmycin SA (DSA), its unnatural enantiomer (-)-DSA, and the demethoxylated analogue (+)-DSI in their DNA complexes provided additional evidence of the tight correlation between the catalytic effect exerted by DNA on the alkylation reaction and the extent of angular twist between the two planar heteroaromatic subunits of these agents. Additionally, comparison of the structural features of the DNA-bound state of a "naked" ligand, such as CPI-indole, with those of various other duocarmycin agents provided useful information for the interpretation of the observed effects on chemical reactivity of the different substitution patterns at the hemispheres of these types of complex.     

Polyurethane‐infiltrated carbon foams: A coupling of thermal and mechanical properties

The thermal and mechanical properties of polyurethane‐infiltrated carbon foam of various densities were investigated. By combining the high thermal conductivity of the carbon foam with the mechanical toughness of the pure polyurethane, a mechanically tough composite (relative to the unfilled foam) that could be used at higher temperatures than the polyurethane's degradation was formed. Both the tensile strength and the modulus increased by an order of magnitude for the composites compared to unfilled foam, while the compressive and shear strengths and moduli of the composites approached values exhibited by pure polyurethane. At both 300 and 400°C, the rectangular blocks of pure polyurethane lost their mechanical integrity due to decomposition in air. Thermogravimetric analysis confirms substantial initial weight loss above 290°C. Filled carbon foam blocks, however, maintain their mechanical integrity at both 300 and 400°C indefinitely, although the bulk of the rectangular block mass is polyurethane. Three different carbon foam densities are examined. As expected, the higher density foams show greater heat transfer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2348–2355, 2003     

Feasibility study on electrically conductive joining of MoSi2 electrodes for spark plugs

Despite the often outstanding functional as well as (high temperature-) mechanical properties of ceramics, their usage is often limited due to their inherent brittleness. This also compromises the joining with metals, which is often indispensable for engineering applications. In this context, electrically conductive ceramics like MoSi₂ are promising materials for the application as electrodes where high temperatures in harsh environments are present (e.g., in spark plugs for large gas engines). Due to the difficult joining of the respective materials, long-term experiments are thereby often still pending. In this work, adhesive bonding, brazing, tungsten inert gas-, and resistance welding were performed to evaluate their applicability for generating electrically conductive as well as mechanically reliable joints between MoSi₂ and Inconel 600, aiming to utilize MoSi₂ electrodes in spark plugs. Fractographic analyses are performed to understand cracks associated with the high (thermo-) mechanical stresses. Additionally, a finite element model was set up for a deeper understanding of the observed fracture behavior. While adhesive bonding is acceptable for short-term experiments at low temperatures, brazing and resistance welding may qualify for fast and reliable manufacturing of spark plugs with ceramic electrodes.     

Model Adherend Surface Effects on Epoxy Cure Reactions

Adherend surface effects on the amine cure of epoxy resins were investivated using finely divided aluminum oxide as high surface area models for aluminum. Calorimetric analysis of simplified crosslinking systems revealed significantly faster reactions which led to lower glass transition temperature materials for activated aluminum oxide filled samples. A monofunctional amine and epoxy were then utilized to obtain soluble reaction products amenable to molecular characterization. These studies similarly showed an increase in the rate of epoxy consumption in the presence of activated aluminum oxide which was attributed to both an increase in the rate of amine addition to epoxy as well as to epoxy homopolymerization. The latter was not observed in the unfilled mixtures. Such changes in reaction mechanism at the adherend surface have implications for the strength and durability of actual adhesive bonds.     

Effect of ferrous and ferric iron impurities on the crystallization of gypsum and sludge formation in wet-process phosphoric acid

The effect of ferrous and ferric iron on the crystallization of calcium sulfate dihydrate, the rate of filtration, and the precipitation of sludge in concentrated acid were investigated. A bench scale unit was used to simulate dihydrate plant conditions. It was found that ferrous iron was oxidized to ferric, and the behavior of the two impurities in the acid was therefore very similar. At low levels of impurities, ferrous and ferric iron improved filtration, but further additions decreased it. Sludge collected from the concentrated acid after five weeks was mainly calcium sulfate hemihydrate and anhydrate. With the addition on 0.5% and 0.75% iron impurities however, the presence of (Fe,Al) 3 KH 14 (PO 4 ) 8 ·4H 2 O was evident in electron micrographs.