Characterization of medieval proteinaceous painting media using gas chromatography and gas chromatography — mass spectrometry

Proteinaceous organic materials used as ancient painting media were investigated by capillary gas chromatography (GC) and capillary gas chromatography — mass spectrometry (GC/MS). Medieval wall paintings made by the tempera technique were considered and their binding media were studied by the characterization of their main chemical components. The basic methodology is based on the determination of amino acids in samples of paint layers after hydrolysis and derivatization and on the comparison with reference proteinaceous materials. Multivariate chemometric techniques were used to facilitate the recognition of the protein source from chromatographic data. To characterize the binders further, a method was developed for the determination of fatty acids, present as minor components, by GC/MS. The use of fused-silica capillary columns coated with selected stationary phases allowed the separation of amino acid and fatty acid derivatives in a single analytical run.     

Formation and dissociation equilibria of intermediate species in the oxidation of cobalt(II)-dipeptide complexes

Summary The oxidation of various cobalt(II)-dipeptide complexes in the presence of both molecular oxygen and hydrogen peroxide is examined. The nature of the oxidant exercises a marked influence on the reaction path. The oxo-intermediate species formed apparently possesses different structures, depending on the oxidant. Moreover, when molecular oxygen is employed, the inertness of the resulting cobalt(III)-dipeptide complexes is much higher, suggesting a different degree of protonation. The effect of the ligand structure on the oxidative process is considered; the reaction rate is found to be strongly influenced by the hydrophobicity of the substituent group and by the presence of amidic hydrogen.     

New selective nickel(II)-N3 nitrogen bond in adenine: Synthesis and structure of [(tren) (adenine) (monochloro)nickel(II)] chloride and [(tren)(imidazole)(monoaqua)nickel(II)] dichloride

With the aim to obtain further insight into the nature of the Ni(II)-nitrogen bond in complexes with nucleobases, we have synthesized two novel Ni(II) ternary complexes constituted by Ni(II), tris(2-aminoethyl)amine (tren) and neutral adenine (AdH) or imidazole (ImH). The reaction of NiCl₂·6H₂O with tren and imidazole yields the ternary [Ni(tren)(ImH)(H₂O)]Cl₂·H₂O complex and the same reaction with adenine instead of imidazole gives the ternary [Ni(tren)(AdH)Cl]Cl complex. The complexes have been studied by spectrophotometric and spectroscopic measurements and by X-ray diffraction. The ternary complex of adenine is monoclinic, space groupC2/c, and exhibits a pseudo-octahedral geometry, being Ni(II) coordinated to the four nitrogen atoms of the tetradentate tren ligand, to a Cl^– ion and to the pyrimidine N3 site of a neutral adenine. Such an exclusive Ni-N3 bonding [2.081(4)Å] is now reported for the first time. The ternary complex of imidazole is monoclinic, space groupP2₁/n. Its pseudo-octahedral geometry is similar to that found in the above adenine complex although a water molecule instead of a Cl^– ion is now present in the coordination sphere. In fact, Ni(II) is coordinated to tetradentate tren, to the imidazole N1 nitrogen and to a water molecule. Electronic and¹H NMR spectra in solution indicate that the octahedral structures found in the solid state are substantially maintained in solution. Furthermore, the present investigation suggests that the adenine Ni-N3 and imidazole Ni-N1 bonds have the same chemical nature, involving mainly - and only partially-bonding. The Ni-N3 bonding is discussed in connection with biological implications and possible applications.     

Influence of membrane surface properties on the growth of neuronal cells isolated from hippocampus

Membranes have become of great interest for tissue engineering application, since they offer the advantage of developing neuronal tissue that may be used in implantable or in vitro hybrid systems for the simulation of brain function. The behaviour of neurons isolated from the hippocampus on membranes with different surface properties was investigated.     

Breakdown kinetics of aggregates from poly(ethylene glycol‐bl‐propylene sulfide) di‐ and triblock copolymers induced by a non‐ionic surfactant

We explored the effects of addition of the nonionic surfactant Triton X‐100 on the stability of aggregates of poly(ethylene glycol‐bl‐propylene sulfide) di‐ and triblock copolymers. Fluorescence spectra of pyrene, used as a probe molecule, elucidated the various stages of transformation from pure copolymeric micelles to surfactant‐rich micelles. Turbidity measurements yielded insight into the mechanism of the interaction, the hydrophobicity of the copolymer driving the process. Triton X‐100 tends to strongly interact with highly hydrophobic copolymers by inserting into the core of the micellar aggregates. On the other hand, Triton X‐100 tends to interact with the corona of micelles formed by less hydrophobic copolymers which, for this reason, are more stable upon addition of this destabilizing agent. Kinetic data give evidence that only monomers, not micelles of surfactant, interact with the copolymer micelles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2477–2487, 2008     

Fluoride Ion Promoted Reactivity of Thiocarbonyl Containing Molecules with Silyl Derivatives: A Novel Access to Allyl Sulfides

Abstract

Fluoride ion induced reaction of allyl- and benzyl-silanes with thiocarbonyls leads, contrary to the corresponding lithium or Grignard reagents, to products of S-functionalization.     

High-throughput heterogeneous catalyst research

With the discovery of abundant and low cost crude oil in the early 1900’s came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them.Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems.We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the hydrodesulfurization of gasoline distillates having 50% more selectivity and 30% more activity for sulfur removal than the state-of-the-art commercial reference.     

A homogenized viscoelastic model for masonry structures

A linear viscous model for evaluating the stresses and strains produced in masonry structures over time is presented. The model is based on rigorous homogenization procedures and the following two assumptions: that the structure is composed of either rigid or elastic blocks, and that the mortar is viscoelastic. The hypothesis of rigid block is particularly suitable for historical masonry, in which stone blocks may be assumed as rigid bodies, while the hypothesis of elastic blocks may be assumed for newly constructed brickwork structures. The hypothesis of viscoelastic mortar is based on the observation that non-linear phenomena may be concentrated in mortar joints. Under these assumptions, constitutive homogenized viscous functions are obtained in an analytical form.Some meaningful cases are discussed: masonry columns subject to minor and major eccentricity, and a masonry panel subject to both horizontal and vertical loads. The major eccentricity case is analysed taking into account both the effect of viscosity and the no-tension hypothesis, whereas the bi-dimensional loading case is analysed to verify the sensitivity of masonry behaviour to viscous function. In the masonry wall considered, the principal stresses are both of compression, and the no-tension assumption may therefore be discounted.