Chemically controlled pattern formation in phase-separating materials

Summary The role of chemical reactions in the selection of patterns in phase-separating mixtures is presented. Linearized theory and computer simulation show that the initial long-wavelength instability characteristic of spinodal decomposition is suppressed by chemical reactions, which restrict domain growth to intermediate length scales even in the late stages of phase separation. Our findings suggest that chemical reactions may provide a novel way to stabilize and tune the steady-state morphology of phase-separating materials. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

On-line preconcentration method for the determination of trace metals in water samples using a fully automated pretreatment system coupled with ICP-AES.

An automated on-line sample-preparation method using a computer-controlled pretreatment system (Auto-Pret AES system) coupled with ICP-AES was developed. In this work, an iminodiacetate chelating resin, packed in a mini-column and installed in the system was employed for the collection/concentration of 13 trace metals, including such toxic metals as Be, Cd, Cr, Cu and Pb. The limits of detection of the proposed method for trace metals were in the range of 0.001 (Be) -0.18 (Pb) ng mL-1. The enrichment factors for metal ions were about 19 times, when 5 mL of samples were used. The sample throughput was 11 h-1. The accuracy and the precision of the method were evaluated using river-water reference materials, SLRS-4 from NRCC, JSAC 0301-1 and JSAC 0302 from the Japan Society for Analytical Chemistry. The proposed method can be favorably applied to the collection/concentration of trace metals in natural water samples.     

Interfaces and typical Gibbs configurations for one-dimensional Kac potentials

Summary We consider a one dimensional Ising spin system with a ferromagnetic Kac potential J(|r|),J having compact support. We study the system in the limit, »0, below the Lebowitz-Penrose critical temperature, where there are two distinct thermodynamic phases with different magnetizations. We prove that the empirical spin average in blocks of size ^–1 (for any positive ) converges, as »0, to one of the two thermodynamic magnetizations, uniformly in the intervals of size ^–p , for any given positivep1. We then show that the intervals where the magnetization is approximately constant have lengths of the order of exp(c ^–1),c>0, and that, when normalized, they converge to independent variables with exponential distribution. We show this by proving large deviation estimates and applying the Ventsel and Friedlin methods to Gibbs random fields. Finally, if the temperature is low enough, we characterize the interface, namely the typical magnetization pattern in the region connecting the two phases.The research has been partially supported by CNR, GNFM, GNSM and by grant SC1CT91-0695 of the Commission of European Communities     

Photochemische synthese von H2Fe3-komplexen und ihre aktivität bei der photokatalytischen hydrierung von olefinen und dienen

The photochemical reaction of the trinuclear complex Fe₃(CO)₁₀NSi(CH₃)₃ under hydrogen leads to substitution of the bridging carbonyl group by two hydrogens. The resulting complex H₂Fe₃(CO)₉NSi(CH₃)₃ acts as a catalyst in the photochemical hydrogenation of olefins and dienes.     

Quantum mechanical description of electrode reactions: Part II. Treatment of compact layer structure at platinum electrodes by means of the extended Hückel molecular orbital method. Pt(111) surfaces

The Iteraltive Extended Hückel Molecular Orbital method has been adapted to calculation of the properties of an electrode and compact layer. Predictions of the stablest orientations, on the Pt(111) surface of species such as H₂O, Pt, OH^?, H, and the halides, F^?, Cl^?, Br^? and I^?, based upon calculation of the total energy corresponding to various internuclear distances, are reported. The calculations correctly predict self-adsorption of Pt on the Pt(111) surface at the face-centered cubic closest-packing position. The H₂O molecule is predicted to locate itself above three adjoining Pt atoms, with the O atom closest to the surface and the H atoms opposite the O. Similar results were obtained for OH^? and the halides. Atomic H, however, is predicted to drop into the plane of centers of the Pt surface atoms, where it would lie between, three adjacent Pt atoms. Application of the method to electrode studies requires only modest amounts of computer time but produces surprisingly reliable qualitative predictions. Compulation of electrochemical quantities such as charge, differential capacitance, surface tension and potential energy as a function of electrode potential will be described in future work.     

H2/CO2 separations in multicomponent metal-adeninate MOFs with multiple chemically distinct pore environments

Metal–organic frameworks constructed from multiple (≥3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn–Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H₂/CO₂ separation ability of bMOF-200. We examine the H₂/CO₂ separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H₂/CO₂ separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H₂ and CO₂ and a significantly improved H₂/CO₂ separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H₂/CO₂ separations.

Tailorable multicomponent MOFs and MOF membranes for efficient H₂/CO₂ separation.     

Analysis of egg-based model wall paintings by use of an innovative combined dot-ELISA and UPLC-based approach

The chemical analysis of egg-based wall paintings—the mezzo fresco technique—is an interesting topic in the characterisation of organic binders. A revised procedure for a dot-enzyme-linked immunosorbent assay (dot-ELISA) able to detect protein components of egg-based wall paintings is reported. In the new dot-ELISA procedure we succeeded in maximizing the staining colour by adjusting the temperature during the staining reaction. Quantification of the colour intensity by visible reflectance spectroscopy resulted in a straight line plot of protein concentration against reflectance in the wavelength range 380–780 nm. The modified dot-ELISA procedure is proposed as a semi-quantitative analytical method for characterisation of protein binders in egg-based paintings. To evaluate its performance, the method was first applied to standard samples (ovalbumin, whole egg, egg white), then to model specimens, and finally to real samples (Giotto’s wall paintings). Moreover, amino acid analysis performed by innovative ultra-performance liquid chromatography was applied both to standards and to model samples and the results were compared with those from the dot-ELISA tests. In particular, after protein hydrolysis (24 h, 114 °C, 6 mol L^?1 HCl) of the samples, amino acid derivatization by use of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate enabled reproducible analysis of amino acids. This UPLC amino acid analysis was rapid and reproducible and was applied for the first time to egg-based paintings. Because the painting technique involved the use of egg-based tempera on fresh lime-based mortar, the study enabled investigation of the effect of the alkaline environment on egg-protein detection by both methods.

Semiempirical Potential in Kinetics Calculations on the HC3N + CN Reaction

The reaction between the cyano radical CN and cyanoacetylene molecule HC3N is of great interest in different astronomical fields, from star-forming regions to planetary atmospheres. In this work, we present a new synergistic theoretical approach for the derivation of the rate coefficient for gas phase neutral-neutral reactions. Statistic RRKM calculations on the Potential Energy Surface are coupled with a semiempirical analysis of the initial bimolecular interaction. The value of the rate coefficient for the HC3N + CN → H + NCCCCN reaction obtained with this method is compared with previous theoretical and experimental investigations, showing strengths and weaknesses of the new presented approach.     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.