Evolution of the interface and metal film morphology in the vapor deposition of Ti on hexadecanethiolate hydrocarbon monolayers on Au

The combination of in situ X-ray photoelectron spectroscopy, infrared reflection spectroscopy, atomic force microscopy, and time-of-flight secondary ion mass spectrometry are used to probe the nature of the evolving interface chemistry and metal morphology arising from Ti vapor deposition onto the surface of a CH(3)(CH(2))(15)S/Au{111} self-assembled monolayer (SAM) at ambient temperature. The results show that for a deposition rate of approximately 0.15 Ti atom.nm(-2).s(-1) a highly nonuniform Ti overlayer is produced via a process in which a large fraction of impinging Ti atoms do not stick to the bare SAM surface. The adsorbed atoms form isolated Ti clusters and react with CH(3) groups to form carbide products at the cluster-SAM interfaces. Further growth of Ti clusters appears to be concentrated at these scattered reaction centers. The SAM molecules in the local vicinity are subsequently degraded to inorganic products, progressing deeper into the monolayer as the deposition proceeds to give an inorganic/organic nanocomposite. A continuous overlayer does not form until metal coverage approaches approximately 50 Ti atoms per SAM molecule. These data indicate that for applications such as molecular device contacts the use of Ti may be highly problematic, suffering from both a highly nonuniform contact area and the presence of extensive inorganic products such as nonstoichiometric carbides and hydrides.     

Préparation d'isoxazoles trisubstitués par réduction chimique et électrochimique d'α-acyl β-nitrostilbènes

Nitration of α-acylstilbenes with dinitrogen tetroxide leads to corresponding Z-α-acyl-β-nitrostilbenes. By chemical or electochemical reduction of these compounds, trisubstituted isoxazoles were prepared in good yields.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Extraction separation of Cs+, Sr2+ and Ba2+ from a mixture of cations forming stable non-extractable complexes with ethylenediamine-N,N, N′,N′-tetraacetic acid in the water-nitrobenzene system

In the two-hase water-nitrobenzene extraction system, a method for gradual separation of Cs⁺, Sr²⁺ and Ba²⁺ from the mixture of cations forming stable non-extractable complexes with ethylenediamine-N, N, N,N-tetraacetic acid in the presence of the sodium salt of dicarbollylcobaltate anion {[-(3)-1, 2-B₉C₂H₁₁]₂ Co(III)}^– and polyethylene glycol ligand with a mean relative molecular mass of 400 (PEG 400), respectively, was developed. In the first extraction step, Cs⁺ was extracted into the organic phase while the other cations studied (Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Co²⁺, Ce³⁺) remained in the aqueous phase. In the second extraction step, Sr²⁺ and Ba²⁺ were extracted into the nitrobenzene phase. Finally, in the following reextraction step, Sr²⁺ was transferred into the aqueous phase while Ba²⁺ remained in the organic phase.     

Rapid separation of phenylthiohydantoin amino acids: ambient pressure ion-mobility mass spectrometry (IMMS)

An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids.     

Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes

A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H(2)Co(dppe)(2)](+), HCo(dppe)(2), [HCo(dppe)(2)(CH(3)CN)](+), and [Co(dppe)(2)(CH(3)CN)](2+), where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H(2)Co(dppe)(2)](+) and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)(2)](+) to form [Co(dppe)(2)](+) and [H(2)Co(dppe)(2)](+), the reaction of [Co(dppe)(2)](+) with H(2), the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.     

Synthesis,crystal structure and luminescent property of a novel H<Subscript>2</Subscript>O-bridged cobalt(II) polymer with one-dimensional chain structure

The coordination compound [Co(C₁₀H₇COO)₂(H₂O)₃]_2n · 4nH₂O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions. The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can be assigned to the intraligand electronic transfer.     

Probing the kinetic landscape of transient peptide-protein interactions by use of peptide (15)n NMR relaxation dispersion spectroscopy: binding of an antithrombin peptide to human prothrombin

Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex.     

Analyse de population dans les calculs LCAO: charges et moments atomiques

Résumé Les auteurs montrent que le moment dipolaire d'une molécule peut, avec une bonne approximation, se réduire à la somme vectorielle des moments atomiques et d'un moment de charges ponctuelles centrées sur les atomes. Les charges ainsi définies sont indépendantes du système d'axes de coordonnées.

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Population analysis by LCAO calculations: Charges and atomic moments

The authors show that the dipole moment of a molecule can be reduced to the vector sum of the atomic moments and of a moment due to point charges centred on atoms with a good accuracy. The so defined charges are independent of the coordinate system.

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Zusammenfassung Die Autoren zeigen, daß das Dipolmoment von Molekülen als Vektorsumme der Atommomente und eines Moments, das von Punktladungen an den Atomen herrührt, dargestellt werden kann. Die dabei definierten Ladungen sind unabhängig vom Koordinatensystem.

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Equipe de Recherche Associée au C.N.R.S. n 22.

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Remerciements. Ce travail a été en partie présenté au 2ème Colloque International des Chimistes Théoriciens d'expression latine (Paris, septembre 1970).Les auteurs remercient les participants à ce Colloque et en particulier Madame A. Pullman et Monsieur P. Claverie pour leurs remarques et leurs suggestions. Leur gratitude va également au Centre National de la Recherche Scientifique pour l'aide matérielle qu'il apporte à ces recherches.     

Epoxide networks as model networks

Summary The equilibrium mechanical behaviour of weak diepoxide-monoepoxide-diamine networks, prepared with an excess of diamine and measured in the rubbery state, was compared with theoretical predictions obtained by using the theory of branching processes. The experimental equilibrium moduli fit well the shape of theoretical curves over a broad range of crosslinking density regardless of whether the contribution by trapped entanglements is considered or not. The data fit equally well the theoretical dependence for the front factor A = 1 without entanglement contribution and forA = (f _e - 2)/f _e , (f _e is the average effective functionality of a junction) with an entanglement contribution based on the contact probability between any two units within elastically active network chains (Langley).Dedicated to Prof. Dr.G. Rehage on the occasion of his 60th birthday.With 5 figures