The chemistry of the phosphates of barium and tetravalent cations in the 1:1 stoichiometry

The chemistry of phosphates of barium and tetravalent cations [BaM^IV(PO₄)₂] is reviewed. Such phosphates crystallise in the C2/m space group for M^IV=Ti, Zr, Hf, Ge, Sn, and Mo, and in the P2₁/n space group for BaTh(PO₄)₂. The existence of BaM^IV(PO₄)₂ in which M^IV=Pb, Ce, and U is further evaluated. Several aspects, such as phase transitions in the compounds with yavapaiite structure, solid solutions of BaM^IV(PO₄)₂ compounds and practical applications are briefly discussed.     

Untersuchungen in den Systemen: Zirkonium-Bor-Kohlenstoff und Zirkonium-Bor-Stickstoff

Zusammenfassung Die Dreistoffe: Zr–B–C und Zr–B–N werden auf Grund von heißgepreßten bzw. im Lichtbogen geschmolzenen Proben mittels röntgenographischer Pulveraufnahmen sowie Gefügebeobachtungen untersucht. Die Aufteilung der Phasenfelder ist durch die Kristallarten der Randsysteme gekennzeichnet, d. h. es wird keine ternäre Phase gebildet. Die sehr stabile Diborid-Phase hat einen sehr geringen homogenen Bereich und nimmt praktisch weder Kohlenstoff noch Stickstoff auf. Zweiphasenfelder bestehen bei: Zr–B–C zwischen: ZrB₂–C und ZrB₂–B₄C. Im Falle: Zr–B–N sind die Verhältnisse im Zr-armen Gebiet durch die Felder: ZrB₂–BN und ZrN-Mk–BN unterhalb 1600° C gekennzeichnet. Bei dieser Temperatur reagiert in Übereinstimmung mit einem Befund vonL. Brewer undH. Haraldsen ZrN mit BN zu Diborid und Stickstoff.Die Phase ZrB₁₂ wird als Hochtemperaturphase bestätgt. In Zr-B-Legierungen mit etwa 50 At % B, die bei 1800° C geglüht wurden, tritt die B 1-Struktur mit einem Gitterparameter:a=4,647–4,677 Å auf, der merkwürdigerweise kleiner ist als jener von ZrC. Die meisten Befunde sprechen für eine Zr-reichere Zusammensetzung von ZrB; vor allem aber besteht eine erhebliche Löslichkeit von ZrB in ZrC bzw. ZrN. Man findet, insbesondere bei: Zr–B–N, Gitterparameter, die einen weitgehenden Übergang von ZrN nach ZrB vortäuschen. Die Proben sind jedoch im Mittelgebiet 50 At % Zr, 25 At % B, Rest (C oder N) stets heterogen (-Zr–Mk+ZrB₂+B 1).8 Abbildungen     

Silver-water interactions: Part I. Model of the inner layer at the metal/water interface

Silver-water interactions, as expressed by the surface potential of the water molecules and the modification of the surface potential of the metal, are determined, at the potential of zero charge, as a function of the superficial structure of the electrode by means of the two more significant approaches, that based on the potential of zero charge-work function relation and that using the differential capacity of the inner-layer and its different components. The surface potential of water g^s(dip) is estimated from the inner-layer capacity while the modification of the surface potential of the metal δ_χ^M is obtained from theoretical calculations. The comparison of the [δ_gc^M − g^S(dip)] values with those deduced from the experimental pzc and work function is more than satisfactory. g^S(dip) is proposed to be equal to 0.19, 0.17 and 0.15 V, and −δ_χ^M equal to 0.41, 0.35 and 0.33 V, respectively for the (111), (100) and (110) faces of silver. Consequently, the strength of the silver-water interactions decreases from (111) to (110).The proposition of a large but electrode charge σ-independent capacitance contribution of the metal to the differential capacity of the inner layer Cⁱ is advanced from theoretical estimates and from the quantitative analysis of the Cⁱ(σ) curve for the mercury/water interface. The Cⁱ(σ) curve continues to represent the σ dependence of g^S(dip) as for the model with a σ- and metal-independent δ_χ^M. The basic change is that the capacity at fixed orientation of the water molecules C(ion) can no longer be identified with the minimum value of Cⁱ at high negative σ. A distance of 0.05 nm between the metal and the water molecules is proposed in order to interpret the low value of C(ion) equal to 8 μF cm⁻².The Cⁱ maximum located at the potential of zero charge for the three low-index faces of silver, is attributed to a maximum value of ∂g^S(dip)/∂σ, whatever the value of g^S(dip) for σ = 0 may be. On the other hand, the proposed estimates of the capacitance contribution of silver lead to an identical value of C(ion) and consequently to an identical structure of the inner layer at fixed orientation of the water molecules for the (111) face of silver as for mercury and the other sp metals. The same close-packed arrangement of the metal atoms at the surface of the electrode would be responsible for this identity.     

Separation and quantitation of long-chain free fatty acids in human serum by high-performance liquid chromatography

A rapid, simple and highly sensitive reversed-phase high-performance liquid chromatographic method is described for the separation and quantitation of fatty acids in human serum using a very reactive fluorescent labeling reagent, 9-anthryldiazomethane. Quantitative esterification proceeds at room temperature without heat or catalysis. Baseline separation of nineteen select fatty acids from a standard mixture was achieved on two C18-bonded silica columns connected in tandem using stepwise gradient elution of an acetonitrile-methanol-water mobile phase. The eluent was monitored by a fluorescence detector (maximum excitation wavelength, 365 nm; maximum emission wavelength, 412 nm). The procedure was applied to the analysis of both saturated and unsaturated long-chain free fatty acids (C8 to C22) extracted from human serum. Sera from fasting and non-fasting subjects were analyzed to show the applicability of this assay to biological samples. Detection limit and recovery of free fatty acids in serum were less than 10 pmol/microliter and greater than 92%, respectively.     

Untersuchungen in den Systemen Thorium-Wolfram-Kohlenstoff und Uran-Wolfram-Kohlenstoff

Zusammenfassung Die Dreistoffe Th—W—C und U—W—C werden an Hand gesinterter und lichtbogengeschmolzener Legierungen röntgenographisch und metallographisch untersucht; eine Phasenfelderaufteilung wird vorgenommen. Thorium löst rd. 6 At% C unter Gitteraufweitung (bisa=5,12 Å). Der Bereich von ThC erstreckt sich bei 1500°C von 38 bis 50 At% C (a=5,30 bis 5,34 Å). Im System Th—W—C treten keine ternären Phasen auf; die Gleichgewichte werden durch die Verbindungen der Randsysteme bestimmt. Im System U—W—C wird die schon früher gefundene ternäre Phase UWC₂ und deren Struktur (a=5,633 Å,b=3,255 Å,c=10,98 Å bei der Nominalzusammensetzung) bestätigt. In der Verbindung UWC₂ wird kein merklicher Austausch von Uran gegen Thorium beobachtet; es treten schon bei kleinen Thoriumgehalten Mehrphasengleichgewichte auf. Die Löslichkeitsbereiche sind in beiden Systemen klein. Auf Grund der beobachteten Umsetzungen können unter Vernachlässigung der Beiträge des Metalls Grenzwerte für die freien Bildungsenthalpien von ThC₂ (–32 bis –23,3 kCal/Mol), bzw. UWC₂ (–37,7 bis –41,2 kCal/Mol) errechnet werden.Mit 14 Abbildungen     

Studies of Benzene Adsorption Layers on Silica Gels by Thermal Analysis and McBain Balance Methods

The Q-TG mass loss and first derivative Q-DTG mass loss accompanying benzene thermodesorption from silica gel samples under quasi-isothermal conditions were studied with a Derivatograph Q-1500 D (MOM, Hungary). The isotherms of adsorption-desorption of benzene vapour on different porous silica gels were measured gravimetrically by using a McBain balance. The benzene mass loss in the adsorption region, obtained from the Q-TG curves, and the adsorption capacity, established gravimetrically, exhibited a satisfactory correlation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis, Crystal Structure and Reactivity of Mo4O6(O2)2(μ3-O)2{(μ2-O,μ3-OC8H14}2(OPMePh2)2: A Self-assembled Tetranuclear Cluster Containing Two Peroxide and Two Trans-Cyclooctanediol Ligands*

The reaction of MoO₂Cl₂(OPMePh₂)₂ with t-butylhydroperoxide (TBHP) in the presence of cis-cyclooctene yields the tetrameric complex Mo₄O₆(O₂)₂(μ₃-O)₂{(μ₂-O,μ₃-OC₈H₁₄}₂(OPMePh₂)₂, (1). Additionally in the absence of cis-cyclooctene MoO(O₂)Cl₂(OPMePh₂)₂, MoO(O₂)₂(H₂O)(OPMePh₂), (2), and two novel yellow compounds can be isolated depending on the quantity of TBHP used and the reaction conditions. Both the starting material MoO₂Cl₂(OPMePh₂)₂ and tetramer 1 are capable of accomplishing the epoxidation of cis-cyclooctene as catalysts. The single crystal X-ray determined structures of complexes 1 and 2 are reported.Dedicated to Professor F. A. “Chief” Cotton on the occasion of his 75th birthday     

Predicting sequences and structures of MHC-binding peptides: a computational combinatorial approach

Peptides bound to MHC molecules on the surface of cells convey critical information about the cellular milieu to immune system T cells. Predicting which peptides can bind an MHC molecule, and understanding their modes of binding, are important in order to design better diagnostic and therapeutic agents for infectious and autoimmune diseases. Due to the difficulty of obtaining sufficient experimental binding data for each human MHC molecule, computational modeling of MHC peptide-binding properties is necessary. This paper describes a computational combinatorial design approach to the prediction of peptides that bind an MHC molecule of known X-ray crystallographic or NMR-determined structure. The procedure uses chemical fragments as models for amino acid residues and produces a set of sequences for peptides predicted to bind in the MHC peptide-binding groove. The probabilities for specific amino acids occurring at each position of the peptide are calculated based on these sequences, and these probabilities show a good agreement with amino acid distributions derived from a MHC-binding peptide database. The method also enables prediction of the three-dimensional structure of MHC-peptide complexes. Docking, linking, and optimization procedures were performed with the XPLOR program [1].     

Improved synthesis of functionalized mesogenic 2,6-bisbenzimidazolylpyridine ligands

A versatile one-pot synthetic platform for the preparation of a range of functionalized 2,6-bisbenzimidazolylpyridine (Bip) derivatives is presented. This protocol significantly reduces the cost and time of previous synthetic routes, while facilitating scale up to multi-gram quantities in good yields (63-90%). The previous synthetic methodology was improved through judicious choice of the reducing agent and solvent in the reduction/ring-closing step. Via this platform, we also successfully accessed a mesogenic Bip ligand and herein report initial liquid crystalline properties of this derivative.     

Diffraction of homogeneous and inhomogeneous plane waves on a doubly corrugated liquid/solid interface

This paper extends the theory of the diffraction of sound on 1D corrugated surfaces to 2D corrugated surfaces. Such surfaces, that are egg crate shaped, diffract incoming sound into all polar directions, which is fundamentally different from 1D corrugated surfaces. A theoretical justification is given for extending the classical grating equation to the case of incident inhomogeneous waves, for 1D corrugated surfaces as well as for 2D corrugated surfaces. Even though the present paper presents a theory which is valid for all angles of incidence, special attention is given to the particular case of the stimulation of surface waves by normal incident sound. The most interesting conclusion is that, depending on the frequency and the incident inhomogeneity, Scholte-Stoneley waves and leaky Rayleigh waves can be generated in different directions. This effect might be of particular interest in the development of surface acoustic wave devices and the basic idea of this steering effect can be of importance for planar actuators.