Trimethylsilylcyclopentadienylchromium(III) complexes with diphenyl-2-pyridylphosphine: synthesis, structural characterisation and catalytic behaviour of [(C6H5)2PC5H4NH][(η-Me3SiCp)CrCl3]

Reaction of CrCl₃ with LiCpSiMe₃ in THF leads to the formation of a solvated intermediate, [(η⁵-Me₃SiCp)CrCl₂(THF)], which in turn reacts with diphenyl-2-pyridylphosphine to yield the complex [(C₆H₅)₂PC₅H₄NH][(η⁵-Me₃SiCp)CrCl₃] (1) in 66% yield. As a secondary product was isolated the neutral complex [(η⁵-Me₃SiCp)CrCl₂{(C₆H₅)₂PC₅H₄N}] (2) in 5% yield. The structure of complex 1 has been determined by single crystal X-ray diffraction. In the anion the metal centre shows a pseudo-octahedral geometry with the centroid of the trimethylsilylcyclopentadienyl ligand occupying the centre of three octahedral sites, and three chloride atoms completing the co-ordination sphere. Complex 1 in the presence of MAO leads to the formation of an active catalyst for the polymerization of ethylene.     

Salt‐Induced Depression of Lower Critical Solution Temperature in a Surface‐Grafted Neutral Thermoresponsive Polymer

Summary: Quartz crystal microbalance with dissipation monitoring (QCM‐D) is employed to determine the effect of salt on the volume phase transition of thermoresponsive polymer brushes. Changes in mass and viscoelasticity of poly(N‐isopropylacrylamide) (PNIPAM) layers grafted from a QCM‐D crystal are measured as a function of temperature, upon contact with aqueous solutions of varying salt concentrations. The phase‐transition temperature of PNIPAM brushes, T_C,graft, quantified from the QCM‐D measurements is found to decrease as the concentration of salt is increased. This phenomenon is explained by the tendency of salt ions to affect the structure of water molecules (Hofmeister effect). However, in contrast to the linear decrease in phase‐transition temperature upon increasing salt concentration observed for free PNIPAM, the trend in T_C,graft for PNIPAM brushes is distinctively non‐linear.

Schematic representation of the effect of salt concentration on the phase transition behavior of thermoresponsive polymer brushes.     

Separation and Preconcentration by Dispersive Liquid�CLiquid Microextraction Procedure: Recent Applications

Dispersive liquid?Cliquid microextraction (DLLME) is a relatively novel miniaturized sample pre-treatment technique. DLLME has been applied for the analysis of a large variety of organic compounds and metal ions in different samples. This paper reviews the more recent applications of this procedure for sample preparation.     

New Triterpenoid and Ergostane Glycosides from the Leaves of Hydrocotyle umbellata L.

Two new triterpenoid glycosides, together with two new ergostane glycosides, umbellatosides A–D ( 1 – 4 , resp.), have been isolated from the leaves of Hydrocotyle umbellata L. Their structures were established by 2D‐NMR spectroscopic techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3β,22β‐dihydroxy‐3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]olean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]oleanolic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 2 ), (3β,11α,26)‐ergosta‐5,24(28)‐diene‐3,11,26‐triol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 3 ), and (3β,11α,21,26)‐ergosta‐5,24(28)‐diene‐3,11,21,26‐tetrol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 4 ).     

Chemogenomic discovery of allosteric antagonists at the GPRC6A receptor

GPRC6A is a Family C G protein-coupled receptor recently discovered and deorphanized by our group. This study integrates chemogenomic ligand inference, homology modeling, compound synthesis, and pharmacological mechanism-of-action studies to disclose two noticeable results of methodological and pharmacological character: (1) chemogenomic lead identification through the first, to our knowledge, ligand inference between two different GPCR families, Families A and C; and (2) the discovery of the most selective GPRC6A allosteric antagonists discovered to date. The unprecedented inference of?pharmacological activity across GPCR families provides proof-of-concept for in?silico approaches against Family C targets based on Family A templates, greatly expanding the prospects of successful drug design and discovery. The antagonists were tested against a panel of seven Family A and C G protein-coupled receptors containing the chemogenomic binding sequence motif where some of the identified GPRC6A antagonists showed some activity. However, three compounds with at least ～3-fold selectivity for GPRC6A were discovered, which present a significant step forward compared with the previously published GPRC6A antagonists, calindol and NPS 2143, which both display ～30-fold selectivity for the calcium-sensing receptor compared to GPRC6A. The antagonists constitute novel research tools toward investigating the signaling mechanism of the GPRC6A receptor at the cellular level and serve as initial ligands for further optimization of potency and selectivity enabling future ex?vivo/in?vivo pharmacological studies.     

Structural characterization and oxidative dehydrogenation activity of V2O5/Ce(x)Zr(1-x)O2/SiO2 catalysts

The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations.     

Short-range interactions between non-ionic surfactant layers

Short-range interactions between surfactant and lipid layers are of great importance in technical applications in complex fluids such as foams, dispersions and emulsions, as well as in the formulation and performance of dispersants, detergents and flocculants. It is also of utmost importance in biological systems where interactions between biomembranes influence a range of processes. The field of short-range interactions has been thoroughly investigated during the past 30 years, following the emergence of a number of techniques to measure interaction forces. Thus, our understanding has increased considerably and it is timely to summarize relevant knowledge accumulated in this area. In this review we focus on the nature of short-range interactions between non-ionic and zwitterionic surfactant and lipid layers exposing their polar groups to the surrounding medium. We discuss the complex interplay of short-range (van der Waals, hydration, steric and other) forces based on recent theoretical and experimental results.     

Chromium(III) complexes with terdentate 2,6-bis(azolylmethyl)pyridine ligands: Synthesis, structures and ethylene polymerization behavior

Reactions of 2,6-bis(bromomethyl)pyridine with 3,5-dimethylpyrazole and 1H-indazole yield the terdentate ligands 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (5) and 2,6-bis(indazol-2-ylmethyl)pyridine (6). The molecular structure of the new compound 6 was determined by single-crystal X-ray diffraction. These ligands react with the CrCl₃(THF)₃ complex in THF to form neutral complexes of general formula [CrCl₃{2,6-bis(azolylmethyl)pyridine-N,N,N}] (7, 8) which are isolated in high yields as stable green solids and characterized by means of elemental analysis, magnetic moments, IR, and mass spectroscopy. Theoretical calculations predict that the thermodynamically preferred structure of the complexes is the fac configuration. After reaction with methylaluminoxane (MAO) the chromium(III) complexes are active in the polymerization of ethylene.     

Enzymatic hydrolysis of native cellulose nanofibrils and other cellulose model films: effect of surface structure

Model films of native cellulose nanofibrils, which contain both crystalline cellulose I and amorphous domains, were used to investigate the dynamics and activities of cellulase enzymes. The enzyme binding and degradation of nanofibril films were compared with those for other films of cellulose, namely, Langmuir-Schaefer and spin-coated regenerated cellulose, as well as cellulose nanocrystal cast films. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency and energy dissipation during incubation at varying enzyme concentrations and experimental temperatures. Structural and morphological changes of the cellulose films upon incubation with enzymes were evaluated by using atomic force microscopy. The QCM-D results revealed that the rate of enzymatic degradation of the nanofibril films was much faster compared to the other types of cellulosic films. Higher enzyme loads did not dramatically increase the already fast degradation rate. Real-time measurements of the coupled contributions of enzyme binding and hydrolytic reactions were fitted to an empirical model that closely described the cellulase activities. The hydrolytic potential of the cellulase mixture was found to be considerably affected by the nature of the substrates, especially their crystallinity and morphology. The implications of these observations are discussed in this report.     

Thermodynamic study of the three isomers of bromo and iodobenzoic acids. Part II

Using our technique of combustion of small amount of a substance, we determined by calorimetry the standard molar enthalpy of formation in the condensed state and atT=298.15 K of the three isomers of bromo and iodobenzoic acids. Associating to these values their standard molar enthalpies of sublimation previously measured, it was possible to determine their standard molar enthalpies of formation in the gaseous state and atT=298.15 K. The experimental values of the thermodynamic properties _f H _m ^o (cr, 298.15 K), _f H _m ^o (cr, 298.15 K), _sub H _m ^o (298.15 K), and _f H _m ^o (g, 298.15 K) are given for the two series. From the experimental value of the standard molar enthalpy of atomization, it was possible to determine an enthalpy value for the C_b-Br and C_b-I bonds. The experimental and theoretical values of the resonance energy of bromo and iodobenzoic acids are compatible. The relative stability of some monosubstituted derivatives of benzoic acid studied in our laboratory is also discussed.Part I is concerned with Ref. 22 (for bromobenzoic acids) and with Ref. 23 (for iodobenzoic acids).