Thermal Restructuring of Silica‐Grafted TiClx Species and Consequences for Epoxidation Catalysis

TiCl₄ grafted to dehydrated silica is an industrially applied catalyst for the epoxidation of propylene. As with many heterogeneous catalysts, the precise nature of the surface species is not yet fully known, prohibiting reliable structure–activity correlations. In this study, the speciation and restructuring of site‐isolated Ti^IV Lewis acid centers was carefully investigated by using a variety of techniques. The initially formed ?SiOTiCl₃ species were found to restructure upon heating through the transfer of Cl ligands to the silica surface, eventually leading to tripodal (?SiO)₃TiCl species. The superior activity and stability of such tripodal species is demonstrated for catalytic olefin epoxidation under continuous flow conditions.     

Brownian Gibbs property for Airy line ensembles

Consider a collection of N Brownian bridges $B_{i}:[-N,N] \to \mathbb{R} $ , B _i (?N)=B _i (N)=0, 1≤i≤N, conditioned not to intersect. The edge-scaling limit of this system is obtained by taking a weak limit as N→∞ of the collection of curves scaled so that the point (0,2^1/2 N) is fixed and space is squeezed, horizontally by a factor of N ^2/3 and vertically by N ^1/3. If a parabola is added to each of the curves of this scaling limit, an x-translation invariant process sometimes called the multi-line Airy process is obtained. We prove the existence of a version of this process (which we call the Airy line ensemble) in which the curves are almost surely everywhere continuous and non-intersecting. This process naturally arises in the study of growth processes and random matrix ensembles, as do related processes with “wanderers” and “outliers”. We formulate our results to treat these relatives as well. Note that the law of the finite collection of Brownian bridges above has the property—called the Brownian Gibbs property—of being invariant under the following action. Select an index 1≤k≤N and erase B _k on a fixed time interval (a,b)?(?N,N); then replace this erased curve with a new curve on (a,b) according to the law of a Brownian bridge between the two existing endpoints (a,B _k (a)) and (b,B _k (b)), conditioned to intersect neither the curve above nor the one below. We show that this property is preserved under the edge-scaling limit and thus establish that the Airy line ensemble has the Brownian Gibbs property. An immediate consequence of the Brownian Gibbs property is a confirmation of the prediction of M. Prähofer and H. Spohn that each line of the Airy line ensemble is locally absolutely continuous with respect to Brownian motion. We also obtain a proof of the long-standing conjecture of K. Johansson that the top line of the Airy line ensemble minus a parabola attains its maximum at a unique point. This establishes the asymptotic law of the transversal fluctuation of last passage percolation with geometric weights. Our probabilistic approach complements the perspective of exactly solvable systems which is often taken in studying the multi-line Airy process, and readily yields several other interesting properties of this process.     

The origin for tubular growth of TiO2 nanotubes: A fluoride rich layer between tube-walls

High resolution Scanning Auger Electron Spectroscopy (AES) is used to demonstrate the compositional variation across self-organized TiO₂ nanotube layers grown in fluoride containing ethylene glycol electrolytes. The analysis results show a distinct fluoride rich layer in between the TiO₂ nanotubes and particularly in the triple points of the hexagonally ordered nanotubular arrays. AES analysis further revealed that extended e-beam exposure leads to a decrease in the fluoride signal (electron beam induced decomposition of fluoride species). The proof of the existence of a fluoride rich layer located between the tube walls strongly supports fluoride dissolution as the reason for a transition from a porous to a tubular morphology.     

A Highly Efficient and Broadly Applicable Cationic Gold Catalyst

Gold catalysts capable of promoting reactions at low‐level loadings under mild conditions are the exception rather than the norm. We examined reactions where the regeneration of cationic gold catalyst (e.g., protodeauration) was the turnover limiting stage. By manipulating electron density on the substituents around phosphorus and introducing steric handles we designed a phosphine ligand that contains two electron‐rich ortho‐biphenyl groups and a cyclohexyl substituent. This ligand formed a gold complex that catalyzed common types of gold‐catalyzed reactions including intra‐ and intermolecular X? H (X=C, N, O) additions to alkynes and cycloisomerizations, with high turnover numbers at room temperature or slightly elevated temperatures (≤50 °C). Our new ligand can be prepared in one step from commercially available starting materials.     

One- and two-phase flow during fluid sampling by a wireline tool

Wireline sampling tools withdraw a few litres of fluid from a permeable formation via a small sink probe pressed against the borehole wall. The aim is to recover, quickly and cheaply, a representative native fluid sample. Unfortunately, the formation in the near wellbore region is invaded by mud filtrate, and withdrawal of nonnative fluid initially is inevitable. It is therefore of interest to estimate the proportion of native fluid in the sample stream, as a function of time.Semi-analytical calculations of one- and two-phase sampling flows are presented, for the special case of constant total fluid mobility in the limits of very deep or very shallow invasion. Both the interaction of the initially cylindrically symmetric invasion profile with the spherically symmetric flow and the capillary shock-forming dynamics of two-phase flow are found to control the character of sample composition variation. The wide variety of sample stream composition histories is displayed.     

Synthesis and lyotropic liquid crystalline behaviour of a taper-shaped phosphonic acid amphiphile

A taper-shaped phosphonic acid, 3,4,5-tris(dodecyloxy)phenylmethylphosphonic acid ( 1 ), was synthesized; its lyotropic liquid crystalline (LLC) behaviour and its ability simultaneously to order and acid-dope polyaniline were examined. It was found that the ability of 1 to form LLC phases in the presence of several hydrophilic solvents is restricted by strong intermolecular interactions between the phosphonic acid head groups (presumably H-bonding). The amphiphile exhibits poor miscibility with pure water and even with strong H-bonding organic solvents such as DMF. However, it forms a lamellar mesophase in the presence of aqueous acid. Upon deprotonation of the phosphonic acid head group with NaOH, the resulting disodium salt of the amphiphile is able to form a well defined lamellar phase with pure water. The propensity of 1 to form lamellar phases is somewhat unusual since its tapered molecular shape should direct it to form an inverted hexagonal LLC phase. These results suggest that intermolecular head group interactions are more important in determining the overall LLC behaviour of this phosphonic acid amphiphile than are the hydrophobic character and shape of the organic tail system. Compound 1 was also found to be sufficiently acidic to act as an acid dopant for the conjugated polymer polyaniline in the emeraldine base form. LLC acid 1 induces the resulting polymeric salt to form an electrically conductive LLC complex with an extended lamellar microstructure. The bulk conductivity of the resulting nanostructured polyaniline salt was found to be only in the semiconducting regime (10 -5 Scm -1 ), due to an unfavourable polyaniline chain conformation in the LLC complex.     

Laser dye DCM,its spectral properties,synthesis and comparison with other dyes in the red

4-Dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (DCM) in dimethyl sulfoxide has a broad tuning range and is most efficient dye yet reported for the 630–680 nm region.     

Copper and native defects in zinc telluride

Zinc telluride crystals were grown from tellurium-rich solutions containing 10¹⁷–10²⁰ cm^?3 atoms of copper. The copper concentrations in these crystals were measured by activation analysis. Hall effect and resistivity measurements were performed. Photoluminescence spectra were also determined. Our interpretation of the different results is that copper brings about both acceptor defects Cu_Zn with a 0·12–0·13 eV ionization energy, and donor defects. The second acceptor level of the zinc vacancy was found to be at 0·15 eV.