Diffusion of aromatic hydrocarbons in silicalite/HZSM-5

Diffusion of benzene and the xylene isomers in silicalite/HZSM-5 has been studied by a wide range of different experimental techniques. The available data are reviewed in an attempt to draw general conclusions concerning the intracrystalline diffusion process. The results for benzene are remarkably consistent, and the conformity between transport and tracer diffusion and between single crystal membrane and ZLC and frequency response data suggests that diffusion is essentially isotropic with no significant difference between the self and “corrected” transport diffusivity. The situation is more complex for p-xylene which shows clear evidence of non-isotropic behavior and a significant difference between tracer and transport diffusivities.     

New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Sorption kinetics: measurement of surface resistance

Adsorption - The problem of measuring sorption kinetics in microporous adsorbents and distinguishing experimentally between surface resistance and internal diffusion is discussed and reviewed with...     

Ultrahigh-sensitivity fiber-optic strain and temperature sensor

We report ultrahigh-sensitivity static strain sensing (noise equivalent strain 相似文献   

Differential scanning calorimetry and Fourier transform infrared spectroscopic studies of phospholipid organization and lipid-peptide interactions in nanoporous substrate-supported lipid model membranes

High-sensitivity differential scanning calorimetry was utilized to examine whether lipids capable of forming an inverted nonlamellar hexagonal II (HII) phase can be deposited into nanoporous substrate-supported arrays. Particularly, we compare the thermotropic phase properties of nanoconfined unsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine lipid bilayers with unsupported dispersions to assess nanoconfinement effects, focusing on the lamellar fluid (Lalpha) to HII phase transition. Experimental results provide direct and clear evidence for the formation of an HII phase upon both heating and cooling. However, a small shift in the Lalpha/HII phase transition temperature, as well as an increase in the magnitude of the associated temperature hysteresis, was observed in the nanoporous substrate-supported system. Additionally, nanoconfinement effects on the interaction and location of the antimicrobial peptide gramicidin S (GS) with nanoporous substrate-supported cardiolipin bilayers were examined by Fourier transform infrared spectroscopy as a function of temperature and phospholipid phase state. Upon heating, GS molecules began to insert into nanoconfined, substrate-supported cardiolipin bilayers at lower temperatures relative to the gel/liquid-crystalline phase transition temperature than into unsupported bilayers. The reduction in the polarity and hydrogen-bonding potential environment of GS in the Lalpha state suggests that GS is located at the polar/apolar interfacial region in both supported and unsupported cardiolipin bilayers and that the capacity of GS to interact with nanoporous substrate-supported cardiolipin bilayers was not significantly hindered by nanoconfinement. These studies further demonstrate the usefulness of supported lipid bilayers inside nanoporous substrates.     

The didactical tetrahedron as a heuristic for analysing the incorporation of digital technologies into classroom practice in support of investigative approaches to teaching mathematics

There have been various proposals to expand the heuristic device of the didactical triangle to form a didactical tetrahedron by adding a fourth vertex to acknowledge the significant role of technology in mediating relations between content, student and teacher. Under such a heuristic, the technology vertex can be interpreted at several levels from that of the material resources present in the classroom to that of the fundamental machinery of schooling itself. At the first level, recent research into teacher thinking and teaching practice involving use of digital technologies indicates that, while many teachers see particular tools and resources as supporting the classroom viability of investigative approaches to mathematics, the practical expressions of this idea in lessons vary in the degree of emphasis they give to a didactic of reconstruction of knowledge, as against reproduction. At the final level, examining key structuring features of teaching practice makes clear the scope and scale of the situational adaptation and professional learning required for teachers to successfully incorporate use of digital tools and resources in support of investigative approaches. These issues are illustrated through examining contrasting cases of classroom use of dynamic geometry in professionally well-regarded mathematics departments in English secondary schools.