Low‐temperature sol–gel transformation of methyl silicon precursors to silica‐based hybrid materials

Six new methyl silicon (IV) precursors of the type [MeSi{ON?C(R)Ar}₃] [when R = Me, Ar = 2‐C₅H₄N ( 1 ), 2‐C₄H₃O ( 2 ) or 2‐C₄H₃S ( 3 ); and when R = H, Ar = 2‐C₅H₄N ( 4 ), 2‐C₄H₃O ( 5 ) or 2‐C₄H₃S ( 6 )] were prepared and structurally characterized by various spectroscopic techniques. Molecular weight measurements and FAB (Fast Atomic Bombardment) mass spectral studies indicated their monomeric nature. ¹H and ¹³C{¹H} NMR spectral studies suggested the oximate ligands to be monodentate in solution, which was confirmed by ²⁹Si{¹H} NMR signals in the region expected for tetra‐coordinated methylsilicon (IV) derivatives. Thermogravimetric analysis of 1 revealed the complex to be thermally labile, decomposing to a hybrid material of definite composition. Two representative compounds ( 2 and 4 ) were studied as single source molecular precursor for low‐temperature transformation to silica‐based hybrid materials using sol–gel technique. Formation of homogenous methyl‐bonded silica materials (MeSiO_3/2) at low sintering temperature was observed. The thermogravimetric analysis of the methylsilica material indicated that silicon‐methyl bond is thermally stable up to a temperature of 400 °C. Reaction of 2 and Al(OPrⁱ)₃ in equimolar ratio in anhydrous toluene yielded a brown‐colored viscous liquid of the composition [MeSi{ON?C(CH₃)C₄H₃O}₃.Al(OPrⁱ)₃]. Spectroscopic techniques ¹H, ¹³C{¹H}, ²⁷Al{¹H} and ²⁹Si{¹H} NMR spectra of the viscous product indicated the presence of tetracoordination around both silicon and aluminum atoms. On hydrolysis it yielded methylated aluminosilicate material with high specific surface area (464 m²/g). Scanning electron micrography confirmed a regular porous structure with porosity in the nanometric range. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of structural and morphological factors on the mechanical properties of the polyethylenes

Force-length relations at ambient temperature have been determined for a set of polyethylenes which represent a wide range in molecular weight and molecular constitution. Taking advantage of previous work from this laboratory, samples have been prepared in such a manner that the important independent structural variables can be identified and isolated and their influence on the different aspects of the deformation process assessed. Partial melting-recrystallization processes appear to play an important role. For the linear polymers there is a direct influence of molecular weight. The influence of molecular weight manifests itself in the structure of the interlamellar zone which has a major influence on the initial modulus as well as the ultimate properties. Copolymers and branched copolymers display quite different behavior. The most striking difference is the invariance of the ultimate properties with molecular weight, branching, and level of crystallinity. From the set of experimental results that are presented the molecular factors involved in the deformation process can be sorted out. It becomes quite evident that all of the basic structural regions, characteristic of semicrystalline polymers, contribute to the observations. Focus solely on the changes in the crystallite, in analogy to the deformation of small-molecule crystalline systems, is inadequate in the case of crystalline polymers.     

Exact potential minimization for a supergravity model

The low energy effective scalar potential arising from the supergravity model proposed by Nilles, Srednicki and Wyler is minimized exactly. Bounds are derived for the parameters of the theory from the requirement that SU(2) × U(1) be broken at the tree level. These results support earlier approximate results.     

String dynamics near a black hole

The dynamics of a string near a Kaluza-Klein black hole are studied. Solutions to the geodesic equations are obtained using the world sheet velocity of light as an expansion parameter. For a string falling into a magnetically charged black hole, it is shown that the compact dimension decreases with the world-sheet coordinate τ.     

Tight focusing of linearly and circularly polarized vortex beams; effect of third-order spherical aberration

Tight focusing of linearly and circularly polarized vortex beams is studied in the presence of third-order spherical aberration, using vectorial Debye–Wolf integral. Results for total intensity distribution are presented for both polarizations. In addition, results for x-, y-, and z-polarization components are presented for the circularly polarized beam. Generation of longitudinal optical vortex in the tightly focused left circularly polarized beam has also been demonstrated by plotting its phase distribution. Compensation for the effect of spherical aberration has been studied in the presence of defocusing. Effect of aberration on the dark core of a tightly focused azimuthally polarized beam is also investigated.     

Characteristic polynomials of linear polyacenes and their subspectrality

Coefficients of characteristic polynomials (CP) of linear polyacenes (LP) have been shown to be obtainable from Pascal’s triangle by using a graph factorisation and squaring technique. Strong subspectrality existing among the members of the linear polyacene series has been shown from the derivation of the CP’s. Thus it has been shown that the entire eigenspectrum of ann-ring LP is included in that of (2n + 1)-ring LP. Correspondence between the eigenspectra of linear chains and LP’s is brought out by a recently developed vertex-alternation and squaring algorithm.     

Total synthesis of a unique tetrasaccharide present in the human clotting factor IX and mammalian Notch 1 receptor

The synthesis of a unique tetrasaccharide linked to the serine 61 of human clotting factor IX through an α-l-fucose residue has been achieved for the first time in excellent yield. All glycosylation and protecting group manipulation steps are high yielding and reproducible for a scale-up preparation. A sequential glycosylation strategy has been used to assemble suitably protected monosaccharide synthons for the preparation of the target tetrasaccharide.     

Influence of projectile breakup on complete fusion

Complete fusion excitation functions for ^11,10B+¹⁵⁹Tb and ^6,7Li+¹⁵⁹Tb have been reported at energies around the respective Coulomb barriers. The measurements show significant suppression of complete fusion cross-sections at energies above the barrier for ¹⁰B+¹⁵⁹Tb and ^6,7Li+¹⁵⁹Tb reactions, when compared to those for ¹¹B+¹⁵⁹Tb. The comparison shows that the extent of suppression of complete fusion cross-sections is correlated with the α-separation energies of the projectiles. Also, the measured incomplete fusion cross-sections show that the α-particle emanating channel is the favoured incomplete fusion process. Inclusive measurement of the α-particles produced in ⁶Li+¹⁵⁹Tb reaction has been carried out. Preliminary CDCC calculations carried out to estimate the α-yield following ⁶Li breaking up into α+d fail to explain the measured α-yield. Transfer processes seem to be important contributors.