Asymmetric reactions of organosilicon compounds and properties of novel optically active organosilanes

Partial reduction of racemic methoxysilanes by 1:1 complexes of lithium aluminium hydride with optically active cinchona and ephedra alkaloids give optically active silanes and methoxysilanes. Optical yields depend on the groups attached to silicon and the alkaloid used but in some cases approach 50%, The method has been used to prepare novel optically active organosilanes, possessing an asymmetric silicon centre, which are either inaccessible by any of the other available routes or would require a time consuming preparation. Such compounds are of use in the study of the mechanism of substitutions at silicon. Attempts have been made to rationalize the results of the asymmetric reductions in terms of differences in sterio and electronic interactions in diastereoisomeric transition states. Circular dichroism and optical rotatory dispersion spectra have been obtained for the optically active products in an attempt to elucidate the absolute configurations of the novel asymmetric organosilanes. The results from these studies provide a useful addition to the data so far accumulated for asymmetrically perturbed aromatic chromophores. Nuclear magnetic resonanoe studies of diastereoisomaric (-)-menthoxysilanes show that these compounds possess resonances extremely useful in the determination of optical purities for asymmetric organosilanes which possess an aromatic group. The effect of variable temperature on the spectra has revealed evidence for the conformational preferences in these compounds. Other diastereoisomeric alkoxysilanes have been prepared and their n.m.r.spectra studied in the hope of establishing trends. Exploratory studies for other asymmetric reactions proceeding at silicon have proved unfruitful.

Design of FBG-based ultra-narrow asymmetric filter for transmission with 0.8 bit/s/Hz spectral efficiency without polarisation multiplexing

We propose a novel approach to ultra-narrow optical filtering based on a specially designed slightly asymmetric filter, which can be fabricated using fibre Bragg gratings. A feasibility of 8×40 Gbit/s DWDM RZ transmission with 0.8 bit/s/Hz spectral efficiency (without polarisation multiplexing) over 1280 km of SMF/DCF link without FEC has been confirmed by numerical modelling. © 2004 Elsevier Inc. All rights reserved.

Mesoporous silicas as versatile supports to tune the palladium-catalyzed selective aerobic oxidation of allylic alcohols

Surfactant templating offers a simple route to synthesize high-surface area silicas with ordered, tunable mesopore architectures. The use of these materials as versatile catalyst supports for palladium nanoparticles has been explored in the aerobic selective oxidation (selox) of allylic alcohols under mild conditions. Families of Pd/mesoporous silicas, synthesized through incipient wetness impregnation of SBA-15, SBA-16, and KIT-6, have been characterized by using nitrogen porosimetry, CO chemisorption, diffuse reflection infrared Fourier transform spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and high-resolution TEM and benchmarked in liquid phase allylic alcohol selox against a Pd/amorphous SiO2 standard. The transition from amorphous to two-dimensional parallel and three-dimensional interpenetrating porous silica networks conferred significant selox rate enhancements associated with higher surface densities of active palladium oxide sites. Dissolved oxygen was essential for insitu stabilization of palladium oxide, and thus maintenance of high activity on-stream, whereas selectivity to the desired aldehyde selox product over competing hydrogenolysis pathways was directed by using palladium metal. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

Hierarchically ordered nanoporous Pd/SBA-15 catalyst for the aerobic selective oxidation of sterically challenging allylic alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol. © 2013 American Chemical Society.

Visual performance of a new bi-aspheric, segmented, asymmetric multifocal IOL

PURPOSE: To assess the visual performance and subjective experience of eyes implanted with a new bi-aspheric, segmented, multifocal intraocular lens: the Mplus X (Topcon Europe Medical, Capelle aan den IJssel, Netherlands). METHODS: Seventeen patients (mean age: 64.0 ± 12.8 years) had binocular implantation (34 eyes) with the Mplus X. Three months after the implantation, assessment was made of: manifest refraction; uncorrected and corrected distance visual acuity; uncorrected and distance corrected near visual acuity; defocus curves in photopic conditions; contrast sensitivity; halometry as an objective measure of glare; and patient satisfaction with unaided near vision using the Near Acuity Visual Questionnaire. RESULTS: Mean residual manifest refraction was -0.13 ± 0.51 diopters (D). Twenty-five eyes (74%) were within a mean spherical equivalent of ±0.50 D. Mean uncorrected distance visual acuity was +0.10 ± 0.12 logMAR monocularly and 0.02 ± 0.09 logMAR binocularly. Thirty-two eyes (94%) could read 0.3 or better without any reading correction and all patients could read 0.3 or better with a reading correction. Mean monocular uncorrected near visual acuity was 0.18 ± 0.16 logMAR, improving to 0.15 ± 0.15 logMAR with distance correction. Mean binocular uncorrected near visual acuity was 0.11 ± 0.11 logMAR, improving to 0.09 ± 0.12 logMAR with distance correction. Mean binocular contrast sensitivity was 1.75 ± 0.14 log units at 3 cycles per degree, 1.88 ± 0.20 log units at 6 cycles per degree, 1.66 ± 0.19 log units at 12 cycles per degree, and 1.11 ± 0.20 log units at 18 cycles per degree. Mean binocular and monocular halometry showed a glare profile of less than 1° of debilitating light scatter. Mean Near Acuity Visual Questionnaire Rasch score (0 = no difficulty, 100 = extreme difficulty) for satisfaction for near vision was 20.43 ± 14.64 log-odd units. CONCLUSIONS: The Mplus X provides a good visual outcome at distance and near with minimal dysphotopsia. Patients were very satisfied with their uncorrected near vision. © SLACK Incorporated.

High-activity, single-site mesoporous Pd/Al2O3 catalysts for selective aerobic oxidation of allylic alcohols

Pd does it alone : Tailored heterogeneous catalysts offer exciting, alternative, clean technologies for regioselective molecular transformations. A mesoporous alumina support stabilizes atomically dispersed PdII surface sites (see picture, C light gray, O red, Pd dark gray, Al purple, H white), thereby dramatically enhancing catalytic performance in the aerobic selective oxidation of alcohols.

Covalent attachment of chiral manganese(III) salen complexes onto functionalised hexagonal mesoporous silica and application to the asymmetric epoxidation of alkenes

Two modified Jacobsen-type catalysts were anchored onto an amine functionalised hexagonal mesoporous silica (HMS) using two distinct anchoring procedures: (i) one was anchored directly through the carboxylic acid functionalised diimine bridge fragment of the complex (CAT1) and (ii) the other through the hydroxyl group on the aldehyde fragment of the complex (CAT2), mediated by cyanuric chloride. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, DRIFT, UV-vis, porosimetry and XPS which showed that the complexes were successfully anchored onto the hexagonal mesoporous silica. These materials acted as active heterogeneous catalysts in the epoxidation of styrene, using m-CPBA as oxidant, and α-methylstyrene, using NaOCl as oxidant. Under the latter conditions they acted also as enantioselective heterogeneous catalysts. Furthermore, when compared to the reaction run in homogeneous phase under similar experimental conditions, an increase in asymmetric induction was observed for the heterogenised CAT1, while the opposite effect was observed for the heterogenised CAT2, despite of CAT2 being more enantioselective than CAT1 in homogeneous phase. These results indicate that the covalent attachment of the Jacobsen catalyst through the diimine bridge leads to improved enantiomeric excess (%ee), whereas covalent attachment through one of the aldehyde fragments results in a negative effect in the %ee. Using α-methylstyrene and NaOCl as oxidant, heterogeneous catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier Inc. All rights reserved.

Asymmetric epoxidation of alkenes by a chiral manganese(III) salen complex anchored onto a functionalised hexagonal mesoporous silica

A Jacobsen-type catalyst was anchored onto an amine functionalised hexagonal mesoporous silica (HMS) through the diimine bridge fragment of the complex. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, FTIR-DRIFT, UV-vis, porosimetry and XPS which showed that the complex was successfully anchored. This material was active in the epoxidation of styrene and α-methylstyrene in dichloromethane at 0°C using, respectively, m-CPBA/NMO and NaOCl. With the former substrate no asymmetric induction was found in the epoxide, whereas with the latter substrate higher %ee was found than in homogeneous phase. Using the latter experimental conditions, catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier B.V. All rights reserved.

Optimal duty cycle and asymmetric VSB filtering in a wavelength allocated DWDM CS-RZ transmission

Impact of duty cycle on the optimisation of ultra-narrow VSB filtering in wavelength allocated CS-RZ Nx40Gbit/s DWDM transmission is investigated. A feasibility has been confirmed of over 600 km with 0.64 bit/s/Hz spectral efficiency.

Performance enhancement of asymmetric filtered 40 Gb/s carrier suppressed return to zero-differential phase shift keying receiver in a 50 GHz grid

The authors present the impact of asymmetric filtering of strong (e.g. 35 GHz) optical filters on the performance of 42.7 Gb/s 67% (carrier suppressed return to zero)-differential phase shift keying systems. The performance is examined (in an amplified spontaneous emission (ASE) noise-limited regime and in the presence of chromatic dispersion) when offsetting the filter at the receiver by substantial amounts via balanced, constructive and destructive single-ended detections. It is found that with a slight offset (vestigial side band) or an offset of almost half of the modulation frequency (single-side band), there is a significant improvement in the calculated 'Q'. © The Institution of Engineering and Technology 2013.

Asymmetric Cipher Protocol Using Decomposition Problem

The asymmetric cipher protocol based on decomposition problem in matrix semiring M over semiring of natural numbers N is presented. The security parameters are defined and preliminary security analysis is presented.

Symmetric and Asymmetric Gaps in Some Fields of Formal Power Series

2000 Mathematics Subject Classification: 03E04, 12J15, 12J25.

Performance evaluation of strongly filtered asymmetric 42.7 Gb/s coherent 50%RZ-BPSK system

We show, by numerical simulation, that the impact of tight optical filtering in high speed coherent 50% RZ-BPSK systems can be greatly reduced by offsetting the filter (equivalent to laser detuning). We show that by offsetting the filter by up to half the filter bandwidth, that system performance is improved by > 2.5 dB in the calculated 'Q' for an OSNR of 12 dB. © 2013 IEEE.