Ligand differentiated complementary Rh-catalyst systems for the enantioselective desymmetrization of meso-cyclic anhydrides

Two distinct systems for the rhodium-catalyzed enantioselective desymmetrization of meso-cyclic anhydrides have been developed. Each system has been optimized and are compatible with the use of in situ prepared organozinc reagents. Rhodium/PHOX species efficiently catalyze the addition of alkyl nucleophiles to glutaric anhydrides, while a rhodium/phosphoramidite system is effective in the enantioselective arylation of succinic and glutaric anhydrides.

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c(3) reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c(3) as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c(3) required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c(3). The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and-for sufficiently high values of c(3)-there is a reversible polymer-gel transformation at a density-dependent floor temperature. (C) 2002 American Institute of Physics.

Electrochemical ammonia gas sensing in nonaqueous systems: A comparison of propylene carbonate with room temperature ffonc liquids

First, the direct and indirect electrochemical oxidation of ammonia has been studied by cyclic voltammetry at glassy carbon electrodes in propylene carbonate. In the case of the indirect oxidation of ammonia, its analytical utility of indirect for ammonia sensing was examined in the range from 10 and 100 ppm by measuring the peak current of new wave resulting from reaction between ammonia and hydroquinone, as function of ammonia concentration, giving a sensitivity 1.29 x 10(-7) A ppm(-1) (r(2)=0.999) and limit-of-detection 5 ppm ammonia. Further, the direct oxidation of ammonia has been investigated in several room temperature ionic liquids (RTILs), namely 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim] [BF4]), 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim] [OTf]), 1-Ethyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim] [NTf2]), 1-butyl-3-methylimidazolium bis(tritluoromethylsulfonyl)imide ([C4mim] [NTf2]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim] [PF6]) on a 10 put diameter Pt microdisk electrode. In four of the RTILs studied, the cyclic voltammetric analysis suggests that ammonia is initially oxidized to nitrogen, N-2, and protons, which are transferred to an ammonia molecule, forming NH4+ via the protonation of the anion(s) (A(-)). However, in [C4mim] [PF6], the protonated anion was formed first, followed by NH4+. In all five RTILs, both HA and NH4+ are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The analytical ability of this work has also been explored further, giving a limit-of-detection close to 50 ppm in [C(2)mim] [NTf2], [C(4)mim] [OTf], [C(4)mim] [BF4], with a sensitivity of ca. 6 x 10(-7) A ppm(-1) (r(2) = 0.999) for all three ionic liquids, showing that the limit of detection was ca. ten times larger than that in propylene carbonate since ammonia in propylene carbonate might be more soluble in comparison with RTILs when considering the higher viscosity of RTILs.

Extended electrochemical windows made accessible by room temperature ionic liquid/organic solvent electrolyte systems

The electrochemical windows of acetonitrile solutions doped with 0.1 m concentrations of several ionic liquids were examined by cyclic voltammetry at gold and platinum microelectrodes. These results were compared with those observed in the commonly used 0.1 m tetrabutylammonium perchlorate/acetonitrile system as well as with neat ionic liquids. The use of a trifluorotris(pentofluoroethyl)phosphate-based ionic liquid, specifically, as supporting electrolyte in acetonitrile solutions affords a wider anodic window, which is attributed to the high stability of the anionic component of these intrinsically conductive and thermally robust compounds.

Metal-Directed Synthesis of Enantiomerially Pure Dimetallic Lanthanide Luminescent Triple-Stranded Helicates

The synthesis and photophysical evaluation of two enatiomerially pure dimetallic lanthanide luminescent triple-stranded helicates is described. The two systems, formed from the chiral (R,R) ligand 1 and (S,S) ligand 2, were produced as single species in solution, where the excitation of either the naphthalene antennae or the pyridiyl units gave rise to Eu(III) emission in a variety of solvents. Excitation of the antennae also gave rise to circularly polarized Eu(III) luminescence emissions for Eu2:13 and Eu2:23 that were of equal intensity and opposite sign, confirming their enantiomeric nature in solution providing a basis upon which we were able to assign the absolute configurations of Eu2:13 and Eu2:23.

Study of the transamidative ring expansion of N--halogenoalkyl--lactams of alkyl chain lengths 2–12 in liquid ammonia and other liquid amines: syntheses of 7-, 8- and 9-membered 1,5-diaza cyclic ketones, including routes to (±)-dihydroperiphylline and (±)-celabenzine

N-(3-Halogenopropyl)-4-phenylazetidin-2-ones undergo amination in liquid ammonia followed by transamidative ring expansion to give the eight-membered 4-phenyl -1,5-diazacyclooctan-2-one in excellent yield. Ring expansion of the amines in liquid ammonia is found to be much more effective than in hydrocarbon solvents. Formation of 7-, 8-, and 9-membered azalactams from the requisite -halogenoalkyl--lactams is an excellent synthetic process, though it is not applicable to 10membered rings. In the cases of rings of 13-, 15- and 17-members, although amination and apparent expansion takes place, the large rings appear not to be stable to ammonia and the final products are acyclic amides. N-[4-Halogenobut-2(Z)-enyl]-4-phenylazetidin-2-one satisfactorily forms a 9-membered (Z)-olefinic azalactam, but the (E)-isomer gives an acyclic amino amide. By using alkyl-substituted -lactam side-chains, C-substituted medium rings can be obtained; the relative instability of N-acyl -lactams to ammonia, however, leads to acylamino amides rather than expanded rings.Employing ethylamine in place of ammonia, it is shown that N-ethylated azalactams are formed satisfactorily, and using allylamine, N-allyl medium rings capable of further elaboration are obtained. The chemistry of these systems is discussed. Using transamidation in liquid ammonia, a short synthesis of the 9-membered spermidine alkaloid (±)-dihydroperiphylline is reported. Synthesis of key intermediates, whose transformation into the 13-membered alkaloids of the celabenzine group has already been effected, has been carried out.X-Ray single-crystal structure determinations for 4-phenyl-1,5-diazacyclononan-2-one, trans-4-phenyl-8-methyl-1,5-diazacyclooctan-2-one and (Z)-4-phenyl-1,5-diazacyclonon-7-en-2-one are reported, and comment is made on certain conformational features.

Berry phase in open quantum systems: a quantum Langevin equation approach

The evolution of a two level system with a slowly varying Hamiltonian, modeled as a spin 1/2 in a slowly varying magnetic field, and interacting with a quantum environment, modeled as a bath of harmonic oscillators is analyzed using a quantum Langevin approach. This allows to easily obtain the dissipation time and the correction to the Berry phase in the case of an adiabatic cyclic evolution.

Fatigue behavior of laser-welded NiTi wires in small-strain cyclic bending

NiTi wires and their weldments are commonly used in micro-electro-mechanical systems (MEMS), and in such applications, cyclic loading are commonly encountered. In this paper, the bending-rotation fatigue (BRF) test was used to study the bending fatigue behavior of NiTi wire laser weldment in the small-strain regime. The fracture mechanism, which includes crack initiation, crack growth and propagation of the weldment in the BRF test, was investigated with the aid of SEM fractography and discussed in terms of the microstructure. It was found that crack initiation was primarily surface-condition dependent. The cracks were found to initiate at the surface defects at the weld zone (WZ) surface, and the crack propagation was assisted by the gas inclusions in the WZ. The weldment was finally fractured in a ductile manner. The fatigue life was found to decrease with increasing surface strain and also with increasing bending frequency (controlled by the rotational speed in the BRF test). In comparison, the fatigue life of the unwelded NiTi wires was higher than their welded counterparts at all strain levels and bending frequencies. The decrease in fatigue resistance of the weldment could be attributed to the surface and microstructural defects introduced during laser welding.

Full-Duplex Spectrum Sharing in Cooperative Single Carrier Systems

In this paper, we propose cyclic prefix single carrier (CP-SC) full-duplex transmission in cooperative spectrum sharing to achieve multipath diversity gain and full-duplex spectral efficiency. Integrating full-duplex transmission into cooperative spectrum sharing systems results in two intrinsic problems: 1) the peak interference power constraint at the PUs are concurrently inflicted on the transmit power at the secondary source (SS) and the secondary relays (SRs); and 2) the residual loop interference occurs between the transmit and the receive antennas at the secondary relays. Thus, examining the effects of residual loop interference under peak interference power constraint at the primary users and maximum transmit power constraints at the SS and the SRs is a particularly challenging problem in frequency selective fading channels. To do so, we derive and quantitatively evaluate the exact and the asymptotic outage probability for several relay selection policies in frequency selective fading channels. Our results manifest that a zero diversity gain is obtained with full-duplex.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Full-Duplex Spectrum Sharing in Cooperative Single Carrier Systems

We propose cyclic prefix single carrier full-duplex transmission in amplify-and-forward cooperative spectrum sharing networks to achieve multipath diversity and full-duplex spectral efficiency. Integrating full-duplex transmission into cooperative spectrum sharing systems results in two intrinsic problems: 1) the residual loop interference occurs between the transmit and the receive antennas at the secondary relays and 2) the primary users simultaneously suffer interference from the secondary source (SS) and the secondary relays (SRs). Thus, examining the effects of residual loop interference under peak interference power constraint at the primary users and maximum transmit power constraints at the SS and the SRs is a particularly challenging problem in frequency selective fading channels. To do so, we derive and quantitatively compare the lower bounds on the outage probability and the corresponding asymptotic outage probability for max–min relay selection, partial relay selection, and maximum interference relay selection policies in frequency selective fading channels. To facilitate comparison, we provide the corresponding analysis for half-duplex. Our results show two complementary regions, named as the signal-to-noise ratio (SNR) dominant region and the residual loop interference dominant region, where the multipath diversity and spatial diversity can be achievable only in the SNR dominant region, however the diversity gain collapses to zero in the residual loop interference dominant region.