Gradient-enhanced heteronuclear correlation spectroscopy: theory and experimental aspects. 1992

A detailed theoretical and experimental treatment is given for gradient-enhanced heteronuclear correlation spectroscopy. Both multiple-quantum and single-quantum sequences are described. In addition to a comparison with conventional experiments using phase cycling, the effects of different gradient combinations are examined with respect to artifacts occurring in the heteronuclear dimension. The influence of gradient performance and diffusion on sensitivity is discussed. Approaches to attain phase-sensitive spectra are also analyzed.     

The effect of multimicrophone noise reduction systems on sound source localization by users of binaural hearing aids

This paper evaluates the influence of three multimicrophone noise reduction algorithms on the ability to localize sound sources. Two recently developed noise reduction techniques for binaural hearing aids were evaluated, namely, the binaural multichannel Wiener filter (MWF) and the binaural multichannel Wiener filter with partial noise estimate (MWF-N), together with a dual-monaural adaptive directional microphone (ADM), which is a widely used noise reduction approach in commercial hearing aids. The influence of the different algorithms on perceived sound source localization and their noise reduction performance was evaluated. It is shown that noise reduction algorithms can have a large influence on localization and that (a) the ADM only preserves localization in the forward direction over azimuths where limited or no noise reduction is obtained; (b) the MWF preserves localization of the target speech component but may distort localization of the noise component. The latter is dependent on signal-to-noise ratio and masking effects; (c) the MWF-N enables correct localization of both the speech and the noise components; (d) the statistical Wiener filter approach introduces a better combination of sound source localization and noise reduction performance than the ADM approach.     

Novel extended tetrathiafulvalenes based on acetylenic spacers: synthesis and electronic properties

A selection of mono- and diacetylenic dithiafulvalenes was synthesized and employed for the construction of extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene or deca-2,4,6,8-tetrayne-1,10-diylidene spacers between the two 1,3-dithiole rings. By stepwise acetylenic scaffolding using (E)-1,2-diethynylethene (DEE) building blocks, an extended TTF containing a total of 18 C(sp) and C(sp(2)) atoms in the spacer was prepared. The versatility of the acetylenic dithiafulvene modules was also established by the efficient synthesis of a thiophene-spaced TTF, employing a palladium-catalyzed cross-coupling reaction. The developed synthetic protocols allow functionalization of the extended TTFs in three general ways: with 1) peripheral substituents on the fulvalene cores, 2) alkynyl moieties laterally appended to the spacer, and 3) cobalt clusters involving acetylenic moieties. Strong chromophoric properties of the extended TTFs were revealed by linear and nonlinear optical spectroscopies. Extensive electrochemical studies and calculations on these compounds are also reported, as well as X-ray crystallographic analyses.     

Ac and dc electrical conductivity of polynuclear metal cluster compounds

Ac and dc electrical conductivity data are presented for two polynuclear metal cluster compounds Au₅₅(PPh)₃)₁₂Cl₆ and Pd₅₆₁Phen₃₆O₂₀₀. The temperature dependence of the low field dc conductivity increases with electrical field, the rate of increase becoming stronger with decreasing temperature. These results are compared with data for granular metal systems, and a close correspondence is observed. The conductivity is found to increase with frequency in analogy to what is observed in amorphous systems. A scaling law for low frequencies that has been recently proposed is shown to describe the data quite well.     

Ground-state equilibrium thermodynamics and switching kinetics of bistable [2]rotaxanes switched in solution, polymer gels, and molecular electronic devices

We report on the kinetics and ground-state thermodynamics associated with electrochemically driven molecular mechanical switching of three bistable [2]rotaxanes in acetonitrile solution, polymer electrolyte gels, and molecular-switch tunnel junctions (MSTJs). For all rotaxanes a pi-electron-deficient cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles one of two recognition sites within a dumbbell component. Two rotaxanes (RATTF4+ and RTTF4+) contain tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) recognition units, but different hydrophilic stoppers. For these rotaxanes, the CBPQT4+ ring encircles predominantly (>90 %) the TTF unit at equilibrium, and this equilibrium is relatively temperature independent. In the third rotaxane (RBPTTF4+), the TTF unit is replaced by a pi-extended analogue (a bispyrrolotetrathiafulvalene (BPTTF) unit), and the CBPQT4+ ring encircles almost equally both recognition sites at equilibrium. This equilibrium exhibits strong temperature dependence. These thermodynamic differences were rationalized by reference to binding constants obtained by isothermal titration calorimetry for the complexation of model guests by the CBPQT4+ host in acetonitrile. For all bistable rotaxanes, oxidation of the TTF (BPTTF) unit is accompanied by movement of the CBPQT4+ ring to the DNP site. Reduction back to TTF0 (BPTTF0) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics are strongly environmentally dependent, yet consistent with a single electromechanical-switching mechanism in acetonitrile, polymer electrolyte gels, and MSTJs. The ground-state equilibrium properties of all three bistable [2]rotaxanes were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs.     

Linearity properties of Shimura varieties, II

Let A=A_{g, 1, n} denote the moduli scheme over Z[1/N] of p.p. g-dimensional abelian varieties with a level n structure; its generic fibre can be described as a Shimura variety. We study its Shimura subvarieties. If x A is an ordinary moduli point in characteristic p, then we formulate a local linearity property in terms of the Serre–Tate group structure on the formal deformation space (= formal completion of A at x). We prove that an irreducible algebraic subvariety of A is a Shimura subvariety if, locally at an ordinary point x, it is formally linear. We show that there is a close connection to a differential-geometrical linearity property in characteristic 0.We apply our results to the study of Oort's conjecture on subvarieties Z A with a dense collection of CM-points. We give a reformulation of this conjecture, and we prove it in a special case.     

Performance of slotted pores in particle manufacture using rotating membrane emulsification

This paper addresses the use of different slotted pores in rotating membrane emulsification technology.Pores of square and rectangular shapes were studied to understand the effect of aspect ratio (1-3.5) and their orientation on oil droplet formation.Increasing the membrane rotation speed decreased the droplet size,and the oil droplets produced were more uniform using slotted pores as compared to circular geometry.At a given rotation speed,the droplet size was mainly determined by the pore size and the fluid velocity of oil through the pore (pore fluid velocity).The ratio of droplet diameter to the equivalent diameter of the slotted pore increased with the pore fluid velocity.At a given pore fluid velocity and rotation speed,pore orientation significantly influences the droplet formation rate: horizontally disposed pores (with their longer side perpendicular to the membrane axis) generate droplets at double the rate of vertically disposed pores.This work indicates practical benefits in the use of slotted membranes over conventional methods.     

Speech intelligibility improvements with hearing aids using bilateral and binaural adaptive multichannel Wiener filtering based noise reduction

This paper evaluates noise reduction techniques in bilateral and binaural hearing aids. Adaptive implementations (on a real-time test platform) of the bilateral and binaural speech distortion weighted multichannel Wiener filter (SDW-MWF) and a competing bilateral fixed beamformer are evaluated. As the SDW-MWF relies on a voice activity detector (VAD), a realistic binaural VAD is also included. The test subjects (both normal hearing subjects and hearing aid users) are tested by an adaptive speech reception threshold (SRT) test in different spatial scenarios, including a realistic cafeteria scenario with nonstationary noise. The main conclusions are: (a) The binaural SDW-MWF can further improve the SRT (up to 2 dB) over the improvements achieved by bilateral algorithms, although a significant difference is only achievable if the binaural SDW-MWF uses a perfect VAD. However, in the cafeteria scenario only the binaural SDW-MWF achieves a significant SRT improvement (2.6 dB with perfect VAD, 2.2 dB with real VAD), for the group of hearing aid users. (b) There is no significant degradation when using a real VAD at the input signal-to-noise ratio (SNR) levels where the hearing aid users reach their SRT. (c) The bilateral SDW-MWF achieves no SRT improvements compared to the bilateral fixed beamformer.     

Unexpected four-membered over six-membered ring formation during the synthesis of azaheterocyclic phosphonates: experimental and theoretical evaluation

The cyclization of functionalized aminophosphonates is studied on both experimental and theoretical grounds. In a recently described route to phosphono-beta-lactams [Stevens C. V.; Vekemans, W.; Moonen, K.; Rammeloo, T. Tetrahedron Lett. 2003, 44, 1619], it was found that starting from an ambident allylic anion only four-membered rings were formed without any trace of six-membered lactams. New anion trapping experiments revealed that the gamma-anion is highly reactive in intermolecular reactions. Ab initio calculations predict higher reaction barriers for the gamma-anion due to restricted rotation about the C-N bond and due to highly strained transition states during ring closure. The sodium or lithium counterion, explicit dimethyl ether solvent molecules, and bulk solvent effects were properly taken into account at various levels of theory.