Analysis of patient self-assessment visual analogue scales

The present paper describes an example of practical analysis of data from an application of visual analogue scales. Potentially useful and simple methods for analysing visual analogue scales are described for effective handling of complex data when the desire is to compare two or more groups of patients. Visual analogue scales were used to assess subjective tolerability in the International Prospective Primary Prevention Study in Hypertension, a large scale clinical trial. The methods are illustrated on the IPPPSH data.     

Triggered single photons and entangled photons from a quantum dot microcavity

Current quantum cryptography systems are limited by the attenuated coherent pulses they use as light sources: a security loophole is opened up by the possibility of multiple-photon pulses. By replacing the source with a single-photon emitter, transmission rates of secure information can be improved. We have investigated the use of single self-assembled InAs/GaAs quantum dots as such single-photon sources, and have seen a tenfold reduction in the multi-photon probability as compared to Poissonian pulses. An extension of our experiment should also allow for the generation of triggered, polarization-entangled photon pairs. The utility of these light sources is currently limited by the low efficiency with which photons are collected. However, by fabricating an optical microcavity containing a single quantum dot, the spontaneous emission rate into a single mode can be enhanced. Using this method, we have seen 78% coupling of single-dot radiation into a single cavity resonance. The enhanced spontaneous decay should also allow for higher photon pulse rates, up to about 3 GHz. Received 8 July 2001 and Received in final form 25 August 2001     

Influence of a single quantum dot state on the characteristics of a microdisk laser

We report a quantum dot microcavity laser with a cw sub-microW lasing threshold, where a significant reduction of the lasing threshold is observed when a single quantum dot (QD) state is aligned with a cavity mode. The quality factor exceeds 15,000 before the system lases. When no QD states are resonant, below threshold the cavity mode initially degrades with increasing pump power, after which saturation occurs and then the cavity mode recovers. We associate the initial cavity mode spoiling with QD state broadening that occurs with increasing pump power.     

Synthesis and pH‐Dependent Spectroscopic Behavior of 2,4,6‐Trisubstituted Pyridine Derivatives

Seven 2,4,6‐trisubstituted pyridine derivatives with N,N‐diethylaniline substituents at the 4‐position were synthesized, and their spectroscopic properties in the absence and presence of acid were studied. The spectral effects of protonation, molar absorptivities, pK_a values, and the structural origins of the observed spectral behavior were ascertained. The pyridine nitrogen was found to be more basic than the diethylamino nitrogen atom. Protonation of the pyridine ring nitrogen is associated with the appearance of a red‐shifted intramolecular charge transfer peak in the UV‐visible spectra. Favorable color indicating properties result from electron‐donating substitution at the 2 and 6 positions of pyridine, which provide a greater absorptivity of the red‐shifted peak associated with protonation of the pyridine nitrogen. These findings will assist in the design and optimization of these compounds for ion‐indicating and pH‐sensing applications.     

S K-edge XAS and DFT calculations on SAM dependent pyruvate formate-lyase activating enzyme: nature of interaction between the Fe4S4 cluster and SAM and its role in reactivity

S K-edge X-ray absorption spectroscopy on the resting oxidized and the S-adenosyl-l-methionine (SAM) bound forms of pyruvate formate-lyase activating enzyme are reported. The data show an increase in pre-edge intensity, which is due to additional contributions from sulfide and thiolate of the Fe(4)S(4) cluster into the C-S σ* orbital. This experimentally demonstrates that there is a backbonding interaction between the Fe(4)S(4) cluster and C-S σ* orbitals of SAM in this inner sphere complex. DFT calculations that reproduce the data indicate that this backbonding is enhanced in the reduced form and that this configurational interaction between the donor and acceptor orbitals facilitates the electron transfer from the cluster to the SAM, which otherwise has a large outer sphere electron transfer barrier. The energy of the reductive cleavage of the C-S bond is sensitive to the dielectric of the protein in the immediate vicinity of the site as a high dielectric stabilizes the more charge separated reactant increasing the reaction barrier. This may provide a mechanism for generation of the 5'-deoxyadenosyl radical upon substrate binding.     

The complexity of central series in nilpotent computable groups

The terms of the upper and lower central series of a nilpotent computable group have computably enumerable Turing degree. We show that the Turing degrees of these terms are independent even when restricted to groups which admit computable orders.     

Tunneling currents that increase with molecular elongation

We present a model molecular system with an unintuitive transport-extension behavior in which the tunneling current increases with forced molecular elongation. The molecule consists of two complementary aromatic units (1,4-anthracenedione and 1,4-anthracenediol) hinged via two ether chains and attached to gold electrodes through thiol-terminated alkenes. The transport properties of the molecule as it is mechanically elongated in a single-molecule pulling setting are computationally investigated using a combination of equilibrium molecular dynamics simulations of the pulling with gDFTB computations of the transport properties in the Landauer limit. Contrary to the usual exponential decay of tunneling currents with increasing molecular length, the simulations indicate that upon elongation electronic transport along the molecule increases 10-fold. The structural origin of this inverted trend in the transport is elucidated via a local current analysis that reveals the dual role played by H-bonds in both stabilizing π-stacking for selected extensions and introducing additional electronic couplings between the complementary aromatic rings that also enhance tunneling currents across the molecule. The simulations illustrate an inverted electromechanical single-molecule switch that is based on a novel class of transport-extension behavior that can be achieved via mechanical manipulation and highlight the remarkable sensitivity of conductance measurements to the molecular conformation.     

Cupric superoxo-mediated intermolecular C-H activation chemistry

The new cupric superoxo complex [LCu(II)(O(2)(?-))](+), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases.     

Recent advances in understanding blue copper proteins

The type 1 (T1) or blue Cu (BC) proteins are a highly studied group of electron transfer (ET) active sites in bioinorganic chemistry. In this review, we cover several more recent results which extend the understanding of the geometric and electronic structure of these interesting Cu ET sites. Spectroscopic methods in tandem with density functional theory (DFT) and time dependent-DFT (TD-DFT) calculations have been used in studies of S → Se variants as well as a series of metal-varied model complexes (M = Mn²⁺ → Zn²⁺). The ligand and metal perturbations further defined the origins of the unique spectral features of BC proteins. These unique spectral features show different temperature dependencies in different T1 sites, and contrasts drawn between their behaviors define the role of the protein in tuning the geometric and electronic structure of the BC site for function. This has been termed the ‘entatic’ or ‘rack-induced’ state in bioinorganic chemistry.