A facile domino metathetic route to a thapsigargin skeleton

A facile synthesis of a 5,7,5-fused ring system that is present in thapsigargins belonging to a novel family of sesquiterpene lactones, guainanolides, using domino enyne-RCM is reported here.     

Recovery of spectral features readout with frequency-chirped laser fields

A data-processing technique is proposed for use with conventional frequency-chirped absorption spectroscopy to ensure accurate mapping of spectral features into time-domain signatures with arbitrarily fast readout chirp rates. This technique recovers the spectrum from a signal that is distorted owing to the fast chirp rate and therefore facilitates fast measurement of the spectral features over a broad spectral range with high resolution. Both numerical simulations and experimental results are presented.     

Two-point time-series measurements of minor-species concentrations in a turbulent nonpremixed flame

We report a technique that is capable of making simultaneous two-point time-series measurements of minor-species concentrations in turbulent flames. The experimental setup, which incorporates picosecond time-resolved laser-induced fluorescence, has a spatial resolution of less than 250 microm and a temporal resolution of less than 100 micros, which spatially and temporally resolve microscales in many turbulent flows. Two-point time-series data are given for a standard turbulent nonpremixed flame at Re= 10,000, including a discussion of potential implications.     

Force field parametrization through fitting on inflection points in isotherms

We present a method to determine potential parameters in molecular simulations of confined systems through fitting on experimental isotherms with inflection points. The procedure uniquely determines the adsorbent-adsorbate interaction parameters and is very sensitive to the size parameter. The inflection points in the isotherms are often related to a subtle interplay between different adsorption sites. If a force field can predict this interplay, it also reproduces the remaining part of the isotherm correctly, i.e., the Henry coefficients and saturation loadings.     

Detection of hypophosphite, phosphite, and orthophosphate in natural geothermal water by ion chromatography

Current doctrine states that phosphorus is incorporated into cells in the pentavalent(V) oxidation state as orthophosphate. However, recent studies show that microorganisms contain enzymes used to metabolize reduced forms of phosphorous, including phosphite(III) and hypophosphite(I), which suggests that there is a natural source for these chemical species. This paper will discuss suppressed conductivity ion chromatography methods developed to detect hypophosphite, phosphite, and orthophosphate in a geothermal water matrix containing fluoride, chloride, bromide, nitrate, hydrogen carbonate and sulfate. All peaks were clearly resolved, and calibrations were linear with estimated 3sigma detection limits of 0.83, 0.39, and 0.35 microM for hypophosphite, phosphite, and orthophosphate, respectively.     

Rifampicin inhibits alpha-synuclein fibrillation and disaggregates fibrils

The aggregation of alpha-synuclein in dopaminergic neurons of the substantia nigra is a critical step in the pathogenesis of Parkinson's disease. We show that the antibiotic rifampicin inhibited alpha-synuclein fibrillation and disaggregated existing fibrils in a concentration-dependent manner. Size-exclusion chromatography data indicated that rifampicin stabilized alpha-synuclein as both a monomer and soluble oligomers comprised of partially folded alpha-synuclein. Experiments using aged samples of rifampicin indicated that the most active species in inhibiting fibrillation and disaggregating fibrils is an oxidation product of rifampicin, which was confirmed in experiments under anaerobic conditions. These results indicate that rifampicin-mediated inhibition of alpha-synuclein fibrillation and disaggregation of fibrils involves preferential stabilization of monomeric and soluble oligomeric forms, and that rifampicin potentially may have therapeutic application for Parkinson's disease.     

Long-time-storage mechanism for Tm:YAG in a magnetic field

We obtained a long-time-storage mechanism for spectral features in thulium ions doped into YAG by applying a magnetic field that splits the electronic ground state. We show experimentally that the storage time can be more than 30 s, which is 3 orders of magnitude longer than that of the metastable state that normally is used for information storage in this material. Level splitting and storage lifetimes for various magnetic field strengths of as much as 5 T were investigated. This storage mechanism will be relevant in the many coherent transient-based signal-processing schemes in which Tm:YAG is being used, and we demonstrate long-time storage in a basic data storage application.     

Implementation of an adaptive umbrella sampling method for the calculation of multidimensional potential of mean force of chemical reactions in solution

We describe the implementation of an adaptive umbrella sampling method, making use of the weighted histogram analysis method, for computing multidimensional potential of mean force for chemical reaction in solution. The approach is illustrated by investigating the effect of aqueous solution on the free energy surface for the proton transfer reaction of [H(3)N-H-NH(3)](+) using a combined quantum mechanical and molecular mechanical AM1/TIP3P potential.     

Trends in exchange coupling for trimethylenemethane-type Bis(semiquinone) biradicals and correlation of magnetic exchange with mixed valency for cross-conjugated systems

A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states.     

Si doped GaAs/AlGaAs terahertz detector and phonon effect on the responsivity

Terahertz detection capability of an n-type heterojunction interfacial work function internal photoemission (HEIWIP) detector is demonstrated. Threshold frequency, f₀, of 3.2 THz (93 μm) was obtained by using n-type GaAs emitter doped to 1 × 10¹⁸ cm⁻³ and Al_0.04Ga_0.96As single barrier structure. The detector shows a broad spectral response from 30 to 3.2 THz (10–93 μm) with peak responsivity of 6.5 A/W at 7.1 THz under a forward bias field of 0.7 kV/cm at 6 K. The peak quantum efficiency and peak detectivity are 19% and 5.5 × 10⁸ Jones, respectively under a bias field of 0.7 kV/cm at 6 K. In addition, the detector can be operated up to 25 K.