Absolute configuration of an iturinic acid as determined by CD spectrum of its DNP-p-methoxyanilide

Absolute configuration of the long chain β-amino acid obtained from the hydrolysate of iturin A has been determined to be R by application of Dnp-aromatic rule. This is the first assignment for the chirality of an iturinic acid.     

A mechanism for transition-metal nanoparticle self-assembly

The four-step mechanism by which transition-metal nanoclusters or bulk-metal films self-assemble from metal salts under reductive conditions has been discovered. The presence of two autocatalytic steps in the same reaction scheme--double autocatalysis--is the key to the sharp "turn-on" feature after an induction period observed in the signature kinetic curves. Predictions of the new mechanism that are tested experimentally include the following: that low concentrations and high temperatures will favor nanoclusters over bulk-metal film formation; that bulk-metal is formed in some, if not many, literature syntheses reporting only Pt(0) nanoclusters; and that added ligands are one key to turning on the new mechanism. Particle-size-dependent metal-ligand bond dissociation energies are another implication from this mechanistic work.     

Limits on the high-energy gamma and neutrino fluxes from the SGR 1806-20 giant flare of 27 December 2004 with the AMANDA-II detector

On 27 December 2004, a giant gamma flare from the Soft Gamma-Ray Repeater 1806-20 saturated many satellite gamma-ray detectors, being the brightest transient event ever observed in the Galaxy. AMANDA-II was used to search for down-going muons indicative of high-energy gammas and/or neutrinos from this object. The data revealed no significant signal, so upper limits (at 90% C.L.) on the normalization constant were set: 0.05(0.5) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the gamma flux and 0.4(6.1) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the high-energy neutrino flux.     

Dielectron widths of the Gamma(1S,2S,3S) resonances

We determine the dielectron widths of the Gamma(1S), Gamma(2S), and Gamma(3S) resonances with better than 2% precision by integrating the cross section of e+e- -->Gamma over the e+e- center-of-mass energy. Using e+e- energy scans of the Gamma resonances at the Cornell Electron Storage Ring and measuring Gamma production with the CLEO detector, we find dielectron widths of 1.252+/-0.004(sigma(stat))+/-0.019(sigma(syst)) keV, 0.581+/-0.004+/-0.009 keV, and 0.413+/-0.004+/-0.006 keV for the Gamma(1S), Gamma(2S), and Gamma(3S), respectively.     

New measurements of Cabibbo-suppressed decays of mesons with the CLEO-c detector

Using of data collected with the CLEO-c detector, we report on first observations and measurements of Cabibbo-suppressed decays of D mesons in the following six decay modes: pi+ pi- pi0 pi0, pi+ pi+ pi- pi- pi0, pi+ pi0 pi0, pi+ pi+ pi- pi0, eta pi0, and omega pi+ pi-. Improved branching fraction measurements in eight other multipion decay modes are also presented. The measured D --> pi pi rates allow us to extract the ratio of isospin amplitudes A(DeltaI = (3/2) / A(DeltaI = (1/2)) = 0.420 +/- 0.014(stat) +/- 0.016(syst) and the strong phase shift of delta1 = (86.4 +/- 2.8 +/- 3.3) degrees, which is quite large and now more precisely determined.     

A high-throughput mammalian protein expression, purification, aliquoting and storage pipeline to assemble a library of the human secretome

In the post-human genome-sequencing era, the availability of recombinant proteins has become crucial for the identification of proteins with therapeutic potential. Based upon bioinformatic coding predictions of the genes for putative secreted proteins, we established a high-throughput protein pipeline (HTPP) for the production of a subset of the human secretome. The HTPP was based on a transient expression system in HEK293-EBNA cells at 100 to 500 mL culture scale, combined with an automated affinity purification procedure targeting >75% purity. This was followed by a semi-automated protein sample logistics to provide biologists with quality-controlled and 96 well formatted protein aliquots amenable to cell-based assays. Over a 4-year period, beginning in 2001, we performed over 7,500 transfections representing over 2,200 registered proteins, including both novel and reference proteins, at an average production of 280 proteins/month with a peak production of 320 proteins/month. All these proteins have been tested in more than 50 different cell-based assays. This article describes the major process steps and highlights the optimization required to maintain novel protein production while supporting both stock replenishment and scale-up productions.     

Thermoelastic behaviour of hexagonal graphite-like boron nitride

Abstract

A synchrotron X-ray diffraction study on hexagonal graphite-like boron nitride (h-BN) was performed under high pressures and temperatures. From the measured P-V-Trelation for h-BN (with a three-dimensional ordering parameter P₃ = 0.9) in the temperature range from 298 to 1273 K and up to 6.7 GPa, the thermoelastic parameters are derived by fitting a modified high temperature Birch-Murnaghan equation of state. The results are: bulk modulus B₀[GPa] = 27.6-0.0081(T[K]-298) and its pressure derivative B¹ = 10.5 + 0.0016(T [K] - 298). These values are for samples with P₃ = 0.9 and are quite different for samples with different values of the order parameter. This parameter is shown to have a leading role in the determination of the thermoelastic properties of h-BN, which explains and reconciles the differences between previous results.     

Determination of the strong phase in D0-->K+pi- using quantum-correlated measurements

We exploit the quantum coherence between pair-produced D0 and D[over]0 in psi(3770) decays to study charm mixing, which is characterized by the parameters x and y, and to make a first determination of the relative strong phase delta between D0-->K+pi- and D[over]0-->K+pi-. Using 281 pb(-1) of e+e- collision data collected with the CLEO-c detector at Ecm=3.77 GeV, as well as branching fraction input and time-integrated measurements of RM identical with (x2 + y2)/2 and RWS identical with Gamma(D0-->K+pi-)/Gamma(D[over]0-->K+pi-) from other experiments, we find cosdelta=1.03(-0.17)(+0.31)+/-0.06, where the uncertainties are statistical and systematic, respectively. By further including other mixing parameter measurements, we obtain an alternate measurement of cosdelta=1.10+/-0.35+/-0.07, as well as x sindelta=(4.4(-1.8)(+2.7)+/-2.9)x10(-3) and delta=(22(-12-11)(+11+9)) degrees .     

Molecular relaxation effects in hydrogen chloride photoacoustic detection

A photoacoustic (PA) sensor has been developed to monitor hydrogen chloride at sub-ppm level in the 1740-nm region. The system was designed to control the process in the novel low-water-peak optical fiber manufacturing process. Relaxation effects in hydrogen chloride PA detection in oxygen–helium and nitrogen–helium gas mixtures are presented, showing that the generation of the PA signal is strongly affected by the ratio of these substances. In addition, the role of water vapor in the PA signal is investigated.     

Supramolecular Recognition Influences Magnetism in [X@HVIV8VV14O54]6− Self‐Assemblies with Symmetry‐Breaking Guest Anions

Mixed‐valence polyoxovanadates(IV/V) have emerged as one of the most intricate class of supramolecular all‐inorganic host species, able to encapsulate a wide variety of smaller guest templates during their self‐assembly formation process. As showcased herein, the incorporation of guests, though governed solely by ultra‐weak electrostatic and van der Waals interactions, can cause drastic effects on the electronic and magnetic characteristics of the shell complex of the polyoxovanadate. We address the question of methodology for the magnetochemical analysis of virtually isostructural {V^IV/V₂₂O₅₄}‐type polyoxoanions of D_2d symmetry enclosing diamagnetic VO₂F₂^? (C_2v), SCN^? (C_∞v), or ClO₄^? (T_d) template anions. These induce different polarization effects related to differences in their geometric structures, symmetry, ion radii, and valence shells, eventually resulting in a supramolecular modulation of magnetic exchange between the V(3d) electrons that are partly delocalized over the {V₂₂O₅₄} shells. We also include the synthesis and characterization of the novel [V^VO₂F₂@HV^IV₈V^V₁₄O₅₄]^6? system that comprises the rarely encountered discrete difluorovanadate anion as a quasi‐isolated guest species.