Dissections: self-assembled aggregates that spontaneously reconfigure their structures when their environment changes

This Communication describes a new strategy for the design of adaptive structures based on reconfigurable mesoscale self-assembly. Several sets of millimeter-scale objects have been designed that can self-assemble into two different, regular aggregates at the interface between an aqueous solution and perfluorodecalin; the choice between the two aggregates is determined by the density of the aqueous phase.     

Simulation of jet-noise excitation in an acoustic progressive wave tube facility

Acoustic excitation produced by jet-engine effluxes was simulated in a progressive wave tube (APWT) facility with a computer-based control system. The APWT siren is driven by a signal generated numerically in a PC and then converted into analog form. Characteristics of the acoustic pressure measured by a microphone are analyzed in digital form and compared with those prescribed for simulation. Divergence is compensated by immediate modification of the driving signal and this action is repeated in the form of iterative process until the test specification is attained. Typical power spectral density (PSD) shapes with maxima at low and high frequencies were simulated. A "tailoring" approach has been also achieved when a test specification was determined directly from field measurements for the particular aircraft under consideration. Since acoustic pressure signals of high level differ from the Gaussian random process model, particularly in terms of asymmetric probability density function, a method has been developed to make the driving signal also non-Gaussian by simulating skewness and kurtosis parameters of the APWT acoustic excitation simultaneously with PSD control. Experimental results with Gaussian and non-Gaussian characteristics obtained for various PSD specifications including sharp and narrow peaks are presented in the paper.     

Squeeze film pressures

Summary As parallel faces separated by a fluid film approach one another, a pressure is developed in the film. The reduced Navier-Stokes equations are solved by transform methods for both rectangular and cylindrical geometries. Relatively high pressures can exist at small asperities on the surfaces as they approach one another.     

Measurement of the positive muon lifetime and determination of the Fermi constant to part-per-million precision

We report a measurement of the positive muon lifetime to a precision of 1.0 ppm; it is the most precise particle lifetime ever measured. The experiment used a time-structured, low-energy muon beam and a segmented plastic scintillator array to record more than 2×10(12) decays. Two different stopping target configurations were employed in independent data-taking periods. The combined results give τ(μ(+)) (MuLan)=2?196?980.3(2.2) ps, more than 15 times as precise as any previous experiment. The muon lifetime gives the most precise value for the Fermi constant: G(F) (MuLan)=1.166?378?8(7)×10(-5) GeV(-2) (0.6 ppm). It is also used to extract the μ(-)p singlet capture rate, which determines the proton's weak induced pseudoscalar coupling g(P).     

Sulfures et disulfures : acidités cinétiques relatives des protons adjacents au soufre

Dibenzyl disulfide is deprotonated at ?78° approximately 7.5 times more rapidly than dibenzyl sulfide, as predicted by a molecular orbital analysis which focuses on the interaction between the carbon lone pair and an adjacent σ * orbital.     

N-methyl-substituted aromatic polyamides

A series of N-methyl-substituted aromatic polyamides derived from the secondary aromatic diamines 4,4′-bis(methylamino)diphenylmethane, 3,3′-bis(methylamino)diphenylmethane, 4,4′-bis(methylamino)benzophenone or 3,3′-bis(methylamino)benzophenone and isophthaloyl dichloride, and terephthaloyl dichloride or 3,3′-diphenylmethane dicarboxylic acid dichloride was prepared by high-temperature solution polymerization in s-tetrachloroethane. Compared with analogous unsubstituted and partly N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures (T_g), reduced crystallinity, improved thermal stability, and good solubility in chlorinated solvents.     

Fully ferrocenated hexanethiolate monolayer-protected gold clusters

The synthesis and compositional analysis of four different gold clusters with protecting monolayers comprised solely of ferrocene hexanethiolate ligands is described. The gold nanoparticles have average core diameters of 1.4, 1.6, 2.0, and 2.2 nm with estimated average atom counts of 55, 140, 225, and 314 Au atoms and average monolayer coverages of 37, 39, 43, and 58 ferrocenated ligands, respectively. The data show unequivocally that the number of ferrocene hexanethiolate ligands bound to each core size is constrained by the steric requirements of the ferrocene head group; the ligand numbers are significantly smaller than those for hexanethiolate ligands bonded to analogous-sized Au cores. Voltammetry of dilute solutions of these nanoparticles shows a large ferrocene oxidation wave and, at more negative potentials, smaller one-electron waves for the quantized double-layer charging of the Au cores. Together, the ferrocenes and core of the ferrocenated Au314 nanoparticle deliver 60 electrons at the ferrocene oxidation potential, which amounts to a very large volume charge capacity, 7x10(9) C/m3, for an undiluted nanoparticle sample.     

Prototype structure of Pb5Ge3O11

The prototypic structure of the optically active ferroelectric Pb₅Ge₃O₁₁ has been deduced from packing considerations and refined from single-crystal diffractometer data. Interleaving segments of the apatite and nasonite structures in layers perpendicular to c gives the lead germanate structure. The space group of the prototype is $\text{P}\text{6}$, with a = 10.190, c = 10.624 Å, and Z = 3. Atomic coordinates were refined to give an R-factor of 0.093 using 463 X-ray reflections. The structure contains tetrahedral GeO₄ groups and double tetrahedral Ge₂O₇ groups in equal numbers. Lead is found in both trigonal pyramid and trigonal prism configurations.     

Quantification of Lysine Acetylation and Succinylation Stoichiometry in Proteins Using Mass Spectrometric Data-Independent Acquisitions (SWATH)

Post-translational modification of lysine residues by N_?-acylation is an important regulator of protein function. Many large-scale protein acylation studies have assessed relative changes of lysine acylation sites after antibody enrichment using mass spectrometry-based proteomics. Although relative acylation fold-changes are important, this does not reveal site occupancy, or stoichiometry, of individual modification sites, which is critical to understand functional consequences. Recently, methods for determining lysine acetylation stoichiometry have been proposed based on ratiometric analysis of endogenous levels to those introduced after quantitative per-acetylation of proteins using stable isotope-labeled acetic anhydride. However, in our hands, we find that these methods can overestimate acetylation stoichiometries because of signal interferences when endogenous levels of acylation are very low, which is especially problematic when using MS1 scans for quantification. In this study, we sought to improve the accuracy of determining acylation stoichiometry using data-independent acquisition (DIA). Specifically, we use SWATH acquisition to comprehensively collect both precursor and fragment ion intensity data. The use of fragment ions for stoichiometry quantification not only reduces interferences but also allows for determination of site-level stoichiometry from peptides with multiple lysine residues. We also demonstrate the novel extension of this method to measurements of succinylation stoichiometry using deuterium-labeled succinic anhydride. Proof of principle SWATH acquisition studies were first performed using bovine serum albumin for both acetylation and succinylation occupancy measurements, followed by the analysis of more complex samples of E. coli cell lysates. Although overall site occupancy was low (<1%), some proteins contained lysines with relatively high acetylation occupancy.

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