Testing copositivity with the help of difference-of-convex optimization

We consider the problem of minimizing an indefinite quadratic form over the nonnegative orthant, or equivalently, the problem of deciding whether a symmetric matrix is copositive. We formulate the problem as a difference of convex functions problem. Using conjugate duality, we show that there is a one-to-one correspondence between their respective critical points and minima. We then apply a subgradient algorithm to approximate those critical points and obtain an efficient heuristic to verify non-copositivity of a matrix.     

Improving riverbed sediment classification using backscatter and depth residual features of multi-beam echo-sounder systems

Riverbed and seafloor sediment classification using acoustic remote sensing techniques is of high interest due to their high coverage capabilities at limited cost. This contribution presents the results of riverbed sediment classification using multi-beam echo-sounder data based on an empirical method. Two data sets are considered, both taken at the Waal River, namely Sint Andries and Nijmegen. This work is a follow-up to the work carried out by Amiri-Simkooei et al. [J. Acoust. Soc. Am. 126(4), 1724-1738 (2009)]. The empirical method bases the classification on features of the backscatter strength and depth residuals. A principal component analysis is used to identify the most appropriate and informative features. Clustering is then applied to the principal components resulting from this set of features to assign a sediment class to each measurement. The results show that the backscatter strength features discriminate between different classes based on the sediment properties, whereas the depth residual features discriminate classes based on riverbed forms such as the "fixed layer" (stone having riprap structure) and riverbed ripples. Combination of these two sets of features is highly recommended because they provide complementary information on both the composition and the structure of the riverbed.     

Syntheses of Enantiomerically Pure 2‐Substituted Pyrrolidin‐3‐ones via Lithiated Alkoxyallenes – An Auxiliary‐Based Synthesis of both Enantiomers of the Antibiotic Anisomycin

The hydrochlorides of both enantiomers of the antibiotic anisomycin were prepared starting with the ‘diacetone‐fructose’‐substituted allene 1 and the N‐Boc‐protected imine precursor 2a . Addition of an excess of lithiated 1 to 2a provided a 2 : 1 mixture 3a of diastereoisomers, which were cyclized to 4a under base promotion (Scheme 2). The two diastereoisomers of 4a were separated and converted into enantiomerically pure pyrrolidin‐3‐ones (2R)‐ 5a and (2S)‐ 5a . A similar sequence yielded the N‐Tos‐protected compounds (2R)‐ 5b and (2S)‐ 5b . Compounds 5a were converted into silyl enol ethers 6 and by subsequent regio‐ and stereoselective hydroboration into pyrrolidine derivatives 7 (Scheme 3). Straightforward functional‐group transformations led to the hydrochlorides 9 of anisomycin (Scheme 3). The (2R) series provided the hydrochloride (2R)‐ 9 of the natural occurring enantiomer, whereas the (2S) series furnished the antipode (2S)‐ 9 . The overall sequence to the natural product involved ten steps with eight purified intermediates and afforded an overall yield of 8%. Our stereochemically divergent approach to this type of hydroxylated pyrrolidines is highly flexible and should easily allow preparation of many analogues.     

Intramolecular Ring-Expansion Reaction (RER) and Intermolecular Coordination of In Situ Generated Cyclic (Amino)(aryl)carbenes (cAArCs)

Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α-elimination of 3-alkoxyisoindolines at high temperatures or by deprotonation of isoindol-2-ium chlorides with sodium or copper(I) acetates at low temperatures. 3-Alkoxy-isoindolines 2 a , b-OR (R=Me, Et, iPr) have been prepared in high yields by the addition of a solution of 2-aryl-1,1-diphenylisoindol-2-ium triflate ( 1 a , b-OTf ; a : aryl=Dipp=2,6-diisopropylphenyl; b : Mesityl-, Mes=2,4,6-trimethylphenyl) to the corresponding alcohol (ROH) with NEt₃ at room temperature. Furthermore, the reaction of 2 a , b-OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol-2-ium chlorides 1 a , b-Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a . Without any additional trapping reagent, in situ generation of 1,1-diphenylisoidolin-3-ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C−H bond of a phenyl substituent, followed by ring-expansion reaction; namely, anthracene derivatives 9-N(H)aryl-10-Ph-C₁₄H₈ 4 a , b ( a : Dipp; b : Mes). These compounds are conveniently synthesized by deprotonation of the isoindol-2-ium chlorides with sodium acetate in high yields. Deprotonation of 1 a-Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a , and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].     

Flexible cue use in nonnative phonetic categorization

Native and nonnative listeners categorized final /v/ versus /f/ in English nonwords. Fricatives followed phonetically long (originally /v/-preceding) or short (originally /f/-preceding) vowels. Vowel duration was constant for each participant and sometimes mismatched other voicing cues. Previous results showed that English but not Dutch listeners (whose L1 has no final voicing contrast) nevertheless used the misleading vowel duration for /v/-/f/ categorization. New analyses showed that Dutch listeners did use vowel duration initially, but quickly reduced its use, whereas the English listeners used it consistently throughout the experiment. Thus, nonnative listeners adapted to the stimuli more flexibly than native listeners did.     

Dispersion curves of photon-induced surface phonon-polaritons and of Brewster modes

The reflectivity for angular scans at constant frequency is calculated in a frequency range which covers a dispersion curve of photon-induced surface phonon-polaritons on α-quartz. Additionally the dispersion of a backbent branch and of Brewster modes is deduced.     

Bleaching-resistant,Near-continuous Single-molecule Fluorescence and FRET Based on Fluorogenic and Transient DNA Binding

Photobleaching of fluorescent probes limits the observation span of typical single-molecule fluorescence measurements and hinders observation of dynamics at long timescales. Here, we present a general strategy to circumvent photobleaching by replenishing fluorescent probes via transient binding of fluorogenic DNAs to complementary DNA strands attached to a target molecule. Our strategy allows observation of near-continuous single-molecule fluorescence for more than an hour, a timescale two orders of magnitude longer than the typical photobleaching time of single fluorophores under our conditions. Using two orthogonal sequences, we show that our method is adaptable to Förster Resonance Energy Transfer (FRET) and that can be used to study the conformational dynamics of dynamic structures, such as DNA Holliday junctions, for extended periods. By adjusting the temporal resolution and observation span, our approach enables capturing the conformational dynamics of proteins and nucleic acids over a wide range of timescales.     

General N=1 supersymmetric flux vacua of massive type IIA string theory

We derive conditions for the existence of four-dimensional N=1 supersymmetric flux vacua of massive type IIA string theory with general supergravity fluxes turned on. For an SU(3) singlet Killing spinor, we show that such flux vacua exist when the internal geometry is nearly K?hler. The geometry is not warped, all the allowed fluxes are proportional to the mass parameter, and the dilaton is fixed by a ratio of (quantized) fluxes. The four-dimensional cosmological constant, while negative, becomes small in the vacuum with the weak string coupling.