Polymerization at the alkylthiolate-Au(111) interface

The density functional theory is used to explore alkylthiolates (RS) bonded to Au(111) and gold adatoms on Au(111). Adsorption of RS to adatoms in a structure characterized as an (RSAu)x polymer is strongly preferred over terrace adsorption. The energetic gain upon polymerization is large enough to drive the required Au(111) reconstruction. The results are discussed in relation to thiolate protected gold nanoparticles and homoleptic gold-thiolate complexes.     

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

Composite quantum chemical methods W1X-1 and CBS-QB3 are used to calculate the gas phase standard enthalpy of formation, entropy, and heat capacity of 38 phosphines and phosphine oxides for which reliable experimental thermochemical information is limited or simply nonexistent. For alkyl phosphines and phosphine oxides, the W1X-1, and CBS-QB3 results are mutually consistent and in excellent agreement with available G3X values and empirical data. In the case of aryl-substituted species, different computational methods show more variation, with G3X enthalpies being furthest from experimental values. The calculated thermochemical data are subsequently used to determine Benson group additivity contributions for 24 Benson groups and group pairs involving phosphorus, thereby allowing fast and accurate estimations of thermochemical data of many organophosphorus compounds of any complexity. Such data are indispensable, for example, in chemical process design or estimating potential hazards of new chemical compounds. © 2018 Wiley Periodicals, Inc.     

Carbon-13 NMR Spectroscopy of the Antileukemic Drug MGBG and Related Bis(Amidinohydrazones) [‘Bis(Guanylhydrazones)’]

The first survey of the carbon-13 NMR spectroscopy of the bis(amidinohydrazones) [‘bis(guanylhydrazones)’] of various glyoxals is reported. The compounds studied included the free base and the dihydrochloride of the investigational antileukemic drug methylglyoxal bis(amidinohydrazone) (MGBG) and the dihydrochloride of the parent compound glyoxal bis(amidinohydrazone), as well as the free bases of seven alkyl- and dialkylglyoxal analogs of these compounds. Spectra were assigned with the aid of off-resonance proton noise decoupled carbon-13 measurements. The results obtained strongly suggest that each of the compounds studied consisted of one of the three or four possible geometrical isomers only, or that (less probably) the isomerization of the compounds is rapid on the NMR time scale. Thus, the results are in line with previous proton NMR and X-ray crystallographic observations, and support the theory that the classical syntheses of the compounds tend to yield     

Conversational quality evaluation of artificial bandwidth extension of telephone speech

Artificial bandwidth extension methods have been developed to improve the quality and intelligibility of narrowband telephone speech and to reduce the difference with wideband speech. Such methods have commonly been evaluated with objective measures or subjective listening-only tests, but conversational evaluations have been rare. This article presents a conversational evaluation of two methods for the artificial bandwidth extension of telephone speech. Bandwidth-extended narrowband speech is compared with narrowband and wideband speech in a test setting including a simulated telephone connection, realistic conversation tasks, and various background noise conditions. The responses of the subjects indicate that speech processed with one of the methods is preferred to narrowband speech in noise, but wideband speech is superior to both narrowband and bandwidth-extended speech. Bandwidth extension was found to be beneficial for telephone conversation in noisy listening conditions.     

Spectral control in anisotropic resonance-domain metamaterials

We introduce a concept to control the spectral and dichroic properties of metamaterials. The approach is based on anisotropic metal nanoparticles and on varying their mutual orientation in a periodic lattice. Even seemingly inconsequential changes in particle ordering strongly modify the dichroic properties of the arrays and result in either very narrow resonances or ultrabroad extinction ranges. The results arise from long-range diffractive coupling between the particles, as determined by the dependence of the array unit cell size on particle ordering.     

Evidence of superatom electronic shells in ligand-stabilized aluminum clusters

Ligand-stabilized aluminum clusters are investigated by density functional theory calculations. Analysis of Kohn-Sham molecular orbitals and projected density of states uncovers an electronic shell structure that adheres to the superatom complex model for ligand-stabilized aluminum clusters. In this current study, we explain how the superatom complex electron-counting rule is influenced by the electron-withdrawing ligand and a dopant atom in the metallic core. The results may guide the prediction of new stable ligand-stabilized (superatom) complexes, regardless of core and electron-withdrawing ligand composition.     

Stable isotope profiles of nitrogen gas indicate denitrification in oxygen-stratified humic lakes

Mid-summer N(2) profiles were analyzed from nine oxygen-stratified, humic-acid-rich lakes using a continuous flow isotope ratio mass spectrometer and a Gasbench II device. Sample preparation steps were performed under water to avoid air contamination. The instrument precision for the δ(15)N measurement was high (0.03‰), but for the whole sampling and analysis procedure the mean deviation between replicate samples was 0.13‰ for the δ(15)N measurements and 5.5% for the N(2) gas concentration analysis. The results show that the Gasbench peripheral was suitable for measurement of the (15)N natural abundance of dissolved nitrogen gas, with denitrification indicated by the oversaturation and slightly (<1‰) depleted δ(15)N values of the dissolved N(2) gas in the suboxic zones of some of the study lakes. Calculated values for the denitrified (excess) N(2) varied between -5.3 and 0.7‰. The denitrification potential was determined using the (15)N tracer method, with results showing nitrate-inducible denitrification and no signs of anaerobic ammonium oxidation (anammox).