Vibrational and electronic spectra of 9,10-dihydrobenzo(a)pyren-7(8H)-one and 7,8,9,10-tetrahydrobenzo(a)pyrene: an experimental and computational study

The molecular geometries, vibrational and UV-vis spectra of 9,10-dihydrobenzo(a)pyrene-7(8H)-one (9,10-H(2)BaP) and 7,8,9,10-tetrahydrobenzo(a)pyrene (7,8,9,10-H(4)BaP) were investigated using density functional theory (DFT-B3LYP), with the triple-ζ 6-311+G(d,p) and Dunning's cc-pVTZ basis sets. From the comparison of infrared experimental and calculated infrared, and Raman data comprehensive assignments are made. The calculated infrared frequencies below 1800 cm(-1) are in good agreement with experimental data, with an average deviation of <4 cm(-1). Using the B3LYP/6-311+G(d,p)//TD-B3LYP/6-311G(d,p) level of theory, transition energies, and oscillator strengths of the 30 lowest electronic absorption bands are assigned to π-π* transitions, with good qualitative agreement between experimental and simulated absorption data. In addition, the HOMO-LUMO gaps and their chemical hardness were analyzed.     

A clipped [3]rotaxane derived from bis-nor-seco-cucurbit[10]uril

This paper describes the synthesis of host 1 by the double bridging reaction of bis-ns-CB[10] with 2 under acidic conditions. Host 1 functions as a double cavity host for aliphatic and aromatic ammonium ions (3-17) in water. Conducting the bridging reaction in the presence of guest 4 delivers [3]rotaxane 1·4(2) by a clipping process.     

"Inosaminoacids": novel inositol-amino acid hybrid structures accessed by microbial arene oxidation

Microbial 1,2-dihydroxylation of sodium benzoate permits the rapid construction of novel inositol-amino acid hybrid structures. Both β- and γ-amino acids are accessible by means of an acylnitroso Diels-Alder cycloaddition.     

Biologically Relevant Metal-Cation Binding Induces Conformational Changes in Heparin Oligosaccharides as Measured by Ion Mobility Mass Spectrometry

Heparin interacts with many proteins and is involved in biological processes such as anticoagulation, angiogenesis, and antitumorigenic activities. These heparin-protein interactions can be influenced by the binding of various metal ions to these complexes. In particular, physiologically relevant metal cations influence heparin-protein conformations through electronic interactions inherent to this polyanion. In this study, we employed ion mobility mass spectrometry (IMMS) to observe conformational changes that occur in fully-sulfated heparin octasaccharides after the successive addition of metal ions. Our results indicate that binding of positive counter ions causes a decrease in collision cross section (CCS) measurements, thus promoting a more compact octasaccharide structure.     

Crystallisation kinetics of some archetypal ionic liquids: isothermal and non-isothermal determination of the Avrami exponent

The properties of ionic liquids give rise to applications in diverse technology areas including mechanical engineering, mining, aerospace and defence. The arbitrary physical property that defines an ionic liquid is a melting point below 100 °C, and as such, an understanding of crystallisation phenomena is extremely important. This is the first report dealing with the mechanism of crystallisation in ionic liquids. Assuming crystallisation of the ionic liquids is a thermal or mass diffusion-controlled process, the values of the isothermal Avrami exponent obtained from three different ionic liquids with three different anions and cations all indicate that growth occurs with a decreasing nucleation rate (n=1.8-2.2). For one of the ionic liquids it was possible to avoid crystallisation by fast cooling and then observe a devitrification upon heating through the glass transition. The isothermal Avrami exponent of devitrification suggested growth with an increasing nucleating rate (n=4.1), compared to a decreasing nucleation rate when crystallisation occurs on cooling from the melt (n=2.0). Two non-isothermal methods were employed to determine the Avrami exponent of devitrification. Both non-isothermal Avrami exponents were in agreement with the isothermal case (n=4.0-4.15). The applicability of JMAK theory suggests that the nucleation event in the ionic liquids selected is a random stochastic process in the volume of the material. Agreement between the isothermal and non-isothermal techniques for determining the Avrami exponent of devitrification suggests that the pre-exponential factor and the activation energy are independent of thermal history. The heating rate dependence of the glass transition enabled the calculation of the fragility index, which suggests that the ionic liquid is a "strong" glass former. This suggests that the temperature dependence of the rate constant could be close to Arrhenius, as assumed by JMAK theory. More generally, therefore, it can be concluded that there is nothing unusual about the crystallisation mechanism of the ionic liquids studied here.     

Cold heteromolecular dipolar collisions

Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule.     

'Shape effects' in metal oxide supported nanoscale gold catalysts

We report the activity of shape-controlled metal oxide (CeO(2), ZnO and Fe(3)O(4)) supported gold catalysts for the steam reforming of methanol (SRM) and the water gas shift (WGS) reactions. Metal oxide nanoshapes, prepared by controlled hydrolysis and thermolysis methods, expose different crystal surfaces, and consequently disperse and stabilize gold differently. We observe that similar to gold supported on CeO(2) shapes exposing the {110} and {111} surfaces, gold supported on the oxygen-rich ZnO {0001} and Fe(3)O(4) {111} surfaces shows higher activity for the SRM and WGS reactions. While the reaction rates vary among the Au-CeO(2), Au-ZnO and Au-Fe(3)O(4) shapes, the apparent activation energies are similar, indicating a common active site. TPR data further indicate that the reaction lightoff coincides with the activation of Au-O-M species on the surface of all three oxide supports evaluated here. Different shapes contain a different number of binding sites for the gold, imparting different overall activity.     

2‐Bromo‐1,3‐bis[2‐(2‐naphthyl)vinyl]benzene benzene hemisolvate and 9‐bromodinaphth[1,2‐a:2′,1′‐j]anthracene

2‐Bromo‐1,3‐bis[2‐(2‐naphthyl)vinyl]benzene benzene hemisolvate, C₃₀H₂₁Br·0.5C₆H₆, (I), with two formula units in the asymmetric unit, exists in the crystal structure in a conformation in which the trans (2‐naphthyl)vinyl substituents on the central bromobenzene moiety appear as nearly fully extended `wings', while 9‐bromodinaphth[1,2‐a:2′,1′‐j]anthracene, C<sub>30</sub>H<sub>17</sub>Br, (II), adopts a highly nonplanar `manta‐ray' shape, with the H atoms in the interior of the molecule within van der Waals contact distances. The packing of the significantly twisted molecules of (I) generates large voids which are filled by benzene solvent molecules, while molecules of (II) stack compactly with all C—Br bonds parallel within the stack.     

Derived categories of sheaves on singular schemes with an application to reconstruction

We prove that the bounded derived category of coherent sheaves with proper support is equivalent to the category of locally-finite, cohomological functors on the perfect derived category of a quasi-projective scheme over a field. We introduce the notions of pseudo-adjoints and Rouquier functors and study them. As an application of these ideas and results, we extend the reconstruction result of Bondal and Orlov to Gorenstein projective varieties.     

Fast computation of spectral centroids

The spectral centroid of a signal is the curve whose value at any given time is the centroid of the corresponding constant-time cross section of the signal’s spectrogram. A spectral centroid provides a noise-robust estimate of how the dominant frequency of a signal changes over time. As such, spectral centroids are an increasingly popular tool in several signal processing applications, such as speech processing. We provide a new, fast and accurate algorithm for the real-time computation of the spectral centroid of a discrete-time signal. In particular, by exploiting discrete Fourier transforms, we show how one can compute the spectral centroid of a signal without ever needing to explicitly compute the signal’s spectrogram. We then apply spectral centroids to an emerging biometrics problem: to determine a person’s heart and breath rates by measuring the Doppler shifts their body movements induce in a continuous wave radar signal. We apply our algorithm to real-world radar data, obtaining heart- and breath-rate estimates that compare well against ground truth.