Infrared transmission equations in a five media system: gas and liquid

Equations are proposed for transmission cells in the presence of multiple reflections and absorption which generate unwanted fringes. These influence adversely band intensity measurements. The infrared (IR) spectra generated with these equations are compared successfully with experimental spectra obtained with BaF₂, ZnSe, and Si windows in parallel mount formation having μm range air gaps. Equations are extended for integration of a variable path length such as in wedge shaped cells that are used to mitigate fringe formations but generate other odd problems such as path length determination. These equations allow the evaluation of the transmission obtained from boxcar cells whose parallelism is a little offset. This phenomenon modifies the fringe intensities. The proposed equations were used to calculate the IR spectra of pure liquid D₂O between BaF₂ and ZnSe windows with path lengths of around 25 μm and compared with experimental spectra. Since the fit was very good it indicates that the proposed equations give better optical properties of pure liquids than that presently available. This is important for liquid used as standards and in particular water used here as reference.     

Quantifying time-varying coordination of multimodal speech signals using correlation map analysis

This paper demonstrates an algorithm for computing the instantaneous correlation coefficient between two signals. The algorithm is the computational engine for analyzing the time-varying coordination between signals, which is called correlation map analysis (CMA). Correlation is computed around any pair of points in the two input signals. Thus, coordination can be assessed across a continuous range of temporal offsets and be detected even when changing over time due to temporal fluctuations. The correlation algorithm has two major features: (i) it is structurally similar to a tunable filter, requiring only one parameter to set its cutoff frequency (and sensitivity), (ii) it can be applied either uni-directionally (computing correlation based only on previous samples) or bi-directionally (computing correlation based on both previous and future samples). Computing instantaneous correlation for a range of time offsets between two signals produces a 2D correlation map, in which correlation is characterized as a function of time and temporal offset. Graphic visualization of the correlation map provides rapid assessment of how correspondence patterns progress through time. The utility of the algorithm and of CMA are exemplified using the spatial and temporal coordination of various audible and visible components associated with linguistic performance.     

Estimating health related costs and savings from balcony acoustic design for road traffic noise

A multi-faceted study is conducted with the objective of estimating the potential fiscal savings in annoyance and sleep disturbance related health costs due to providing improved building acoustic design standards. This study uses balcony acoustic treatments in response to road traffic noise as an example. The study area is the State of Queensland in Australia, where regional road traffic noise mapping data is used in conjunction with standard dose–response curves to estimate the population exposure levels. The background and the importance of using the selected road traffic noise indicators are discussed. In order to achieve the objective, correlations between the mapping indicator (L_{A10 (18 hour)}) and the dose response curve indicators (L_den and L_night) are established via analysis on a large database of road traffic noise measurement data. The existing noise exposure of the study area is used to estimate the fiscal reductions in health related costs through the application of simple estimations of costs per person per year per degree of annoyance or sleep disturbance. The results demonstrate that balcony acoustic treatments may provide a significant benefit towards reducing the health related costs of road traffic noise in a community.     

Mechanism of W(CO)6 sonolysis in diphenylmethane

The present work analyses the mechanism of W₂C/C nanocomposite formation during sonolysis of W(CO)₆ in diphenylmethane (DPhM) solutions. Carbon supported WC_x nanoparticles attract much interest as an alternative fuel cell electrocatalysts. Sonolysis of neat DPhM under the effect of 20 kHz power ultrasound in argon at 80 °C yields a sonopolymer as a solid product and acetylene, hydrogen, methane, diacetylene and benzene as gaseous products. Diacetylene is formed due to the secondary sonochemical dimerisation of acetylene obtained at the primary stage of DPhM sonolysis. FTIR and μ-Raman studies show that the sonopolymer consists of a mixture of some polymeric partially oxidized aromatic species, and disordered carbon. Sonolysis of W(CO)₆ in diphenylmethane solutions follows the first order kinetics. This process yields monodispersed 2-3 nm X-ray amorphous WC_x nanoparticles embedded in amorphous sonopolymer. The annealing of air sensitive as-prepared solids in an inert atmosphere at 600 °C causes formation of stable W₂C/C nanocomposite with W₂C average particle size in the range of 4-7 nm and hexagonal carbon fine particles with the average size of 30-40 nm. Kinetic study revealed that tungsten carbide is formed inside the cavitation bubble due to the reaction of tungsten nanoparticles originated from primary sonolysis of W(CO)₆ with acetylene produced as a result of diphenylmethane sonochemical degradation.     

Fluorescent Dynamic Covalent Polymers for DNA Complexation and Templated Assembly

Dynamic covalent polymers (DCPs) offer opportunities as adaptive materials of particular interest for targeting, sensing and delivery of biological molecules. In this view, combining cationic units and fluorescent units along DCP chains is attractive for achieving optical probes for the recognition and delivery of nucleic acids. Here, we report on the design of acylhydrazone-based DCPs combining cationic arginine units with π-conjugated fluorescent moieties based on thiophene-ethynyl-fluorene cores. Two types of fluorescent building blocks bearing neutral or cationic side groups on the fluorene moiety are considered in order to assess the role of the number of cationic units on complexation with DNA. The (chir)optical properties of the building blocks, the DCPs, and their complexes with several types of DNA are explored, providing details on the formation of supramolecular complexes and on their stability in aqueous solutions. The DNA-templated formation of DCPs is demonstrated, which provides new perspectives on the assembly of fluorescent DCP based on the nucleic acid structure.     

Authentication of Iranian Saffron (Crocus sativus) Using Stable Isotopes δ13C and δ2H and Metabolites Quantification

Saffron is a very high value-added ingredient used in the food supplement market and contains a high level of safranal. Adding synthetic safranal to saffron, which is significantly cheaper, and falsifying the origin of saffron may represent recurrent fraud. Saffron from different countries was analyzed to determine the stable isotope ratios δ¹³C and δ²H from safranal by gas chromatography coupled with isotope-ratio mass spectrometry (GC-C/P-IRMS) and the concentration of saffron metabolites with ultra-high performance liquid chromatography coupled with diode array detector (UHPLC-DAD). The isotopic analysis highlighted a higher ratio of δ²H in synthetic safranal than in natural safranal; the mean values were 36‰ (+/− 40) and −210‰ (+/− 35), respectively. The δ¹³C between Iranian, Spanish and other saffron was significantly different and represents median values of −28.62‰, −30.12‰ and −30.70‰, respectively. Moreover, linear and quadratic discriminant analyses (LDA and QDA) were computed using the two isotope ratios of safranal and the saffron metabolites. A first QDA showed that trans-crocetin and the δ¹³C of safranal, picrocrocin, and crocin C3 concentrations clearly differentiated Iranian saffron from other origins. A second model identified δ¹³C, trans-crocetin, crocin C2, crocin C3, and picrocrocin as good predictors to discriminate saffron samples from Iran, Spain, or other origins, with a total ability score classification matrix of 100% and a prediction matrix of 82.5%. This combined approach may be a useful tool to authenticate the origin of unknown saffron.     

An introduction to variational quantum algorithms for combinatorial optimization problems

4OR - Noisy intermediate-scale quantum computers (NISQ computers) are now readily available, motivating many researchers to experiment with Variational Quantum Algorithms (VQAs). Among them, the...     

Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols**

A flurry of recent research has centered on harnessing the power of nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous development of well-defined nickel (pre)catalysts with diverse structure and reactivity. In this report, we present ten different bench-stable, 18-electron, formally zero-valent nickel–olefin complexes that are competent pre-catalysts in various reactions. Our investigation includes preparations of novel, bench-stable Ni(COD)(L) complexes (COD=1,5-cyclooctadiene), in which L=quinone, cyclopentadienone, thiophene-S-oxide, and fulvene. Characterization by NMR, IR, single-crystal X-ray diffraction, cyclic voltammetry, thermogravimetric analysis, and natural bond orbital analysis sheds light on the structure, bonding, and properties of these complexes. Applications in an assortment of nickel-catalyzed reactions underscore the complementary nature of the different pre-catalysts within this toolkit.