Low‐noise,vibrational phase‐sensitive chemical imaging by balanced detection RIKE

We perform a back‐to‐back comparison between two nonlinear vibrational imaging techniques: stimulated Raman scattering (SRS) and balanced detection Raman‐induced Kerr effect (BD‐RIKE). Using a compact fiber‐based laser system for generation of pump and Stokes signals, we image polymer beads as well as human hepatocytes under the same experimental conditions. We show that BD‐RIKE, despite the slightly lower signal levels, consistently offers an improved signal‐to‐noise ratio with respect to SRS, resulting in significantly higher image quality. Importantly, we observe that such quality is not affected by the static birefringence of the sample, which makes BD‐RIKE a robust and attractive alternative to SRS. We also highlight a unique advantage of the technique, which is its capability to easily access both the real and imaginary parts of the nonlinear susceptibility, thus allowing for vibrational phase imaging. The phase information can be readily obtained from BD‐RIKE with minimal experimental effort and provides an additional chemical selectivity channel for coherent Raman microscopy. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermodynamics of mechanical transduction of surface confined receptor/ligand reactions

Chemomechanics of surface stress is discussed in terms of interfacial thermodynamics. In the first section the paper shows how to quantitatively describe the chemical equilibrium of a receptor/ligand binding reaction confined at a solid-liquid interface and how the overall work of the reaction splits into chemical and surface work, that appears as a surface pressure. In the second section this thermodynamic model is applied to describe the experimental results of microcantilever bending induced by DNA hybridization occurring onto one of its faces.     

Long-lasting exponential spreading in periodically driven quantum systems

Using a dynamical model relevant to cold-atom experiments, we show that long-lasting exponential spreading of wave packets in momentum space is possible. Numerical results are explained via a pseudoclassical map, both qualitatively and quantitatively. Possible applications of our findings are also briefly discussed.     

B(1)(+)/actual flip angle and reception sensitivity mapping methods: simulation and comparison

Knowledge of the spatial distribution of transmission field B₁⁺ and reception sensitivity maps is important in high-field (≥3 T) human magnetic resonance (MR) imaging for several reasons: these include post-acquisition correction of intensity inhomogeneities, which may affect the quality of images; modeling and design of radiofrequency (RF) coils and pulses; validating theoretical models for electromagnetic field calculations; testing the compatibility with MR environment of biomedical implants. Moreover, inhomogeneities in the RF field are an essential source of error for quantitative MR spectroscopy. Recent studies have also shown that B₁⁺ and reception sensitivity maps can be used for direct calculation of tissue electrical parameters and for estimating the local specific absorption rate (SAR) in vivo.Several B₁⁺ mapping techniques have been introduced in the past few years based on actual flip angle (FA) mapping, but, to date, none has emerged as a standard. For reception sensitivity calculation, the signal intensity equation can be used where the nominal FA distribution must be replaced with the actual FA distribution calculated by one of the B₁⁺ mapping techniques.This study introduces a quantitative comparison between two known methods for B₁⁺/actual FA and reception sensitivity mapping: the double-angle method (DAM) and the fitting (FIT) method. Experimental data obtained using DAM and FIT methods are also compared with numerical simulation results.     

The use of cation exchange matrix separation coupled with ICP-MS to directly determine platinum group element (PGE) and other trace element emissions from passenger cars equipped with diesel particulate filters (DPF)

Inductively coupled plasma-mass spectrometry coupled with cation exchange matrix separation has been optimised for the direct determination of platinum group element (PGE) and trace element emissions from a diesel engine car. After matrix separation method detection limits of 1.6 ng g(-1) for Pd, 0.4 ng g(-1) for Rh and 4.3 ng g(-1) for Pt were achieved, the method was validated against the certified reference material BCR 723, urban road dust. The test vehicle was fitted with new and aged catalytic converters with and without diesel particulate filters (DPF). Samples were collected after three consecutive New European Driving Cycle (NEDC) of the particulate and "soluble" phases using a home-made sampler optimised for trace element analysis. Emission factors for the PGEs ranged from 0.021 ng km(-1) for Rh to 70.5 ng km(-1) for Pt; when a DPF was fitted, the emission factors for the PGEs actually used in the catalysts dropped by up to 97% (for Pt). Trace element emission factors were found to drop by a maximum of 92% for Ni to a minimum of 18% for Y when a DPF was fitted; a new DPF was also found to cause a reduction of up to 86% in the emission of particulate matter.     

Stochastic equilibrium assignment with variable demand: Theoretical and implementation issues

Recently, it has been pointed out that transport models should reflect all significant traveler choice behavior. In particular, trip generation, trip distribution, modal split as well as route choice should be modeled in a consistent process based on the equilibrium between transport supply and travel demand. In this paper a general fixed-point approach that allows dealing with multi-user stochastic equilibrium assignment with variable demand is presented. The main focus was on investigating the effectiveness of internal and external approaches and of different algorithmic specifications based on the method of successive averages within the internal approach. The vector demand function was assumed non-separable, non-symmetric cost functions were adopted and implementation issues, such updating step and convergence criterion, were investigated. In particular the aim was threefold: (i) compare the internal and the external approaches; (ii) investigate the effectiveness of different algorithmic specifications to solve the variable demand equilibrium assignment problem through the internal approach; (iii) investigate the incidence of the number of the links with non-separable and/or asymmetrical cost functions. The proposed analyses were carried out with respect to two real-scale urban networks regarding medium-size urban contexts in Italy.     

Determination of monohydroxylated metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) from wastewater-treatment plants

A high-performance liquid chromatography separation coupled with mass spectrometry via an electrospray interface is proposed for the determination of the hydroxylated derivatives of polycyclic aromatic hydrocarbons (OH-PAHs) in treated and untreated wastewaters and suspended solids from sewage treatment plants (STPs). The developed SPE procedure was applied to spiked wastewater samples, with recovery yields (1000?mL; 100?ng?L^?1 spiking level) in the 65–87% (RSD: 6–12%) range for the selected OH-PAHs. The limits of detections ranged between 0.3 and 3.2?ng?L^?1, depending on the selected compound and on the investigated matrix. The proposed method was applied to the determination of the selected analytes in real samples from a sewage-treatment plant (STP). The investigated OH-PAHs were detected mainly in the particulate fraction. The exhibited mean concentrations of positive samples (as the sum of dissolved and particulate matter) in the STP final effluent ranged from 15 to 68?ng?L^?1.     

HMDST as Useful Tool in Organic Synthesis: A Further Step in the Delivery of Sulfur Functionalities

Abstract

Bis(trimethylsilyl)sulfide (HMDST) was demostrated to be a very efficient reagent in the delivery of sulfur functionalities, allowing us to synthesize a wide range of thiocarbonyl compounds. The most reactive derivatives were trapped with suitable dienes, leading to the synthesis of different heterocyclic molecules with an high degree of chemo- and regioselectivity. Recently, the mildness of this methodology also allowed us to obtain particularly reactive thiooxocompounds, such as thioformylsilanes, α,β-unsaturated thioaldehydes, thioketones, thioacylsilanes, and thioacylstannanes.     

Organic Stereochemistry. Part 4

This Part 4 continues a general presentation of the principles of stereochemistry with special reference to medicinal compounds and their interactions with biological systems. Here, we discuss and illustrate two major aspects of conformational isomerism, namely a) the concept of torsional isomerism about single bonds, and b) the intertwined conformational and configurational aspects of the stereochemistry of cyclic systems. The review begins with a brief reminder of the history and thermodynamics of conformational isomerism, and goes on to explain and illustrate the conventions and graphical representations used for conformers. Examples are then examined, beginning with ethane, the simplest one, and building up to more complex cases, documenting the attractive or repulsive role of substituents. A similar approach is applied when dealing with cyclic systems, although here the presentation necessarily takes into account configurational aspects specific to cyclic systems. The pharmacological implications of the concepts discussed here will be presented in Part 6.