Two‐phase flow electrosynthesis: Comparing N‐octyl‐2‐pyrrolidone–aqueous and acetonitrile–aqueous three‐phase boundary reactions

A microfluidic double channel device is employed to study reactions at flowing liquid–liquid junctions in contact with a boron‐doped diamond (BDD) working electrode. The rectangular flow cell is calibrated for both single‐phase liquid flow and biphasic liquid–liquid flow for the case of (i) the immiscible N‐octyl‐2‐pyrrolidone (NOP)–aqueous electrolyte system and (ii) the immiscible acetonitrile–aqueous electrolyte system. The influence of flow speed and liquid viscosity on the position of the phase boundary and mass transport‐controlled limiting currents are examined. In contrast to the NOP–aqueous electrolyte case, the acetonitrile–aqueous electrolyte system is shown to behave close to ideal without ‘undercutting’ of the organic phase under the aqueous phase. The limiting current for three‐phase boundary reactions is only weakly dependent on flow rate but directly proportional to the concentration and the diffusion coefficient in the organic phase. Acetonitrile as a commonly employed synthetic solvent is shown here to allow effective three‐phase boundary processes to occur due to a lower viscosity enabling faster diffusion. N‐butylferrocene is shown to be oxidised at the acetonitrile–aqueous electrolyte interface about 12 times faster when compared with the same process at the NOP–aqueous electrolyte interface. Conditions suitable for clean two‐phase electrosynthetic processes without intentionally added supporting electrolyte in the organic phase are proposed. Copyright © 2008 John Wiley & Sons, Ltd.     

Two‐Phase Flow Characterization by Automated Digital Image Analysis. Part 2: Application of PDIA for Sizing Sprays

A series of experiments were conducted in order to assess the robustness and accuracy of a recently developed digital image analysis technique (PDIA). This paper investigates the application of the PDIA technique to the sizing of relatively small fuel droplets of diameters in the range 5 to 30 μm produced by a pressure‐swirl atomizer. The measurement performance of the PDIA system has been assessed in terms of individual object diameters and also number and volume probability density functions of diameter in comparison to phase Doppler anemometry (PDA) data obtained under identical conditions. PDIA measurements revealed good agreement with spray data obtained by PDA at a measurement location 36 diameters downstream from the nozzle orifice with differences in the arithmetic mean diameter, D₁₀ and volume mean diameter, D₃₀ of approximately 5 and 3% respectively. The PDIA technique was shown to detect the presence of very large, predominantly non‐spherical droplets whose diameters were in excess of 100 μm. These droplets, although few in number constitute a significant proportion of the total spray volume and would have otherwise been either erroneously measured or have passed through the probe volume undetected using PDA due to non‐sphericity. Smaller objects may also be measured correctly by both methods although sensitivity to signal‐to‐noise ratio, for both methods can generate spurious and contradictory errors.     

基于光学相干层析成像技术的强散射介质光学特性测量

利用光学相干层析成像技术对强散射介质的光学特性进行了测量研究.通过理论模拟分析了镜面反射条件下散射系数及各向异性因子对外差效应因子的影响.提出镜面反射情况下利用广义惠更斯菲涅尔模型提取材料光学特性的算法.通过对不同浓度的IntralipidTM溶液的测量,获得了可靠的光学散射特性实验结果,并研究了散射系数与其浓度之间的...     

Quantitative phase retrieval in X‐ray Zernike phase contrast microscopy

In recent years, increasing attention has been devoted to X‐ray phase contrast imaging, since it can provide high‐contrast images by using phase variations. Among the different existing techniques, Zernike phase contrast microscopy is one of the most popular phase‐sensitive techniques for investigating the fine structure of the sample at high spatial resolution. In X‐ray Zernike phase contrast microscopy, the image contrast is indeed a mixture of absorption and phase contrast. Therefore, this technique just provides qualitative information on the object, which makes the interpretation of the image difficult. In this contribution, an approach is proposed for quantitative phase retrieval in X‐ray Zernike phase contrast microscopy. By shifting the phase of the direct light by π/2 and 3π/2, two images of the same object are measured successively. The phase information of the object can then be quantitatively retrieved by a proper combination of the measured images. Numerical experiments were carried out and the results confirmed the feasibility of the proposed method. It is expected that the proposed method will find widespread applications in biology, materials science and so on.     

The Scattering Problem in PT‐Symmetric Periodic Structures of 1D Two‐Material Waveguide Networks

A PT‐symmetric periodic structure with two‐material waveguide networks is constructed. In this study, how changing the number of cells affects the transmission properties is investigated. The results show that the PT‐unbroken (broken) region of the system is only determined by the cell structure, regardless of the number of unit cells. This means that any system has the same exceptional points (EPs), regardless of the number of cells and as long as the cell structure is consistent. In addition, it is confirmed that the coherent perfect absorbers and lasers (CPA lasers) occur in our model. The transfer matrix method is used to derive a sufficient condition for achieving the CPA laser point. A simple, effective formula for predicting the CPA laser state in an N unit cell system is derived.     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Absorption and Scattering of Light by Silver and Gold Nanodisks and Nanoprisms

We study the influence of the shape of silver and gold nanoparticles on the spectra of absorption and scattering of the optical-range electromagnetic radiation. We perform numerical calculations of the cross sections of absorption and scattering of light on the basis of the FDTD method for the particles having the shape of a disk and a triangular prism. We establish that the positions of plasmon resonance peaks and the spectral distributions of intensities differ significantly for nanoparticles of different shapes even when the characteristic sizes of the particles are equal. The calculations carried out thus demonstrate that, along with the size and material of the plasmonic particle, its shape is yet another factor that essentially determines its optical features. The results of the study can be utilized in the development of the spectroscopic method of determining the shape of the metal nanoparticles and the quantitative estimate of their characteristic sizes.     

Kinetics and mechanisms of gas‐phase elimination of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine

The gas‐phase elimination kinetics of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine (320–380 °C; 40–150 Torr) in a seasoned reaction vessel are homogeneous, unimolecular and obey a first‐order rate law. These elimination processes involve two parallel reactions. The first gives ethanol and the corresponding 2‐ethoxyethenamine. The latter compound further decomposes to ethylene, CO and the corresponding amine. The second parallel reaction produce ethane and the corresponding ethyl ester of an α‐amino acid. The following Arrhenius expressions are given as: For 2,2‐diethoxyethyl amine For 2,2‐diethoxy‐N,N‐diethylethanamine Comparative kinetic and thermodynamic parameters of the overall, the parallel and the consecutive reactions lead to consider two types of mechanisms in terms of a concerted polar cyclic transition state structures. Copyright © 2008 John Wiley & Sons, Ltd.     

Observation of carbon‐facilitated phase transformation of titanium dioxide forming mixed‐phase titania by confocal Raman microscopy

Confocal Raman microscopy, a relatively new and advanced technique, is found to be suitable for imaging the chemical morphology below the submicrometer scale. It has been employed to probe the phase transformation of carbon‐containing titania (TiO₂) nanopowder and titania thin film subjected to laser annealing. The observation of phase transformation from the anatase phase to the rutile phase at high laser power annealing is attributed to carbon inclusion inside or on the surface of titania. Upon annealing, carbon could react with the oxygen of titania and create oxygen vacancies favoring the transformation from the anatase to the rutile phase. This study provides evidence for the carbon‐assisted phase transformation for creating carbon‐containing mixed‐phase titanium dioxide by laser annealing. We explicitly focus on the presence of carbon in the phase transformation of TiO₂ using confocal Raman microscopy. In all of the investigated samples, mixed anatase/rutile phases with carbon specifically was found at the rutile site. X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive spectroscopy (EDS) studies have been performed in addition to Raman mapping to verify the mixed‐phase titania formation. Copyright © 2010 John Wiley & Sons, Ltd.     

Using the T‐Matrix Method for Light Scattering Computations by Non‐axisymmetric Particles: Superellipsoids and Realistically Shaped Particles

Light scattering by non‐axisymmetric particles is commonly needed in particle characterization and other fields. After much work devoted to volume discretization methods to compute scattering by such particles, there is renewed interest in the T‐matrix method. We extended the null‐field method with discrete sources for T‐matrix computation and implemented the superellipsoid shape using an implicit equation. Additionally, a triangular surface patch model of a realistically shaped particle can be used for scattering computations. In this paper some exemplary results of scattering by non‐axisymmetric particles are presented.     

Variable‐temperature Raman spectro‐microscopy for a comprehensive analysis of the conformational order in PEGylated lipids

The investigation of phase transitions and associated changes in the conformational order of lipids is of importance in various research areas dealing with phenomena such as the formation and fusion of vesicles, transmembrane diffusion and membrane interactions with drugs and proteins. In this article, we have focused on the study of thermotropic phase behaviors and associated changes in the conformational order of two newly developed synthetic PEGylated lipids trademarked as QuSomes. In contrast to conventional phospholipids, this new kind of lipid forms liposomes spontaneously upon hydration, without the supply of external activation energy. Variable‐temperature Raman spectro‐microscopy has been employed in order to plot the transition temperature profiles showing the phase behavior of these new lipids composed of 1,2‐dimyristoyl‐rac‐glycerol‐3‐dodecaethylene glycol (GDM‐12) and 1,2‐distearoyl‐rac‐glycerol‐3‐triicosaethylene glycol (GDS‐23). Furthermore, several spectral indicators were calculated and correlated which allowed for the deduction of various aspects of molecular structure as well as intramolecular motion and intermolecular interactions. To confirm the observations, differential scanning calorimetry (DSC) was applied and revealed a good agreement with the Raman spectroscopy results. Finally, this information may find application in various studies including the development of lipid‐based novel substances and drug delivery systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Few‐optical‐cycle light pulses with passive carrier‐envelope phase stabilization

One of the most advanced frontiers of ultrafast optics is the control of carrier‐envelope phase (CEP) ϕ of light pulses, which enables the generation of optical waveforms with reproducible electric field profile. Such control is important for pulses with few‐optical‐cycle duration, for which a CEP variation produces a strong change in the waveform, so that strongly nonlinear optical phenomena, such as multiphoton absorption, above‐threshold ionization and high‐harmonic generation become CEP‐dependent. In particular, CEP control is the prerequisite for the production of isolated attosecond pulses. Standard laser systems generate pulses that are CEP unstable; the CEP can be stabilized using either active or passive methods. Passive, all‐optical schemes rely on difference‐frequency generation (DFG) between two pulses sharing the same CEP: in this process the phases of the two pulses add up with opposite signs, leading to cancellation of the shot‐to‐shot CEP fluctuations. This paper presents an overview of passive CEP stabilization schemes, starting from the basic concepts and progressing to the details of the practical implementations of the idea. The passive approach allows the generation of CEP‐controlled few‐optical‐cycle pulses covering a very broad range of parameters in terms of carrier frequency (from visible to mid‐IR), energy (up to several mJs) and repetition rate (up to hundreds of kHz)     

High‐throughput synchrotron X‐ray diffraction for combinatorial phase mapping

Discovery of new materials drives the deployment of new technologies. Complex technological requirements demand precisely tailored material functionalities, and materials scientists are driven to search for these new materials in compositionally complex and often non‐equilibrium spaces containing three, four or more elements. The phase behavior of these high‐order composition spaces is mostly unknown and unexplored. High‐throughput methods can offer strategies for efficiently searching complex and multi‐dimensional material genomes for these much needed new materials and can also suggest a processing pathway for synthesizing them. However, high‐throughput structural characterization is still relatively under‐developed for rapid material discovery. Here, a synchrotron X‐ray diffraction and fluorescence experiment for rapid measurement of both X‐ray powder patterns and compositions for an array of samples in a material library is presented. The experiment is capable of measuring more than 5000 samples per day, as demonstrated by the acquisition of high‐quality powder patterns in a bismuth–vanadium–iron oxide composition library. A detailed discussion of the scattering geometry and its ability to be tailored for different material systems is provided, with specific attention given to the characterization of fiber textured thin films. The described prototype facility is capable of meeting the structural characterization needs for the first generation of high‐throughput material genomic searches.     

Rotational disorder in 2‐piperidyl‐5‐nitro‐6 ‐methylpyridine: structural phase transition and its vibrational characteristics

X‐ray diffraction (XRD) studies have shown that 2‐piperidyl‐5‐nitro‐6‐methylpyridine, C₁₁H₁₅N₃O₂, undergoes a structural phase transition at T = 240 K. The room temperature structure is tetragonal, space group I4₁/a, with the unit‐cell dimensions a = 13.993(2) and c = 23.585(5) Å. The pyridine ring takes trans conformation with respect to the piperidine unit. While pyridine is well ordered, the piperidine moiety shows apparent disorder resulting from a libration about the linking N C bond. The low‐temperature phase is monoclinic, space group I2/a. Contraction of the unit‐cell volume by 2.3% at 170 K enables the C H···O linkage between the molecules of the neighbouring stacks. As result, the asymmetric unit becomes bi‐molecular. The thermal librations of the piperidine and methyl groups become considerably reduced at 170 K and nearly fully reduced at about 100 K. The IR spectra and polarised Raman spectra agree with the X‐ray structure and confirm the disorder effect on the piperidine ring. The assignment of the bands observed was made on the basis of DFT chemical quantum calculations. Copyright © 2008 John Wiley & Sons, Ltd.     

Gas‐phase Acidities of 2‐Aryl‐2‐chloro‐1,1,1‐trifluoroethanes and Related Compounds. Experimental and Computational Studies

The gas‐phase acidities (GA) of 2‐aryl‐2‐chloro‐1,1,1‐trifluoroethanes ( 1a ), 2‐aryl‐2‐fluoro‐1,1,1‐trifluoroethanes ( 2a ), and related compounds, XC₆H₄CH(Z)R where Z = Cl ( 1 ) or F ( 2 ) and R = C₂F₅ ( b ), t‐C₄F₉ ( c ), C(CF₃)₂C₂F₅ ( d ), C(CF₃)₂Me ( e ), Me ( f ), H ( g ), were investigated experimentally and computationally. On the basis of an excellent linear correlation (R² > 0.99) of acidities of 1c , 1d , 1e , 1f and 2c , 2d , 2e , 2f where there is no fluorine atom at β‐position to the deprotonation site with the corrected number of fluorine atoms contained in the fluorinated alkyl group, the extent of β‐fluorine negative hyperconjugation of the CF₃ and C₂F₅ groups (ΔG^o_β‐F) was evaluated. The GA_el values given by subtraction ΔG^o_β‐F from the apparent GA value were considered to represent the electronic effect of the substituent X. The substituent effects on the GA_el values and GA values for 1c , 1d , 1e , 1f and 2c , 2d , 2e , 2f were successfully analyzed in terms of the Yukawa–Tsuno equation. The variation of resonance demand parameter r^? with the R group observed for various XC₆H₄CH(Z)R was linearly related to the GA (GA_el) value of the respective phenyl‐substituted fluorinated alkanes. On the other hand, the corresponding correlation for the ρ values provided three lines for ArCH(Cl)R, ArCH(F)R and ArCH₂R, respectively. These results supported our previous conclusion that the r^? and ρ values are governed by the thermodynamic stability of the parent ion (ring substituent = H). Other factors arising from an atom bonded to the acidic center also influence the ρ value. Copyright © 2016 John Wiley & Sons, Ltd.     

Alignment of low‐dose X‐ray fluorescence tomography images using differential phase contrast

X‐ray fluorescence nanotomography provides unprecedented sensitivity for studies of trace metal distributions in whole biological cells. Dose fractionation, in which one acquires very low dose individual projections and then obtains high statistics reconstructions as signal from a voxel is brought together (Hegerl & Hoppe, 1976), requires accurate alignment of these individual projections so as to correct for rotation stage runout. It is shown here that differential phase contrast at 10.2 keV beam energy offers the potential for accurate cross‐correlation alignment of successive projections, by demonstrating that successive low dose, 3 ms per pixel, images acquired at the same specimen position and rotation angle have a narrower and smoother cross‐correlation function (1.5 pixels FWHM at 300 nm pixel size) than that obtained from zinc fluorescence images (25 pixels FWHM). The differential phase contrast alignment resolution is thus well below the 700 nm × 500 nm beam spot size used in this demonstration, so that dose fractionation should be possible for reduced‐dose, more rapidly acquired, fluorescence nanotomography experiments.     

Real-time coloured visualization of phase flows by the schlieren method

A coloured real-time visualizer of optical inhomogeneities comprising a bichromatic schlieren system, video camera and colour monitor has been developed. The schlieren system represents a function Foucault-Hilbert transformation provided with an amplitude spatial frequency filter, or a quadrant Foucault knife edge. Two colour-coded complementary Toepler-grams are obtained in the exit plane of this schlieren system. Their summed image is then recorded by the video camera and displayed on the screen of the colour monitor. The schlieren photograph of internal gravity waves, generated by the cylindrical body motion in the reservoir filled with the stratified liquid, is presented.