Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Axisymmetric stagnation point flow and mass transfer for power-law fluids

The boundary-layer equations for axisymmetric stagnation point flow of a power-law fluid are solved by a similarity transformation, and values of the wall shear rate are obtained. Theoretical expressions for local and average Sherwood numbers are derived from the convective diffusion equation for systems with high Schmidt numbers. The results can be used to predict diffusion coefficients of dilute species in fluids with specified power-law characteristics.     

Experimental measurements and computational modeling of the flow field in an idealized human oropharynx

The velocity field in the central sagittal plane of an idealized representation of the human oropharynx (HOP) during steady inspiration, simulating oral inhalation through an inhaler mouthpiece, was measured experimentally using endoscopic particle image velocimetry (PIV). Measurements were made at three flow rates: 15, 30, and 90 L/min, which correspond to a wide range of physiological conditions. Extensive tests were performed to verify the veracity of the PIV data. The flow was also modeled computationally using Reynolds-averaged Navier–Stokes (RANS) computational fluid dynamics (CFD) methods. The PIV data clearly indicate the complex nature of HOP flow, with three-dimensionality and several regions of separation and recirculation evident. Comparison of the experimental and computational results shows that, although the RANS CFD reproduces the basic features of the flow, it does not adequately capture the increased viscous effects at lower Reynolds numbers. The results demonstrate the need for more development and validation of CFD modeling, in particular RANS methods, in these flows.     

A Fluorescent Activatable AND‐Gate Chemokine CCL2 Enables In Vivo Detection of Metastasis‐Associated Macrophages

We report the novel chemical design of fluorescent activatable chemokines as highly specific functional probes for imaging subpopulations of immune cells in live tumours. Activatable chemokines behave as AND‐gates since they emit only after receptor binding and intracellular activation, showing enhanced selectivity over existing agents. We have applied this strategy to produce mCCL2‐MAF as the first probe for in vivo detection of metastasis‐associated macrophages in a preclinical model of lung metastasis. This strategy will accelerate the preparation of new chemokine‐based probes for imaging immune cell function in tumours.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Brillouin scattering of light by spin waves in ferromagnetic nanorods

We report the investigations of spin wave modes of arrays of Ni and Co nanorods using Brillouin light scattering. We have revealed the significant influence of spin wave modes along the nanorod axis in contrast to infinite magnetic nanowires. Unusual optical properties featuring an inverted Stokes/anti-Stokes asymmetry of the Brillouin scattering spectra have been observed. The spectrum of spin wave modes in the nanorod array has been calculated and compared with the experiment. Experimental observations are explained in terms of a combined numerical–analytical approach taking into account both the low aspect ratio of individual magnetic nanorods and dipolar magnetic coupling between the nanorods in the array. The optical studies of spin-wave modes in nanorod metamaterials with low aspect ratio nanorods have revealed new magnetic and magneto-optical properties compared to continuous magnetic films or infinite magnetic nanowires. Such magnetic artificial materials are important class of active metamaterials needed for prospective data storage and signal processing applications.     

Platin

Ohne Zusammenfassung     

A Square Well Atomic Potential: NO2 Treated Iron-Doped ZSM-5 Zeolite

Treating iron-doped ZSM-5 zeolite with NO₂ produced a complete change in the parameters of its ⁵⁷Fe Mössbauer spectrum. The intensity of the absorption showed a dramatic decrease at 40–70 K with smooth, but anharmonic, behavior above this temperature. The results can be interpreted in terms of the modification of the iron environment to form an approximately square-well potential. This results in an asymmetric potential in which the iron becomes frozen in one region at low temperatures.     

61Ni Mössbauer spectra of fine Ni particles

We report the first measurements of fine Ni particles from⁶¹Ni Mössbauer spectroscopy. The average hyperfine field of the 10 nm particles at 4.2K is measured to be 7.7(4) T, compared to the measured value for Ni foil of 7.5(3) T. Application of an external field of 6 T to the fine particles causes a reduction of the hyperfine splitting to 1.5(6) T, a consequence of the negative hyperfine field at Ni nuclei. These results are discussed in terms of fine particle effects.