Investigation of W/O microemulsion droplets by contrast variation light scattering

Dynamic and static light scattering experiments have been performed at various molar ratios (γ) of water to AOT and temperatures on water-in-oil (W/O) microemulsions dispersed in n-heptane, n-octane, and n-nonane. Size and shape fluctuations of microemulsion droplets are determined with very high precision because polydispersity influences the characteristic features of scattering data as well as the hydrodynamic radius withγ. Self-consistent interpretation of dynamic and static light scattering data using optical properties and packing consideration on the basis of the layered sphere model are obtained. The estimated extent of polydispersity index of 17% is found, whereas the polydispersity is independent of the alkane types. The geometrical parameters, e.g., hydrodynamic radius, area per head group of the surfactant molecule and thickness of the surfactant layer of microemulsion droplets are also estimated and compared in three different n-alkane types. The best interpretation of the temperature dependence of data has shown a transition from spherical droplets to ellipsoid aggregates with increasing temperature. Axial ratio increases with increase of temperature and the longer the alkane the larger is the axial ratio. The parameters describing the polydispersity and shape change are in agreement with theoretical and experimental results found in the literature     

Influence of hydrodynamic slip on convective transport in flow past a circular cylinder

The presence of a finite tangential velocity on a hydrodynamically slipping surface is known to reduce vorticity production in bluff body flows substantially while at the same time enhancing its convection downstream and into the wake. Here, we investigate the effect of hydrodynamic slippage on the convective heat transfer (scalar transport) from a heated isothermal circular cylinder placed in a uniform cross-flow of an incompressible fluid through analytical and simulation techniques. At low Reynolds (\({\textit{Re}}\ll 1\)) and high Péclet (\({\textit{Pe}}\gg 1\)) numbers, our theoretical analysis based on Oseen and thermal boundary layer equations allows for an explicit determination of the dependence of the thermal transport on the non-dimensional slip length \(l_s\). In this case, the surface-averaged Nusselt number, Nu transitions gradually between the asymptotic limits of \(Nu \sim {\textit{Pe}}^{1/3}\) and \(Nu \sim {\textit{Pe}}^{1/2}\) for no-slip (\(l_s \rightarrow 0\)) and shear-free (\(l_s \rightarrow \infty \)) boundaries, respectively. Boundary layer analysis also shows that the scaling \(Nu \sim {\textit{Pe}}^{1/2}\) holds for a shear-free cylinder surface in the asymptotic limit of \({\textit{Re}}\gg 1\) so that the corresponding heat transfer rate becomes independent of the fluid viscosity. At finite \({\textit{Re}}\), results from our two-dimensional simulations confirm the scaling \(Nu \sim {\textit{Pe}}^{1/2}\) for a shear-free boundary over the range \(0.1 \le {\textit{Re}}\le 10^3\) and \(0.1\le {\textit{Pr}}\le 10\). A gradual transition from the lower asymptotic limit corresponding to a no-slip surface, to the upper limit for a shear-free boundary, with \(l_s\), is observed in both the maximum slip velocity and the Nu. The local time-averaged Nusselt number \(Nu_{\theta }\) for a shear-free surface exceeds the one for a no-slip surface all along the cylinder boundary except over the downstream portion where unsteady separation and flow reversal lead to an appreciable rise in the local heat transfer rates, especially at high \({\textit{Re}}\) and Pr. At a Reynolds number of \(10^3\), the formation of secondary recirculating eddy pairs results in appearance of additional local maxima in \(Nu_{\theta }\) at locations that are in close proximity to the mean secondary stagnation points. As a consequence, Nu exhibits a non-monotonic variation with \(l_s\) increasing initially from its lowermost value for a no-slip surface and then decreasing before rising gradually toward the upper asymptotic limit for a shear-free cylinder. A non-monotonic dependence of the spanwise-averaged Nu on \(l_s\) is observed in three dimensions as well with the three-dimensional wake instabilities that appear at sufficiently low \(l_s\), strongly influencing the convective thermal transport from the cylinder. The analogy between heat transfer and single-component mass transfer implies that our results can directly be applied to determine the dependency of convective mass transfer of a single solute on hydrodynamic slip length in similar configurations through straightforward replacement of Nu and \({\textit{Pr}}\) with Sherwood and Schmidt numbers, respectively.     

Microwave‐assisted facile synthesis of propargylamine library by robust nitro functionalized cross‐linked polystyrene resin supported Cu NPs

In the present investigation, we study catalytic activity of copper nanoparticles stabilized onto a nitro functionalized polystyrene resin (Cu NPs@ Nitro‐Resin). The size of stabilized copper nanoparticles was found between 3 and 9 nm. This work reports a cost‐effective and sustainable protocol for the synthesis of propargylamines. Herein, we have developed microwave‐assisted synthesis of propargylamine from 3 components coupling of aldehyde, alkynes, and amines (A³ coupling) in truly heterogeneous catalytic system. Reaction parameters, such as solvent, catalyst concentration reaction time, and recyclability, were investigated, and reaction conditions were optimized. The present method has advantages such as environmentally benign, ease to handle, short reaction time (≈25 min), excellent yields (98%), low E‐factor (0.15), and high atom economy (94%).     

Effects of cartilaginous rings on airflow and particle transport through simplified and realistic models of human upper respiratory tracts

In the present study, computational fluid dynamics （CFD） is used to investigate inspiratory and expiratory airflow characteristics in the human upper respiratory tract for the purpose of identifying the probable locations of particle deposition and the wall injury. Computed tomography （CT） scan data was used to reconstruct a three dimensional respiratory tract from trachea to first generation bronchi. To compare, a simplified model of respiratory tract based on Weibel was also used in the study. The steady state results are obtained for an airflow rate of 45 L/min, corresponding to the heavy breathing condition. The velocity distribution, wall shear stress, static pressure and particle deposition are compared for inspiratory flows in simplified and realistic models and expiratory flows in realistic model only. The results show that the location of cartilaginous rings is susceptible to wall injury and local particle deposition.     

Promoting electrochemical conversion of CO2 to formate with rich oxygen vacancies in nanoporous tin oxides

Defect engineering, especially oxygen vacancies (O-vacancies) introduction into metal oxide materials has been proved to be an effective strategy to manipulate their surface electron exchange processes. However, quantitative investigation of O-vacancies on CO₂ electroreduction still remains rather ambiguous. Herein, a series of nanoporous tin oxide (SnO_x) materials have been prepared by thermal treatment at various temperatures and reaction conditions. The annealing temperature dependent O-vacancies property of the SnOx was revealed and attributed to the balance tunning of the desorption of oxygen species and the continous oxidation of SnO_x. The as-prepared nanoporous SnO_x with 300 °C treatment was found to be highest O-vacant material and showed an impressive CO₂RR activity and selectivity towards the conversion of CO₂ into formic acid (up to 88.6%), and superior HCOOH incomplete current density to other samples. The ideal performance of the O-vacancies rich SnO_x-300 material can be ascribed to the high delocalized electron density inducing much enhanced adsorption of CO₂ with O binding and benefiting the subsequent reduction with high selectively forming of formic acid.     

Water-soluble dendritic core-shell-type architectures based on polyglycerol for solubilization of hydrophobic drugs

Since many potential drugs are poorly water soluble, there is a high demand for solubilization agents. Here, we describe the synthesis of dendritic core-shell-type architectures based on hyperbranched polyglycerol for the solubilization of hydrophobic drugs. Amphiphilic macromolecules containing hydrophobic biphenyl groups in the core were synthesized in an efficient three- or four-step procedure by employing Suzuki-coupling reactions. These species were then used to solubilize the commercial drug nimodipine, a calcium antagonist used for the treatment of heart diseases and neurological deficits. Pyrene was also used as a hydrophobic model compound. It turned out that the transport properties of the dendritic polyglycerol derivatives, which are based on hydrophobic host-guest interactions, depend strongly on the degree and type of core functionalization. In the case of the multifunctional nimodipine, additional specific polymer-drug interactions could be tailored by this flexible core design, as detected by UV spectroscopy. The enhancement of solubilization increased 300-fold for nimodipine and 6000-fold for pyrene at a polymer concentration of 10 wt%. The sizes of the polymer-drug complexes were determined by both dynamic light scattering (DLS) experiments and transmission electron microscopy (TEM), and extremely well-defined aggregates with diameters of approximately 10 nm in the presence of a drug were observed. These findings together with a low critical aggregate concentration of 4x10(-6) mol L-1 indicate the controlled self-assembly of the presented amphiphilic dendritic core-shell-type architectures rather than a unimolecular transport behavior.     

Quasi-anomalous diffusion processes in entangled solutions of wormlike surfactant micelles

In this article, we present a detailed analysis of the dynamic properties of entangled solutions of semi-flexible, threadlike surfactant micelles. These aggregates were formed by self-association processes in aqueous solutions of cationic surfactants such as cetylpyridinium chloride (CPyCl) or cetyltrimethylammonium bromide (CTAB) after the addition of different amounts of sodium salicylate (NaSal). We performed dynamic light scattering (DLS) experiments in combination with rheological measurements in order to investigate the dynamic properties of these viscoelastic surfactant solutions. In all samples, we observed three distinct relaxation regimes: initial monoexponential decay, followed by a power-law behavior at intermediate observation times. A second monoexponential region was detected at very long times, and this terminal regime described the viscoelastic features of the samples. The fast decay mode was induced by local cooperative motions in the gellike network. The intermediate and slowest decay modes point to the existence of quasi-anomalous diffusion processes. These phenomena are characterized by linear-diffusion properties at long times, and they obeyed anomalous logarithmic slow-dynamics behavior at intermediate time zones. The anomalous diffusion properties at intermediate time scales can be induced by the bending motions of the rod-shaped micelles between two entanglement points. This regime, which was more extended at lower temperatures, was described by the power-law form of the correlation function. The power-law exponent depended on the chemical structure of the surfactants and the temperature. The power-law regime shifted toward earlier times as the gellike network evolved. The slowest mode of the correlation function coincided very well with the shear stress relaxation times of the three-dimensional, transient networks. We observed that the temperature dependence of the slowest mode followed Arrhenius laws. This result provides experimental evidence for thermally activated topological relaxation processes of random fluid phases. We obtained activation energies of approximately 30 kcal/mol, and these data coincided well with previously reported literature values, which were determined in similar surfactant solutions. Characteristic "screening lengths", over which viscous effects became important, could also be determined from the activation energy. The elastic modulus G0, calculated from the slowest mode of the correlation function, was in pretty good agreement with rheological data. The light-scattering spectra were consistent with the theoretical model of dynamical coupling of the concentration fluctuations to viscoelasticity. Since only minute sample volumes are required for advanced DLS experiments, this method to extract viscoelasticity is well suited for advanced studies of gellike biomaterials.     

Thermoelastic stability analysis of laminated composite plates: An analytical approach

The paper presents Chebyshev series based analytical solutions for the postbuckling response of the moderately thick laminated composite rectangular plates with and without elastic foundations. The plate is assumed to be subjected to in-plane mechanical, thermal and thermomechanical loadings. In-plane mechanical loading consists of uniaxial, biaxial, shear loadings and their combinations. The temperature induced loading is due to either uniform temperature or a linearly varying temperature across the thickness. The mathematical formulation is based on higher order shear deformation theory (HSDT) and von-Karman nonlinear kinematics. The elastic foundation is modeled as shear deformable with cubic nonlinearity. The thermal and mechanical properties of the composites are assumed to be temperature dependent. The quadratic extrapolation technique is used for linearization and fast converging finite double Chebyshev series is used for spatial discretization of the governing nonlinear equations of equilibrium. The effects of plate parameters and foundation parameters on buckling and postbuckling response of the plate are presented.     

Development of Nitroreductase-Activatable Fluoroquinolone Prodrugs Exhibiting Attenuated Magnesium Ion Binding

Fluoroquinolones such as levofloxacin and ciprofloxacin are potent antibiotics prescribed to treat various bacterial infections. Recent studies have also identified prominent examples as promising anti-cancer agents. However, significant off-target effects observed in human patients have precluded their wide-spread clinical use. For instance, upon systemic administration, overt toxicity toward eukaryotic organelles (i. e., mitochondria) can result to the destruction of healthy tissue. Moreover, fluoroquinolones feature a β-ketoacid motif which binds to and strips magnesium ions from cartilage, leading to rupture of the Achilles tendon. In this study, we have masked the β-ketoacid of levofloxacin and ciprofloxacin (as well as two quinolones) with a nitroreductase (NTR)-responsive warhead appended through a new self-immolative prodrug linker. The resulting β-ketoester functional group was found to be remarkably resistant toward spontaneous hydrolysis, esterase activity, as well as other ester-cleaving enzymatic systems. Further testing also reveal no cross-reactivity against commonly encountered biologically relevant analytes (e. g., ROS and thiols). Importantly, we demonstrate that upon esterification, the binding toward magnesium ions was attenuated based on an in vitro fluorescent competition assay with the unmodified parent drug.