A Fully Integrated Continuous‐Flow System for Asymmetric Catalysis: Enantioselective Hydrogenation with Supported Ionic Liquid Phase Catalysts Using Supercritical CO2 as the Mobile Phase

A continuous‐flow process based on a chiral transition‐metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO₂) as the mobile phase is presented for asymmetric catalytic transformations of low‐volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high‐pressure continuous‐flow setup, the product was isolated in analytically pure form without the use of any organic co‐solvent and with no detectable catalyst leaching. Phase‐behaviour studies and high‐pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO₂. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long‐term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L ^?1 h^?1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger‐scale application.     

Dirac reduction for nonholonomic mechanical systems and semidirect products

This paper develops the theory of Dirac reduction by symmetry for nonholonomic systems on Lie groups with broken symmetry. The reduction is carried out for the Dirac structures, as well as for the associated Lagrange–Dirac and Hamilton–Dirac dynamical systems. This reduction procedure is accompanied by reduction of the associated variational structures on both Lagrangian and Hamiltonian sides. The reduced dynamical systems obtained are called the implicit Euler–Poincaré–Suslov equations with advected parameters and the implicit Lie–Poisson–Suslov equations with advected parameters. The theory is illustrated with the help of finite and infinite dimensional examples. It is shown that equations of motion for second order Rivlin–Ericksen fluids can be formulated as an infinite dimensional nonholonomic system in the framework of the present paper.     

Aspects of trapping efficiency and matrix effects in the development of a restricted‐access‐media‐based trap‐and‐elute liquid chromatography with mass spectrometry method

Online restricted access media with liquid chromatography and tandem mass spectrometry for the direct analysis of small molecules in biological fluids represents an interesting alternative to time‐demanding traditional sample preparation techniques. In this study, important considerations concerning the development of a restricted access media with liquid chromatography and tandem mass spectrometry method for the analysis of dansylated estrogens in biological matrix are presented. Parameters influencing peak tailing and trapping efficiency were evaluated. The key factors included the ion strength of the mobile phase, a loading flow rate of the sample onto the trap column, and selection of a proper stationary phase of the trap column for a given set of analytes. These parameters have proven to be essential for minimizing any unwanted chromatographic peak tailing. The bulk derivatization of the analytes in the biological fluids and its relationship to the observed matrix effects was evaluated as well.     

A hybrid nanofluid analysis near a parabolic stretched surface

Two dimensional incompressible steady viscous nano-fluid flow with the impacts of heat generation and porous medium is examined numerically. For this objective Ti₆Al₄v are taken as nano-particles dispersed in different base fluids such as methanol, engine oil and water. Basically in this study we will compare three different nano-fluids to assess their flow behaviour and thermal performance. The flow model is developed under certain assumptions. The two dimensional non-linear PDEs are converted into non-linear ODEs with suitable transformation. The numerical procedure is adopted to find the results by using Bvp4c technique in MATLAB. Moreover, graphs are generated for various parameters against the temperature and velocity profiles. The fluid behaviour for different parameter is examined on velocity and temperature profile. It is depicted that for high values of volume fraction and curvature parameter nano-particles leads to high velocity and temperature profile. Moreover, velocity profile decreases for permeability parameter, while temperature profile enhances for heat generation parameter. The influence of Nusselt number and skin friction also assessed. The model of entropy generation is also presented.     

Prandtl Number in Classical Hard-Sphere and One-Component Plasma Fluids

The Prandtl number is evaluated for the three-dimensional hard-sphere and one-component plasma fluids, from the dilute weakly coupled regime up to a dense strongly coupled regime near the fluid-solid phase transition. In both cases, numerical values of order unity are obtained. The Prandtl number increases on approaching the freezing point, where it reaches a quasi-universal value for simple dielectric fluids of about ≃1.7. Relations to two-dimensional fluids are briefly discussed.     

Application of magnetic solid phase extraction in separation and enrichment of glycoproteins and glycopeptides

The analysis of endogenous glycoproteins and glycopeptides in human body fluids is of great importance for screening and discovering disease biomarkers with clinical significance. However, the presence of interfering substances makes the direct quantitative detection of low-abundance glycoproteins and glycopeptides in human body fluids one of the great challenges in analytical chemistry. Magnetic solid phase extraction (MSPE) has the advantages of easy preparation, low cost and good magnetic responsiveness. Magnetic adsorbents are the core of MSPE technology, and magnetic adsorbents based on different functional materials are widely used in the quantitative analysis of glycoproteins and glycopeptides in human body fluids, making it possible to analyze glycoproteins and glycopeptides with low abundance as well as multiple types, which provides a technical platform for screening and evaluating glycoproteins and glycopeptides in body fluids as disease biomarkers. In this paper, we focus on the recent advances in the application of MSPE technology and magnetic adsorbents for the separation and enrichment of glycoproteins and glycopeptides in human body fluids, and the future trends and application prospects in this field are also presented.     

Confined ferrofluid droplet in crossed magnetic fields

When a ferrofluid drop is trapped in a horizontal Hele-Shaw cell and subjected to a vertical magnetic field, a fingering instability results in the droplet evolving into a complex branched structure. This fingering instability depends on the magnetic field ramp rate but also depends critically on the initial state of the droplet. Small perturbations in the initial droplet can have a large influence on the resulting final pattern. By simultaneously applying a stabilizing (horizontal) azimuthal magnetic field, we gain more control over the mode selection mechanism. We perform a linear stability analysis that shows that any single mode can be selected by appropriately adjusting the strengths of the applied fields. This offers a unique and accurate mode selection mechanism for this confined magnetic fluid system. We present the results of numerical simulations that demonstrate that this mode selection mechanism is quite robust and “overpowers” any initial perturbations on the droplet. This provides a predictable way to obtain patterns with any desired number of fingers.     

Numerical study for the electrified instability of viscoelastic cylindrical dielectric fluid film surrounded by a conducting gas

The linear electrohydrodynamic cylindrical instability of annular Walters B^′${\mathrm{B}}^{\prime }$ viscoelastic dielectric fluid layer surrounded by a conducting gas in the presence of radial electric field is investigated. The obtained dispersion relation is found to be complicated and cannot be treated theoretically easily. Two limiting cases of interest are investigated, when the inertia is dominant, and when both the kinematic viscosity and viscoelasticity are high, and the corresponding new stability conditions are obtained for both cases. We solve the eigenvalue problem numerically using the continuation method which gives better results than the classical non-linear solvers such as Newton and Secant methods. It is found that the applied radial electric field has a dual role on the stability of the considered system, depending of the chosen wavenumbers range. Both the kinematic viscoelasticity and liquid depth are found to have stabilizing effects, while both the kinematic viscosity and surface tension have destabilizing effects on the considered system. The stability or instability breaks down for critical wavenumber values at which the growth rate vanishes. The behaviors of both the maximum growth rate and the corresponding dominant wavenumber are discussed in detail corresponding to the effect of all physical parameters. Finally a comparison between the results obtained here for Walters B^′${\mathrm{B}}^{\prime }$ viscoelastic fluids, and those obtained here too if the fluid is replaced by a Rivlin–Ericksen viscoelastic one is achieved. The limiting cases of absence of electric field and/or kinematic viscoelasticity are also investigated in detail.     

微粉化技术提高水不溶性药物溶解度

药物的微粉化可以改善颗粒的润湿性,进而提高水不溶性药物的溶解度和溶解速率。目前普遍采用的药物微粒化技术主要包括机械研磨、超临界流体过程、低温喷淋和溶剂蒸发沉积过程。本文介绍了这些微粉化制备技术的基本原理以及该类技术的应用进展。     

超临界流体化学热力学

本文简要介绍了超临界流体的基本概念和性质,评述了化学热力学在超临界萃取、超临界态化学反应、超临界流体制备材料等方面的作用和研究进展,讨论了二氧化碳-离子液体两相体系的热力学行为。