Iodine(III)-mediated generation of nitrogen-tethered orthoquinol acetates for the construction of oxygenated indole,quinoline, and phenanthridine alkaloid motifs

Functionalized indole and quinoline derivatives are conveniently prepared from nitrogen-tethered 2-methoxyphenols via phenyliodine(III) diacetate mediated oxidative acetoxylation, followed by a fluoride- or base-induced intramolecular nucleophilic addition reaction. This regioselective Michael-type addition step is further discussed in view of the rearrangement of orthoquinol acetate intermediates into paraquinol acetates that is sometimes observed in situ. Application of this methodology to the synthesis of a functionalized phenanthridine, and its potential for the construction of polyoxygenated lycorine-type alkaloid skeleta are here described.     

Can sonication enhance release from liquid-core capsules with a hydrogel membrane?

The objective is to investigate the influence of sonication on the mechanical and release properties of hydrogel capsules. A new fabrication process is developed to fabricate millimetric capsules made of a highly-viscous liquid core protected by a thin hyperelastic alginate membrane. At high intensities and/or long exposure times, sonication can lead to the capsule rupture, because it induces fatigue in the membrane. Below the breakup threshold, no remnant effect of sonication is, however, measured on the capsule mechanical properties. The release is studied by sonicating capsules filled with blue dextran suspended in an aqueous solution. The mass release that results from sonication is found to be proportional to the sonication duration time and pressure wave amplitude. A possible physical interpretation is that the acoustic streaming flow induced by the ultrasonic wave enhances convection in the vicinity of the capsule membrane and thus mass release. We have finally quantified the passive release subsequent to low-intensity sonications: it is on average identical to the one measured on non-sonicated capsules. Overall the membrane therefore recovers its physical and mechanical properties after sonication. If sonication leads to an increase in porosity of the capsule membrane, the increase is temporary and reverses back at the end of the ultrasonic stimulation.     

A synthetic Schlieren method for the measurement of the topography of a liquid interface

An optical method for the measurement of the instantaneous topography of the interface between two transparent fluids, named free-surface synthetic Schlieren (FS-SS), is characterised. This method is based on the analysis of the refracted image of a random dot pattern visualized through the interface. The apparent displacement field between the refracted image and a reference image obtained when the surface is flat is determined using a digital image correlation (DIC) algorithm. A numerical integration of this displacement field, based on a least square inversion of the gradient operator, is used for the reconstruction of the instantaneous surface height, allowing for an excellent spatial resolution with a low computational cost. The main limitation of the method, namely the ray crossing (caustics) due to strong curvature and/or large surface-pattern distance, is discussed. Validation experiments using a transparent solid model with a wavy surface or plane waves at a water–air interface are presented, and some additional time-resolved measurements of circular waves generated by a water drop impact are discussed.     

A Data-Driven Space-Time-Parameter Reduced-Order Model with Manifold Learning for Coupled Problems: Application to Deformable Capsules Flowing in Microchannels

An innovative data-driven model-order reduction technique is proposed to model dilute micrometric or nanometric suspensions of microcapsules, i.e., microdrops protected in a thin hyperelastic membrane, which are used in Healthcare as innovative drug vehicles. We consider a microcapsule flowing in a similar-size microfluidic channel and vary systematically the governing parameter, namely the capillary number, ratio of the viscous to elastic forces, and the confinement ratio, ratio of the capsule to tube size. The resulting space-time-parameter problem is solved using two global POD reduced bases, determined in the offline stage for the space and parameter variables, respectively. A suitable low-order spatial reduced basis is then computed in the online stage for any new parameter instance. The time evolution of the capsule dynamics is achieved by identifying the nonlinear low-order manifold of the reduced variables; for that, a point cloud of reduced data is computed and a diffuse approximation method is used. Numerical comparisons between the full-order fluid-structure interaction model and the reduced-order one confirm both accuracy and stability of the reduction technique over the whole admissible parameter domain. We believe that such an approach can be applied to a broad range of coupled problems especially involving quasistatic models of structural mechanics.     

Comparison between measurements of elasticity and free amino group content of ovalbumin microcapsule membranes: discrimination of the cross-linking degree

Gold nanoparticle-doped poly(2-vinylpyridine) (P2VP) microcapsules and foam films were synthesized and assembled at the P2VP chloroform solution/HAuCl(4) aqueous solution interface at 25 °C. It was found that Au nanoparticles with the average diameter of 2.1 nm were homogeneously embedded in and adsorbed on the walls of the capsules and foams, the nanoparticles were composed of Au(0) and Au(III) with the molar ratio of about 75/25, and the mass percent of Au elements was measured to be 19.65%. The formation of the nanostructures was attributed to the self-assembly of P2VP at the liquid/liquid interface, the simultaneous reduction of AuCl(4)(-) ions by a small amount of ethanol in the chloroform and adsorption of AuCl(4)(-) ions. After irradiated by UV-light for 1h, the average diameter of the nanoparticles was found to be 2.2 nm, and the AuCl(4)(-) ions were transformed to Au(0) completely. The catalytic performance of these composite nanostructures were evaluated by using the reduction of 4-nitrophenol (4-NP) by potassium borohydride in aqueous solutions. The catalytic activity was very high in the first cycle, decreased rapidly and slightly in the second and third cycles, respectively, due to the aggregation of some nanoparticles, and stabilized after the third cycle.     

Characterization of the mechanical properties of cross-linked serum albumin microcapsules: effect of size and protein concentration

A microfluidic technique is used to characterize the mechanical behavior of capsules that are produced in a two-step process: first, an emulsification step to form droplets, followed by a cross-linking step to encapsulate the droplets within a thin membrane composed of cross-linked proteins. The objective is to study the influence of the capsule size and protein concentration on the membrane mechanical properties. The microcapsules are fabricated by cross-linking of human serum albumin (HSA) with concentrations from 15 to 35 % (w/v). A wide range of capsule radii (～40–450 μm) is obtained by varying the stirring speed in the emulsification step. For each stirring speed, a low threshold value in protein concentration is found, below which no coherent capsules could be produced. The smaller the stirring speed, the lower the concentration can be. Increasing the concentration from the threshold value and considering capsules of a given size, we show that the surface shear modulus of the membrane increases with the concentration following a sigmoidal curve. The increase in mechanical resistance reveals a higher degree of cross-linking in the membrane. Varying the stirring speed, we find that the surface shear modulus strongly increases with the capsule radius: its increase is two orders of magnitude larger than the increase in size for the capsules under consideration. It demonstrates that the cross-linking reaction is a function of the emulsion size distribution and that capsules produced in batch through emulsification processes inherently have a distribution in mechanical resistance.