A continuous flow cascade of multi-step catalytic reactions is a cutting-edge concept to revolutionize stepwise catalytic synthesis yet is still challenging in practical applications. Herein, a ...method for practical one-pot cascade catalysis is developed by combining Pickering emulsions with continuous flow. Our method involves co-localization of different catalytically active sub-compartments within droplets of a Pickering emulsion yielding cell-like microreactors, which can be packed in a column reactor for continuous flow cascade catalysis. As exemplified by two chemo-enzymatic cascade reactions for the synthesis of chiral cyanohydrins and chiral ester, 5 - 420 fold enhancement in the catalysis efficiency and as high as 99% enantioselectivity were obtained even over a period of 80 - 240 h. The compartmentalization effect and enriching-reactant properties arising from the biomimetic microreactor are theoretically and experimentally identified as the key factors for boosting the catalysis efficiency and for regulating the kinetics of cascade catalysis.
Controlling localization of multiple metal nanoparticles on a single support is at the cutting edge of designing cascade catalysts, but is still a scientific and technological challenge because of ...the lack of nanostructured materials that can not only host metal nanoparticles in different sub-compartments but also enable efficient molecular transport between different metals. Herein we report a multicompartmentalized mesoporous organosilica with spatially separated sub-compartments that are connected by short nanochannels. Such a unique structure allows co-localization of Ru and Pd nanoparticles in a nanoscale proximal fashion. The so designed cascade catalyst exhibits an order of magnitude activity enhancement in the sequential hydrogenation of nitroarenes to cyclohexylamines compared with its mono/bi-metallic counterparts. Crucially, an interesting phenomenon of neighboring metal-assisted hydrogenation via hydrogen spillover is observed, contributing to the significant enhancement in catalytic efficiency. The multicompartmentalized architectures along with the revealed mechanism of accelerated hydrogenation provide vast opportunity for designing efficient cascade catalysts.
Abstract
Robust millimeter-sized spherical particles with controlled compositions and microstructures hold promises of important practical applications especially in relation to continuous flow ...cascade catalysis. However, the efficient fabrication methods for producing such particles remain scare. Here, we demonstrate a liquid marble approach to fabricate robust mm-sized porous supraparticles (SPs) through the bottom-up assembly of silica nanoparticles in the presence of strength additive or surface interactions, without the need for the specific liquid-repellent surfaces used by the existing methods. As the proof of the concept, our method was exemplified by fabricating biomimetic cascade catalysts through assembly of two types of well-defined catalytically active nanoparticles. The obtained SP-based cascade catalysts work well in industrially preferred fixed-bed reactors, exhibiting excellent catalysis efficiency, controlled reaction kinetics, high enantioselectivity (99% ee) and outstanding stability (200~500 h) in the cascades of ketone hydrogenation-kinetic resolution and amine racemization-kinetic resolution. The excellent catalytic performances are attributed to the structural features, reconciling close proximity of different catalytic sites and their sufficient spatial isolation.
Abstract
The design of effective CO
2
capture materials is an ongoing challenge. Here we report a concept to overcome current limitations associated with both liquid and solid CO
2
capture materials ...by exploiting a solid-liquid hybrid superparticle (SLHSP). The fabrication of SLHSP involves assembly of hydrophobic silica nanoparticles on the liquid marble surface, and co-assembly of hydrophilic silica nanoparticles and tetraethylenepentamine within the interior of the liquid marble. The strong interfacial adsorption force and the strong interactions between amine and silica are identified to be key elements for high robustness. The developed SLHSPs exhibit excellent CO
2
sorption capacity, high sorption rate, long-term stability and reduced amine loss in industrially preferred fixed bed setups. The outstanding performances are attributed to the unique structure which hierarchically organizes the liquid and solid at microscales.
The degree of shrinkage of particle stabilised bubbles of various sizes, in a polydisperse bubble dispersion, has been investigated in the light of the finite adsorption times for the particles and ...the disproportionation kinetics of the bubbles. For the case where the system contains an abundance of particles we find a threshold radius, above which bubbles are stabilised without any significant reduction in their size. Bubbles with an initial radius below this threshold on the other hand undergo a large degree of shrinkage prior to stabilisation. As the ratio of the available particles to the bubbles is reduced, it is shown that the final bubble size, for the larger bubbles in the distribution, becomes increasingly governed by the number of particles, rather than their adsorption time per se. For systems with "adsorption controlled" shrinkage ratio, the final bubble distribution is found to be wider than the initial one, while for a "particle number controlled" case it is actually narrower. Starting from a unimodal bubble size distribution, we predict that at intermediate times, prior to the full stabilisation of all bubbles, the distribution breaks up into a bimodal one. However, the effect is transient and a unimodal final bubble size distribution is recovered, when all the bubbles are stabilised by the particles.
With the resource-intensive meat industry accounting for over 50% of food-linked emissions, plant protein consumption is an inevitable need of the hour. Despite its significance, the key barrier to ...adoption of plant proteins is their astringent off-sensation, typically associated with high friction and consequently poor lubrication performance. Herein, we demonstrate that by transforming plant proteins into physically cross-linked microgels, it is possible to improve their lubricity remarkably, dependent on their volume fractions, as evidenced by combining tribology using biomimetic tongue-like surface with atomic force microscopy, dynamic light scattering, rheology and adsorption measurements. Experimental findings which are fully supported by numerical modelling reveal that these non-lipidic microgels not only decrease boundary friction by an order of magnitude as compared to native protein but also replicate the lubrication performance of a 20:80 oil/water emulsion. These plant protein microgels offer a much-needed platform to design the next-generation of healthy, palatable and sustainable foods.
Conventionally, methanol is the solvent of choice in the synthesis of gamma-cyclodextrin metal-organic frameworks (γ-CD-MOFs), but using ethanol as a replacement could allow for a more food-grade ...synthesis condition. Therefore, the aim of the study was to compare the γ-CD-MOFs synthesised with both methanol and ethanol. The γ-CD-MOFs were characterised by scanning electron microscopy (SEM), surface area and pore measurement, Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The encapsulation efficiency (EE) and loading capacity (LC) of the γ-CD-MOFs were also determined for curcumin, using methanol, ethanol and a mixture of the two as encapsulation solvent. It was found that γ-CD-MOFs synthesised by methanol and ethanol do not differ greatly, the most significant difference being the larger crystal size of γ-CD-MOFs crystallised from ethanol. However, the change in solvent significantly influenced the EE and LC of the crystals. The higher solubility of curcumin in ethanol reduced interactions with the γ-CD-MOFs and resulted in lowered EE and LC. This suggests that different solvents should be used to deliberately manipulate the EE and LC of target compounds for better use of γ-CD-MOFs as their encapsulating and delivery agents.
Air bubbles have been formed using partially hydrophobic silica nanoparticles as the stabilizer. The particles were of primary particle size 20 nm, chemically treated to different degrees with ...dichlorodimethylsilane to render them partially hydrophobic. Above a certain bubble size range (typically 80-μm diameter), the bubbles seemed to be almost indefinitely stable, while for any size above 20 μm their stability against disproportionation is far better than bubbles stabilized by any protein film investigated in previous studies. A possible theoretical justification for this observation is presented. Bubbles could be formed by shaking water with the particles, but a much higher volume fraction of bubbles was obtained by pressurizing the aqueous phase to 5 atm overnight followed by suddenly releasing the pressure to nucleate bubbles within the silica dispersion. Sonicating the silica dispersion before nucleation also gave more bubbles, which were also found to be more stable. There appeared to be an optimum degree of surface hydrophobicity that gave maximum foamability and foam stability, where around 20−33% of the silanol groups on the silica surface had been converted to dimethylsilane groups. However, a sharp increase in stability occurred when between 1.8 and 2 mol dm-3 NaCl was also included in the aqueous phase. The change in stability due to inclusion of salt can be rationalized in terms of changes occurring in the value of the particle contact angle. The effects of increasing sonication and an optimum surface chemical treatment can be explained by the need to make the particles sufficiently hydrophobic so that they adsorb strongly enough, while at the same time minimizing their tendency to aggregate in the bulk aqueous phase, which hinders their adsorption. Furthermore, confocal laser scanning microscopy of the bubble dispersions suggests that a large volume fraction of stable bubbles is only formed when the particles adsorbed to the bubbles are also part of a spanning silica particle network in the bulk aqueous solution, forming a weak gel with a finite yield stress.
Surface texture sensation is significant for business success, in particular for solid surfaces for most of the materials; including foods. Mechanisms of roughness perception are still unknown, ...especially under different conditions such as lubricants with varying viscosities, different temperatures, or under different force loads during the observation of the surface. This work aims to determine the effect of those unknown factors, with applied sensory tests on 62 healthy participants. Roughness sensation of fingertip was tested under different lubricants including water and diluted syrup solutions at room temperature (25C) and body temperature (37C) by using simple pair‐wise comparison to observe the just noticeable difference threshold and perception levels. Additionally, in this research applied force load during roughness observation was tested with pair‐wise ranking method to illustrate its possible effect on human sensation. Obtained results showed that human's capability of roughness discrimination reduces with increased viscosity of the lubricant, where the influence of the temperature was not found to be significant. Moreover, the increase in the applied force load showed an increase in the sensitivity of roughness discrimination. Observed effects of the applied factors were also used for estimating the oral sensation of texture during eating. These findings are significant for our fundamental understanding to texture perception, and for the development of new food products with controlled textural features.
Practical applications
Texture discrimination ability, more specifically roughness discrimination capability, is a significant factor for preference and appreciation for a wide range of materials, including food, furniture, or fabric. To explore the mechanism of sensation capability through tactile senses, it is necessary to identify the relevant factors and define characteristics that dominate the process involved. The results that will be obtained under these principles will be helpful for the industry in the development and optimization of new products, especially for the individuals' with special needs. With this exploratory study, we illustrate differential thresholds of tactile senses under changing conditions of surface lubrication and applied force load. Also, the tests were carried out under different temperatures to understand the oral sensation capability. The results and correlations may provide useful information about texture sensitivity and also methodologies could be applied to general sensory studies.
The stabilization of air bubbles by hydrophobically modified silica particles has been investigated in detail. The silica particles used had a nominal primary particle size of 20 nm and were made ...hydrophobic by treatment with dichlorodimethylsilane to yield particles with varying percent grafting of alkyl chains (“% SiOR”). Contact-angle (θ) measurements of pure water droplets on flats made from compressed samples of the particles showed a steep increase in θ above ca. 20% SiOR. Other measurements also showed a significant increase in θ when the salt concentration was raised to 1−3 mol dm-3. Bubbles were formed in a sonicated dispersion of particles by suddenly lowering the pressure. Maximum stability was obtained with 33% SiOR particles and 2−3 mol dm-3 NaCl. Under these conditions, θ was around 40°. Above a threshold size of around 70 μm, bubbles were extremely stable to disproportionation and coalescence and bubble stability increased significantly with an increase in the NaCl concentration from 0.5 to 3 mol dm-3. Furthermore, rheological measurements showed that at NaCl concentrations in this range weak particle gels were formed with a finite yield stress. The strength of these gels increased with an increasing NaCl concentration between 0.5 and 3 mol dm-3 and with an increasing time of aging the dispersions, implicating this as part of the mechanism leading to an increased bubble stability in these systems. Dispersions in the absence of NaCl showed little or no foamability at all. Use of CaCl2 and Al(NO)3 at similar ionic strengths showed that equivalent stability could not be obtained with these salts. Atomic force microscopy (AFM) measurements of the adhesion between a pure (0% SiOR) silica sphere and flat showed a significant increase in the adhesion between 0.5 and 3 mol dm-3 NaCl, even though in this concentration range no significant change in the electrostatic repulsion might be expected. It is concluded that the increased particle−particle adhesion, effective hydrophobicity, and bubble-stabilization properties of the particles at high NaCl concentrations are probably due to the collapse of protruding polysilicic acid chains on the surface of the silica.
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