Mass Transfer Of Molecules Research Articles

Reaction-Initiated Single-Molecule Tracking of Mass Transfer in Core-Shell Mesoporous Silica Particles.

Understanding the host-guest interactions in porous materials is of great importance in the field of separation science. Probing it at the single-molecule level uncovers the inter- and intraparticle inhomogeneity and establishes structure-property relationships for guiding the design of porous materials for better separation performance. In this work, we investigated the dynamics of host-guest interactions in core-shell mesoporous silica particles under in situ conditions by using a fluorogenic reaction-initiated single-molecule tracking (riSMT) approach. Taking advantage of the low fluorescence background, three-dimensional (3D) tracking of the dynamics of the molecules inside the mesoporous silica pore was achieved with high spatial precision. Compared to the commonly used two-dimensional (2D) tracking method, the 3D tracking results show that the diffusion coefficients of the molecules are three times larger on average. Using riSMT, we quantitatively analyzed the mass transfer of probe molecules in the mesoporous silica pore, including the fraction of adsorption versus diffusion, diffusion coefficients, and residence time. Large interparticle inhomogeneity was revealed and is expected to contribute to the peak broadening for separation application at the ensemble level. We further investigated the impact of electrostatic interaction on the mass transfer of molecules in the mesoporous silica pore and discovered that the primary effect is on the fraction rather than their diffusion rates of resorufin molecules undergoing diffusion.

Insights and Heuristics for Predicting Diffusion Rates of Chemical Warfare Agents in Zirconium Metal-Organic Frameworks.

Designing nanoporous catalysts to destroy chemical warfare agents (CWAs) and environmental contaminants requires consideration of both intrinsic catalytic activity and the mass transfer of molecules in and out of the pores. Polar adsorbates such as CWAs experience a heterogeneous environment in many metal-organic frameworks (MOFs) due to the arrangement of the metal nodes and organic linkers of the MOF. However, quantitative relationships between the pore architecture and the resulting diffusion properties of polar molecules have not been established. We used molecular dynamics simulations to calculate the diffusion coefficients of the CWA simulant dimethyl methyl phosphonate (DMMP) in a diverse set of 776 MOFs with Zr6 nodes. We developed a 4-parameter machine learning model to predict DMMP diffusivities in Zr6 MOFs and found the model to be transferable to the CWA sarin. We then developed a simplified heuristic based on the machine learning model that the node-node distance and accessible surface area should be maximized to find MOFs with rapid CWA diffusion.

Rapid Quantification of Mass Transfer Barriers in Metal–Organic Framework Crystals

Although mass transfer of molecules in and out of porous materials such as zeolites and metal–organic frameworks impacts many applications, the fast and reproducible measurement of intracrystalline...

Vapor-Stripping and Encapsulating to Construct Particles with Time-Controlled Asymmetry and Anisotropy

An innovative chemical vapor sublimation and deposition (CVSD) process was shown to produce nanoscale anisotropic hybrid materials. Taking advantage of controlled thermodynamic properties and the mass transfer of molecules, this process allowed for water vapor sublimation from an iced template/substrate and stagewise vapor deposition of poly-p-xylylene onto the sublimating ice substrate. In this study, the use of sensitive soybean agglutinin (SBA) protein tubes was demonstrated as an example to prepare the anisotropic hybrid material based on the CVSD process. The rationale of a timing parameter, Δt, was controlled to program the sublimation of the SBA-ice templates and the deposition of poly-p-xylylene during the CVSD process. As a result of this control, a stripping stage occurred, during which SBA tubes were exposed on the particle surface, and a subsequent encapsulation stage enabled the transformation of the ice templates into a nanometer-sized anisotropic hybrid material of poly-p-xylylene as the matrix with encapsulated SBA tubes. The timing parameter Δt and the controlled stripping and encapsulating stages during CVSD represent a straightforward and intriguing mechanism stemming from physical chemistry fundamentals for the fabrication of hybrid materials from sensitive molecules and with predetermined sizes and asymmetrical shapes. A simulation analysis showed consistency with the experimental results and controllability of the timing mechanism with predictable particle sizes.

Factors affecting the stability of water-oil-water emulsion films

Water-oil-water (oily) liquid films appear between the droplets in water-in-oil emulsions. Here we report results from systematic experiments, aimed to clarify how several important factors affect the stability and drainage of such oily films, in the presence of the nonionic oil-soluble surfactant Span 80. These results reveal that: (1) At Span 80 concentrations around the CMC, the film lifetime coincides with the duration of film drainage. When the oily films reach a critical thickness of around 40nm, unstable thinner black spots of thickness <10nm are formed due to attractive van der Waals forces, and the films rupture within seconds; (2) At intermediate concentrations of 3–30 times the CMC, the films are again unstable, but their lifetime increases significantly with Span 80 concentration, due to a longer drainage time and higher stability of the formed thin black spots. The increased drainage time is explained with a faster surfactant adsorption which leads to lower interfacial tension and, hence, to lower capillary pressure driving the film thinning. (3) At even higher Span 80 concentrations (around and above 100 CMC) the drainage time approaches a constant value, ≈600s. The films live much longer which is due mostly to the increased stability of the thin black films, formed after the black spot expansion. The film drainage time at intermediate and high Span concentrations agrees very well with the theoretical predictions. Surprisingly, the addition of 500mM NaCl into the aqueous phase leads to formation of non-equilibrium thick oil films, with drainage time >1h. This effect is explained with a mass transfer of molecules between the aqueous and the oil phases which keeps the oil films out of equilibrium for a long period. These results can be used to explain and control the formation and stability of water-in-oil emulsions, in the presence of nonionic oil-soluble surfactants.

Plasmodesmata “in Communicado”

Cell-to-cell communication is fundamental to multicellular life. For this to occur effectively there must be pathways and dynamic networks for communication. These might depend upon electrical or chemical signals or the mass transfer of molecules between adjacent cells. Molecular communication occurs either via an extra-cellular pathway or through physical structures, called plasmodesmata, that connect the cytoplasm of neighboring cells. Plasmodesmata bridge the rigid physical barrier presented by the cell wall to extend the symplasm from single cells to tissue domains that have functional importance for tissue growth, development, and defense. Although recent years have seen advances in our knowledge of the physical nature of PD, the trafficked molecules, and of the wider processes they affect, our knowledge of PD structure and function is still relatively rudimentary. This article will consider the technical/experimental difficulties hindering PD research and suggest priorities in the future research effort that might advance the field at a significantly faster rate.