Diffusion-induced instability in chemically reacting systems: Steady-state multiplicity,oscillation, and chaos

The dynamical behavior of two coupled cells or reactors is described. The cells are coupled by diffusion, e.g., through a semipermeable membrane, and the chemical reactions and initial or feed concentrations of all species are the same in the two cells. Each cell has only a single stable steady state in the absence of coupling, and the coupled system may exhibit multiple steady states, periodic oscillation, or chaos. The attractors of the coupled system may be either homogeneous (the two cells have equal concentrations) or inhomogeneous. Three two-variable kinetic models are examined: the Brusselator, a model of the chlorine dioxide-iodine-malonic acid reaction, and the Degn-Harrison model. The dynamical behavior of the coupled system is determined by the nonlinearities in the uncoupled subsystems and by two ratios, that of the diffusion constants of the two species and that of the area of the membrane to the product of the membrane thickness and the volume of a cell.     

The potential of autofluorescence for the detection of single living cells for label-free cell sorting in microfluidic systems

A novel method for studying unlabeled living mammalian cells based on their autofluorescence (AF) signal in a prototype microfluidic device is presented. When combined, cellular AF detection and microfluidic devices have the potential to facilitate high-throughput analysis of different cell populations. To demonstrate this, unlabeled cultured cells in microfluidic devices were excited with a 488 nm excitation light and the AF emission (> 505 nm) was detected using a confocal fluorescence microscope (CFM). For example, a simple microfluidic three-port glass microstructure was used together with conventional electroosmotic flow (EOF) to switch the direction of the fluid flow. As a means to test the potential of AF-based cell sorting in this microfluidic device, granulocytes were successfully differentiated from human red blood cells (RBCs) based on differences in AF. This study demonstrated the use of a simple microfabricated device to perform high-throughput live cell detection and differentiation without the need for cell-specific fluorescent labeling dyes and thereby reducing the sample preparation time. Hence, the combined use of microfluidic devices and cell AF may have many applications in single-cell analysis.     

Superspreading driven by Marangoni flow

The spontaneous spreading (called superspreading) of aqueous trisiloxane ethoxylate surfactant solutions on hydrophobic solid surfaces is a fascinating phenomenon with several practical applications. For example, the ability of trisiloxane ethoxylate surfactants to enhance the spreading of spray solutions on waxy weed leaf surfaces, such as velvetleaf (Abutilion theophrasti), makes them excellent wetting agents for herbicide applications. The superspreading ability of silicone surfactants has been known for decades, but its mechanism is still not well understood. In this paper, we suggest that the spreading of trisiloxane ethoxylates is controlled by a surface tension gradient, which forms when a drop of surfactant solution is placed on a solid surface. The proposed model suggests that, as the spreading front stretches, the surface tension increases (the surfactant concentration becomes lower) at the front relative to the top of the droplet, thereby establishing a dynamic surface tension gradient. The driving force for spreading is due to the Marangoni effect, and our experiments showed that the higher the gradient, the faster the spreading. A simple model describing the phenomenon of superspreading is presented. We also suggest that the superspreading behavior of trisiloxane ethoxylates is a consequence of the molecular configuration at the air/water surface (i.e. small and compact hydrophobic part), as shown by molecular dynamics modeling. We also found that the aggregates and vesicles formed in trisiloxane solutions do not initiate the spreading process and therefore these structures are not a requirement for the superspreading process.     

From an electron micrograph to a postage stamp

Soon following Dan Shechtman’s discovery of quasicrystals, Ágnes Csanády and her associates started producing beautiful quasicrystals of flowerlike morphology. The image of one of their specimen appeared on the Israeli postage stamp honoring Shechtman’s discovery, his Nobel Prize, and the International Year of Crystallography.     

James D. Watson 88—the discovery of the double helix was an iconic event in structural chemistry

The ingenuity of James D. Watson and Francis Crick, the convergence of the advances in X-ray crystallography, the accumulated knowledge of structural chemistry, and the breakthroughs in chemical methods of analysis led to the discovery of the double helix structure of DNA. The discovery catapulted Watson to a career that helped DNA and the applications of the knowledge about its structure triumph in biomedical sciences. Watson’s eighty-eighth birthday is an occasion to have a look at his path to success, his personality, and assess his legacy.     

Direct electrophilic monofluoromethylation

Monofluoromethyl derivatives of various nucleophiles have been synthesized using a new electrophilic monofluoromethylating reagent developed. The S-(monofluoromethyl)diarylsulfonium tetrafluoroborate has been shown to be effective for the introduction of an electrophilic monofluoromethyl group into C, S, O, N, and P nucleophiles. This methodology has been expanded for the synthesis of various biologically important compounds.     

Nanoparticles prepared by self-assembly of Chitosan and poly-γ-glutamic acid

The present paper describes the preparation and characterization of novel biodegradable nanoparticles based on self-assembly of poly-gamma-glutamic acid (γ-PGA) and chitosan (CH). The nanosystems were stable in aqueous media at low pH conditions. Solubility of the systems was determined by turbidity measurements. Surface charge and mobility were measured electrophoretically. The particle size and the size distribution of the polyelectrolyte complexes were identified by dynamic light scattering and transmission electron microscopy (TEM). It was found that the size and size distribution of the nanosystems depends on the concentrations of γ-PGA and CH solutions and their ratio as well as on the pH of the mixture and the order of addition. The diameter of individual particles was in the range of 20–285 nm measured by TEM, and the average hydrodynamic diameters were between 150 and 330 nm. These biodegradable, self-assembling stable nanocomplexes might be useful for several biomedical applications.     

Sydney Brenner (1927–2019)—One of the greats of our science on new frontiers

Structural Chemistry - Sydney Brenner was among those who created the modern science of molecular genetics. He was primarily an experimentalist yet his philosophical views on science will also have...     

Structural chemistry at Lomonosov Moscow State University: a special issue

Structural Chemistry -     

Characterization of Turbulent Structures in a Transonic Backward-Facing Step Flow

A transonic backward-facing step flow, at a free stream Mach number of 0.8 and a Reynolds number of 1.86 × 10⁵ with respect to the step height, was investigated experimentally by means of planar and stereo Particle Image Velocimetry (PIV) measurements for multiple fields of view. The primary aim of this analysis is to examine whether the large temporal variations of the reattachment location is associated with the presence of large scale coherent flow structures. The mean flow reattaches ≈6.1±0.2 times the step height downstream of the step. This value fluctuates temporally as much as ±3 step heights. Measurements of the wake flow in horizontal planes show that the strong variations of the reattachment length are associated with spanwise variations of the streamwise velocity. Two-point correlations revealed large–scale coherent regions with a length of up to 7 step heights and a dominant spanwise wave-length of 1.5…2.5 step heights. Furthermore, close to the step large structures are found, which span more than 5 step heights in spanwise direction. The Reynolds stress distribution of the separated region strongly suggests that the initial streamwise momentum is transferred to the vertical component as well as to the spanwise component in comparable portions by the deformation of the initial Kelvin-Helmholtz vortices and the generation of secondary ones. As a result, the separated shear layer is characterized by eddies of various sizes and orientations. The mean flow field only shows the primary separation bubble and a secondary recirculation region. No stationary streamwise vortices could be found for the tested Reynolds number.