Can electric fields drive chemistry for an aqueous microdroplet?

Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood. Using a coarse-grained electron model that describes structural organization and electron densities for water droplets without the expense of ab initio methods, we investigate the electric field distributions at the air-water interface to understand the origin of surface reactivity. We find that electric field alignments along free O–H bonds at the surface are ~16 MV/cm larger on average than that found for O–H bonds in the interior of the water droplet. Furthermore, electric field distributions can be an order of magnitude larger than the average due to non-linear coupling of intramolecular solvent polarization with intermolecular solvent modes which may contribute to even greater surface reactivity for weakening or breaking chemical bonds at the droplet surface.

Structure-function relationships in mitochondrial transcriptional condensates

Phase separation organizes many membraneless structures in cells. The functional consequences of concentrating cellular machinery into biomolecular condensates, however, is largely unclear. Here, we use in vitro reconstitutions, in vivo studies, and computational modelling to uncover structure-function relationships of mitochondrial (mt-) transcriptional condensates. In vitro, we find that the core mt-transcription machinery — consisting of POLRMT, TFAM, TFB2M, and DNA — forms viscoelastic, multi-phasic condensates. Strikingly, the rates of condensate-mediated transcription are considerably lower than equivalent reactions in bulk solution. Dampened rates are associated with reduced diffusivities of components that become kinetically arrested in non-equilibrium, vesicular condensates. Perturbation of mt-components in vivo and computational simulations recapitulate the transcription-dependent reorganizations observed in vitro. Our findings demonstrate close, bidirectional interdependence between structure and function of transcriptional condensates.

Severe Plastic Deformation and Phase Transformations in High Entropy Alloys: A Review

This review discusses an area of expertise that is at the intersection of three large parts of materials science. These are phase transformations, severe plastic deformation (SPD), and high-entropy alloys (HEA). First, SPD makes it possible to determine the borders of single-phase regions of existence of a multicomponent solid solution in HEAs. An important feature of SPD is that using these technologies, it is possible to obtain second-phase nanoparticles included in a matrix with a grain size of several tens of nanometers. Such materials have a very high specific density of internal boundaries. These boundaries serve as pathways for accelerated diffusion. As a result of the annealing of HEAs subjected to SPD, it is possible to accurately determine the border temperature of a single-phase solid solution area on the multicomponent phase diagram of the HEA. Secondly, SPD itself induces phase transformations in HEAs. Among these transformations is the decomposition of a single-phase solid solution with the formation of nanoparticles of the second phase, the formation of high-pressure phases, amorphization, as well as spinodal decomposition. Thirdly, during SPD, a large number of new grain boundaries (GBs) are formed due to the crystallites refinement. Segregation layers exist at these new GBs. The concentration of the components in GBs differs from that in the bulk solid solution. As a result of the formation of a large number of new GBs, atoms leave the bulk solution and form segregation layers. Thus, the composition of the solid solution in the volume also changes. All these processes make it possible to purposefully influence the composition, structure and useful properties of HEAs, especially for medical applications.

Directing Min protein patterns with advective bulk flow

We theoretically predict and experimentally show that the propagation direction of in vitro Min protein patterns can be controlled by a hydrodynamic flow of the bulk solution. We find downstream propagation of Min wave patterns relative to the bulk flow direction for low MinE:MinD concentration ratios, but upstream propagation for large MinE:MinD ratios, with multistability of both propagation directions in between. A theoretical model for the Min system reveals the mechanism underlying the upstream propagation and links it to the fast conformational switching of MinE in the bulk. For high MinE:MinD ratios, upstream propagation can be reproduced by a reduced model in which increased MinD bulk concentrations on the upstream side promote protein attachment and hence, propagation in that direction. For low MinE:D ratios, downstream propagation is described by the minimal model, as additionally confirmed by experiments with a non-switching MinE mutant. No advection takes place on the membrane surface where the protein patterns form, but advective bulk flow shifts the protein-concentration profiles in the bulk relative to the membrane-bound pattern. From a broader perspective, differential flows in a bulk volume relative to a surface are a relevant general feature in bulk-surface coupled systems. Our study shows how such a differential flow can control surface-pattern propagation and demonstrates how the global pattern's response may depend on specific molecular features of the reaction kinetics.

Accelerated synthesis of energetic precursor cage compounds using confined volume systems

Confined volume systems, such as microdroplets, Leidenfrost droplets, or thin films, can accelerate chemical reactions. Acceleration occurs due to the evaporation of solvent, the increase in reactant concentration, and the higher surface-to-volume ratios amongst other phenomena. Performing reactions in confined volume systems derived from mass spectrometry ionization sources or Leidenfrost droplets allows for reaction conditions to be changed quickly for rapid screening in a time efficient and cost-saving manner. Compared to solution phase reactions, confined volume systems also reduce waste by screening reaction conditions in smaller volumes prior to scaling. Herein, the condensation of glyoxal with benzylamine (BA) to form hexabenzylhexaazaisowurtzitane (HBIW), an intermediate to the highly desired energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), was explored. Five confined volume systems were compared to evaluate which technique was ideal for forming this complex cage structure. Substituted amines were also explored as BA replacements to screen alternative cage structure intermediates and evaluate how these accelerated techniques could apply to novel reactions, discover alternative reagents to form the cage compound, and improve synthetic routes for the preparation of CL-20. Ultimately, reaction acceleration is ideal for predicting the success of novel reactions prior to scaling up and determining if the expected products form, all while saving time and reducing costs. Acceleration factors and conversion ratios for each reaction were assessed by comparing the amount of product formed to the traditional bulk solution phase synthesis.

Effect of Magnesium on the Hydrophobicity of Sphalerite

The use of untreated recycled water has negative effects in the flotation of zinc sulfide ores due to the presence of dissolved species, such as magnesium and calcium. Although it has been found that magnesium is a more potent depressant than calcium, it has not been investigated in this role or for the effect of adding sodium carbonate. The results of an investigation to evaluate the effect of magnesium on the hydrophobicity of Cu-activated sphalerite conditioned with Sodium Isopropyl Xanthate (SIPX) are presented. Zeta potential of natural and Cu-activated sphalerite as a function of the conditioning pH and Cu(II) concentration, respectively, was first evaluated. Later, the effect of pH and presence of magnesium on the contact angle of Cu-activated sphalerite conditioned with SIPX was studied; it was also evaluated the effect of sodium carbonate to counteract the effect of magnesium. Cu-activation enhances the zeta potential of sphalerite up to a concentration of 5 mg/L. Contact angle tests, thermodynamic simulation, and surface analysis showed that magnesium hydroxide precipitates on the sphalerite surface at pH 9.6, decreasing its hydrophobicity. Addition of sodium carbonate as alkalinizing agent precipitates the magnesium in the form of a species that remained dispersed in the bulk solution, favoring the contact angle of Cu-activated sphalerite and, consequently, its hydrophobicity. It is concluded that the use of sodium carbonate as alkalinizing agent favors the precipitation of magnesium as hydromagnesite (Mg5(OH)2(CO3)4∙4H2O) instead of hydroxide allowing the recovery of sphalerite.

Colorimetric Sensing with Gold Nanoparticles on Electrowetting-Based Digital Microfluidics

Digital microfluidic (DMF) has been a unique tool for manipulating micro-droplets with high flexibility and accuracy. To extend the application of DMF for automatic and in-site detection, it is promising to introduce colorimetric sensing based on gold nanoparticles (AuNPs), which have advantages including high sensitivity, label-free, biocompatibility, and easy surface modification. However, there is still a lack of studies for investigating the movement and stability of AuNPs for in-site detection on the electrowetting-based digital microfluidics. Herein, to demonstrate the ability of DMF for colorimetric sensing with AuNPs, we investigated the electrowetting property of the AuNPs droplets on the hydrophobic interface of the DMF chip and examined the stability of the AuNPs on DMF as well as the influence of evaporation to the colorimetric sensing. As a result, we found that the electrowetting of AuNPs fits to a modified Young–Lippmann equation, which suggests that a higher voltage is required to actuate AuNPs droplets compared with actuating water droplets. Moreover, the stability of AuNPs was maintained during the processing of electrowetting. We also proved that the evaporation of droplets has a limited influence on the detections that last several minutes. Finally, a model experiment for the detection of Hg2+ was carried out with similar results to the detections in bulk solution. The proposed method can be further extended to a wide range of AuNPs-based detection for label-free, automatic, and low-cost detection of small molecules, biomarkers, and metal ions.

Intracellular nanoscale architecture as a master regulator of calcium carbonate crystallization in marine microalgae

Unicellular marine microalgae are responsible for one of the largest carbon sinks on Earth. This is in part due to intracellular formation of calcium carbonate scales termed coccoliths. Traditionally, the influence of changing environmental conditions on this process has been estimated using poorly constrained analogies to crystallization mechanisms in bulk solution, yielding ambiguous predictions. Here, we elucidated the intracellular nanoscale environment of coccolith formation in the model species Pleurochrysis carterae using cryoelectron tomography. By visualizing cells at various stages of the crystallization process, we reconstructed a timeline of coccolith development. The three-dimensional data portray the native-state structural details of coccolith formation, uncovering the crystallization mechanism, and how it is spatially and temporally controlled. Most strikingly, the developing crystals are only tens of nanometers away from delimiting membranes, resulting in a highly confined volume for crystal growth. We calculate that the number of soluble ions that can be found in such a minute volume at any given time point is less than the number needed to allow the growth of a single atomic layer of the crystal and that the uptake of single protons can markedly affect nominal pH values. In such extreme confinement, the crystallization process is expected to depend primarily on the regulation of ion fluxes by the living cell, and nominal ion concentrations, such as pH, become the result, rather than a driver, of the crystallization process. These findings call for a new perspective on coccolith formation that does not rely exclusively on solution chemistry.

Adsorption Mechanism of High-Concentration of Ammonium onto Chinese Natural Zeolite by Experimental Optimization and Theoretical Computation

Background Natural zeolite, abundant hierarchically porous structure aluminosilicate mineral, have high affinity to ammonium in solution. A considerable amount of literature has been published on the removal of ammonium in waters by zeolite, but mainly focused on the low-content and even trace ammonium. Few literatures were reported about the natural zeolite as adsorbent to remove high-level of ammonium in coal chemical wastewater. Therefore, adsorption mechanism of high-concentration ammonium in aqueous solution using Chinese natural zeolite was disclosed by the strategy of experimental optimization combining with Molecular Dynamics simulation. ResultsThe natural zeolite presented unique adsorption performances for high- ammonium distinguish from that of low ammonium, which were characterized as exhibiting faster adsorption rate, greater loading capacity and apparent desorption. The hybrid physical-chemical adsorption as the mechanism was induced from the adsorption kinetics and isotherm study in 4000 mg-N/L solution. Besides to the electrostatic attraction between the framework and guest ammonium exchanged by metal cations in the zeolite framework, the existence of the chemical bonding and hydrogen bonding forces was supported experimentally from the ion exchange capacity (IEC) investigation by the great disequilibrium between the total exchanged metal cations and ammonium. Moreover, the above were confirmed theoretically by the calculated results in the perspective of bonding strength in MD simulation. Considering comprehensively, we concluded physisorption dominated the initial adsorption stage as multilayer adsorption and chemisorption governed the subsequent adsorption process as monolayer form. Besides, the putative explanation for the desorption-occurrence was given that most ammonium concentrated in the channel openings physically, and transferred into the bulk solution preferentially through the mesopores and macropores. Conclusions Overall, we have demonstrated that the Chinese natural zeolite had the potential to capture high-concentration ammonium in wastewater remediation effectively. Considering with several research thinking comprehensively, this investigation enriched the adsorption mechanism research, and provided a novel insight for designing a workable approach for rapidly alleviating subsequent water decontamination processes using low-cost abundant minerals.