Project description:Titania microspheres have attracted substantial attention for a variety of applications, including ion scavenging, catalysis, and energy generation, though most synthetic techniques are limited to a few basic morphologies and narrow size ranges. Here, an intensified microfluidic strategy for continuous synthesis of anatase titania microspheres is presented. In-flow photo crosslinking, incorporated with a flow reactor and polar aprotic solvent, enables access to precursor compositions up to an order of magnitude higher than those previously reported, with size tunability approaching two orders of magnitude. Morphological and surface area effects associated with precursor composition are explored, resulting in hollow, yolk-shell, macroporous, and dense titania microspheres containing no detectable rutile phase and possessing surface areas exceeding 350 m2 g-1 post calcination. Furthermore, effects of calcination temperature and time on the surface area, crystallinity and phase composition, and morphology of the synthesized titania microspheres are studied in detail. The synthesized microspheres are shown to remain completely in the anatase phase, even at temperatures up to 900 °C, far beyond the expected phase transition temperature. Thus, the breadth of attainable morphologies, specific surface areas, and phase compositions present a variety of intriguing substrate candidates for such applications as heterogeneous (photo) catalysis, adsorption and ion capture, electrochemistry, and photovoltaics.
Project description:Janus droplets can function as excellent templates for fabricating physically and chemically anisotropic particles. Here, we report new surfactant-laden Janus droplets with curvature controllability and enhanced stability against coalescence, suitable for fabricating shape-anisotropic polymer microparticles. Using a microfluidic flow-focusing device on a glass chip, nanoliter-sized biphasic droplets, comprising an acrylate monomer segment and a silicone-oil (SO) segment containing a surfactant, were produced in a co-flowing aqueous polyvinyl alcohol (PVA) solution. At equilibrium, the droplets formed a Janus geometry based on the minimization of interfacial energy, and each of the two Janus segments were uniform in size with coefficient-of-variation values below 3%. By varying the concentration of the surfactant in the SO phase, the curvature of the interface between the two lobes could be shifted among concave, planar, and convex shapes. In addition, the Janus droplets exhibited significantly improved stability against coalescence compared with previously reported Janus droplets carrying no surfactant that coalesced rapidly. Finally, via off-chip photopolymerization, concave-convex, planar-convex, and biconvex lens-shaped particles were fabricated.
Project description:The combustion of fossil-derived fuels has a significant impact on atmospheric carbon dioxide (CO(2)) levels and correspondingly is an important contributor to anthropogenic global climate change. Plants have evolved photosynthetic mechanisms in which solar energy is used to fix CO(2) into carbohydrates. Thus, combustion of biofuels, derived from plant biomass, can be considered a potentially carbon neutral process. One of the major limitations for efficient conversion of plant biomass to biofuels is the recalcitrant nature of the plant cell wall, which is composed mostly of lignocellulosic materials (lignin, cellulose, and hemicellulose). The heteropolymer xylan represents the most abundant hemicellulosic polysaccharide and is composed primarily of xylose, arabinose, and glucuronic acid. Microbes have evolved a plethora of enzymatic strategies for hydrolyzing xylan into its constituent sugars for subsequent fermentation to biofuels. Therefore, microorganisms are considered an important source of biocatalysts in the emerging biofuel industry. To produce an optimized enzymatic cocktail for xylan deconstruction, it will be valuable to gain insight at the molecular level of the chemical linkages and the mechanisms by which these enzymes recognize their substrates and catalyze their reactions. Recent advances in genomics, proteomics, and structural biology have revolutionized our understanding of the microbial xylanolytic enzymes. This review focuses on current understanding of the molecular basis for substrate specificity and catalysis by enzymes involved in xylan deconstruction.
Project description:A common type of cytoskeletal morphology involves multiple microtubules converging with their minus ends at the microtubule organizing center (MTOC). The cargo-motor complex will experience ballistic transport when bound to microtubules or diffusive transport when unbound. This machinery allows for sequestering and subsequent dispersal of dynein-transported cargo. The general principles governing dynamics, efficiency, and tunability of such transport in the MTOC vicinity are not fully understood. To address this, we develop a one-dimensional model that includes advective transport toward an attractor (such as the MTOC) and diffusive transport that allows particles to reach absorbing boundaries (such as cellular membranes). We calculated the mean first passage time (MFPT) for cargo to reach the boundaries as a measure of the effectiveness of sequestering (large MFPT) and diffusive dispersal (low MFPT). We show that the MFPT experiences a dramatic growth, transitioning from a low to high MFPT regime (dispersal to sequestering) over a window of cargo on-/off-rates that is close to in vivo values. Furthermore, increasing either the on-rate (attachment) or off-rate (detachment) can result in optimal dispersal when the attractor is placed asymmetrically. Finally, we also describe a regime of rare events where the MFPT scales exponentially with motor velocity and the escape location becomes exponentially sensitive to the attractor positioning. Our results suggest that structures such as the MTOC allow for the sensitive control of the spatial and temporal features of transport and corresponding function under physiological conditions.
Project description:Colloidal crystals (CCs) are periodic arrays of monodisperse microparticles. Such CCs are very attractive as they can be potentially applicable as versatile photonic devices such as reflective displays, sensors, lasers, and so forth. In this article, we describe a promising methodology for synthesizing monodisperse magnetite microparticles whose diameters are controllable in the range of 100-200 nm only by adjusting the base concentration of the reaction solution. Moreover, monodisperse magnetite microparticles in aqueous suspensions spontaneously form the CC structures under an external magnetic field, leading to the appearance of Bragg reflection colors. The reflection peak can be blue-shifted from 730 nm to 570 nm by the increase in the external magnetic field from 28 mT to 220 mT. Moreover, the reflection properties of CCs in suspension depend on the microparticle concentration in suspension and the diameter of the magnetite microparticles. Both fine-control of microparticle diameter and investigation of magneto-optical properties of CCs would contribute to the technological developments in full-color reflective displays and sensors by utilizing these monodisperse magnetite microparticles.
Project description:The Lipid A family of glycolipids, found in the outer membranes of all Gram-negative bacteria, exhibits considerable structural diversity in both lipid and glycan moieties. The lack of facile methods to prepare analogues of these natural products represents a major roadblock in understanding the relationship between their structure and immunomodulatory activities. Here we present a modular, cell-free multienzymatic platform to access these structure-activity relationships. By individually purifying 19 Escherichia coli proteins and reconstituting them in vitro in the presence of acetyl-CoA, UDP- N-acetylglucosamine, NADPH, and ATP, we have developed a system capable of synthesizing Lipid IVA, the first bioactive intermediate in the Lipid A pathway. Our reconstituted multienzyme system revealed considerable promiscuity for orthologs with distinct substrate specificity, as illustrated by swapping enzymes from distantly related cyanobacterial and Pseudomonas species. Analysis of the agonistic and antagonistic activities of the resulting products against the THP-1 human monocytic cell line revealed hitherto unrecognized trends, while opening the door to harnessing the potent biological activities of these complex glycolipid natural products.
Project description:In the context of a biorefinery, lignocellulosic materials represent an important source of raw material for the bioconversion of cellulose, hemicellulose, and lignin into value-added products, such as xylose for fermentation, oligosaccharides, and bioplastics for packaging. Among the most abundant lignocellulosic materials in Brazil, sugarcane bagasse biomass stands out, as it is rich in cellulose and hemicellulose. In this context, through an experimental design, this study developed a robust enzyme cocktail containing xylanases and accessory enzymes to complete the hydrolysis of xylan from sugarcane bagasse, obtaining a low xylose yield and concentration (9% and 1.8 g/L, respectively, observed in experiment number 16 from the complete hydrolysis of a xylan assay), a fermentable sugar that is important in the production of second-generation ethanol, and a high xylooligosaccharides (XOS) yield and concentration (93.1% and 19.6 g/L, respectively, obtained from a xylooligosaccharides production assay); in general, xylan has prebiotic activities that favor an improvement in intestinal functions, with immunological and antimicrobial actions and other benefits to human health. In addition to completely hydrolyzing the sugarcane bagasse xylan, this enzymatic cocktail has great potential to be applied in other sources of lignocellulosic biomass for the conversion of xylan into xylose and XOS due to its enzymes content, involving both main chain and pendant groups hydrolysis of hemicelluloses.
Project description:Reducing platinum group metal (PGM) loadings in fuel cells and electrolyzers is paramount for cost reductions and getting hydrogen to scale to help decarbonize the global economy. Conventional PGM nanoparticle-based ink-cast electrocatalysts lose performance at high current densities owing to mass transport resistances that arise due to the use of ionomer binders. Herein, we report the development of binder-free extended-surface thin-film platinum electrocatalysts with tunable nanoscale morphology and periodic spacing. The electrocatalysts are prepared by sputtering various loadings of platinum on Al2O3 nanostructures templated from self-assembled block copolymer (BCP) thin films on glassy carbon substrates. Testing for oxygen reduction on a rotating disk electrode setup with ultralow PGM loadings (5.8 μgPt cm-2) demonstrates electrocatalyst performance that rivals commercial platinum electrocatalysts in terms of mass activity (380 mA mgPt-1 at 0.9 V vs RHE) while surpassing commercial catalysts in terms of stability (mass activity loss: 11-13% after 20,000 potential cycles). Moreover, catalyst performance probed as a function of nanoscale feature size and morphology reveals an inverse correlation between feature size and electroactivity, as well as the superiority of cylindrical morphologies over lamellae, presenting BCP templating as a fabrication pathway toward stable, tunable catalyst geometries.
Project description:Vitrification in a dilute colloidal system needs an asymmetric particle composition (a mixture of nano and micro colloids) to materialize. The volume fraction of the large particles increases (up to ≈0.58) driven by depletion forces produced by the smaller colloids. Such entropic forces are short-ranged and attractive. We found a different type of dynamical arrest in an extremely dilute asymmetric mixture of nanovesicles and polystyrene microparticles, where energy, instead of entropy, is the main protagonist to drive the arrest. Furthermore, when the vesicles go through the gel-fluid phase transition, the mean square displacements of the microparticles suffer a sudden splitting indicating a viscous jump. If the vesicles are doped with negatively charged lipids, particles and vesicles repel each other and the rheology of the mixture becomes athermal and Newtonian. Our findings are important to understand caging phenomena in biological systems, where diverse electrostatic distributions are present.