Coalescence driven self-organization of growing nanodroplets around a microcap

The coalescence between growing droplets is important for the surface coverage and spatial arrangements of droplets on surfaces. In this work, total internal reflection fluorescence (TIRF) microscopy is utilized to in-situ investigate the formation of nanodroplets around the rim of a polymer microcap, with sub-micron spatial and millisecond temporal resolution. We observe that the coalescence among droplets occurs frequently during their growth by solvent exchange. Our experimental results show that the position of the droplet from two merged droplets is related to the size of the parent droplets. The position of the coalesced droplet and the ratio of parent droplet sizes obey a scaling law, reflecting a coalescence preference based on the size inequality. As a result of droplet coalescence, the angles between the centroids of two neighbouring droplets increase with time, obeying a nearly symmetrical arrangement of droplets at various time intervals. The evolution of the position and number from coalescence of growing droplets is modelled. The mechanism for coalescence driven self-organization of growing droplets is general, applicable to microcaps of different sizes and droplets of different liquids. The understanding from this work may be valuable for positioning nanodroplets by nucleation and growth without using templates.Comment: 10 pages, 9 figure

An engineered nanosugar enables rapid and sustained glucose-responsive insulin delivery in diabetic mice

Glucose-responsive insulin-delivery platforms that are sensitive to dynamic glucose concentration fluctuations and provide both rapid and prolonged insulin release have great potential to control hyperglycemia and avoid hypoglycemia diabetes. Here, biodegradable and charge-switchable phytoglycogen nanoparticles capable of glucose-stimulated insulin release are engineered. The nanoparticles are "nanosugars" bearing glucose-sensitive phenylboronic acid groups and amine moieties that allow effective complexation with insulin (approximate to 95% loading capacity) to form nanocomplexes. A single subcutaneous injection of nanocomplexes shows a rapid and efficient response to a glucose challenge in two distinct diabetic mouse models, resulting in optimal blood glucose levels (below 200 mg dL(-1)) for up to 13 h. The morphology of the nanocomplexes is found to be key to controlling rapid and extended glucose-regulated insulin delivery in vivo. These studies reveal that the injected nanocomplexes enabled efficient insulin release in the mouse, with optimal bioavailability, pharmacokinetics, and safety profiles. These results highlight a promising strategy for the development of a glucose-responsive insulin delivery system based on a natural and biodegradable nanosugar

Surface engineering for mechanically robust superhydrophobic films

© 2016 Dr. Brendan Paul DyettThe inherent surface roughness of superhydrophobic surfaces renders them mechanically fragile and limits their use in many applications from self-cleaning to anti-fouling. With the view of improving the mechanical durability of these films several steps have been taken to both identify and understand the underlying principles for the apparent dichotomy between superhydrophobicity and mechanical durability. Rough surface coatings with variable surface roughness have been developed and examined using atomic force and electron microscopy, contact angle goniometry nanoindentation as well as industry based mechanical testing. Prepared predominately by bottom up strategies such as sol-gel processing, a diverse variety of superhydrophobic surfaces were prepared exhibiting contact angles greater than 150° and sliding angles less than 10°. Subsequently, several synthetic protocols have been developed to overcome these difficulties. Within conventional sol-gel derived coatings, by normalizing against the surface topology, the enhancement in abrasion resistance can be correlated to crosslinked polymer material property ratios H/E and H3/E2, providing a rationale for polymer choice to wear improve wear behavior in future coatings. Understanding of geometric limitations led to the development of polymer spheres prepared through emulsion synthesis which were utilized as sacrificial templates within a siloxane matrix to yield films with crater-like surface roughness. Surface roughness was controlled through the template geometry and concentration. The intrinsic hydrophobicity of the MTMS matrix provides enhanced longevity towards wear. This was subsequently improved through the development of polyhedral silsequioxane chemistry. Further design of the crater-like surface was inspired by mimicking the fascinating assembly of particles in natural materials. Hierarchical assembly of anisotropic particles to achieve mutually exclusive properties inspired work toward the preparation of biomimetic, superhydrophobic coatings predominantly from the incorporation of silica and polyaniline fibers and rods into craterlike surfaces

Formation of surface nanodroplets of viscous liquids by solvent exchange

Surface nanodroplets are essential units for many compartmentalised processes from catalysis, liquid-liquid reactions, crystallization, wetting and more. Current techniques for producing submicron droplets are mainly based on top-down approaches, which are increasingly limited as scale reduces. Herein, solvent exchange is demonstrated as a simple solution-based approach for the formation of surface nanodroplets with intermediate and extremely high viscosity (1 000 000 cSt). By solvent exchange, the viscous droplet liquid dissolves in a good solvent that is then displaced by a poor solvent to yield surface droplets for the oversaturaion pulse at the mixing front. Within controlled flow conditions, the geometry of droplets of low and intermediate viscosity liquids can be tailored on the nano and microscale by controlling the flow rate. Meanwhile for extremely viscous liquids, the droplet size is shown to be dependent on the liquid temperature. This work demonstrates that solvent exchange offers a versatile tool for the formation of droplets with a wide range of viscosity

Splitting droplets through coalescence of two different three-phase contact lines

Moving contact lines of more than two phases dictate a large number of interfacial phenomena. Despite their significance in fundamental and applied processes, the contact lines at a junction of four-phases (two immiscible liquids, a solid and gas) have been addressed only in a few investigations. Here, we report an intriguing phenomenon that follows after the four phases oil, water, solid and gas make contact through the coalescence of two different three-phase contact lines. We combine experimental studies and theoretical analyses to reveal and rationalize the dynamics exhibited upon the coalescence between the contact line of a micron-sized oil droplet and the receding contact line of a millimeter-sized water drop that covers the oil droplet on the substrate. We find that after the coalescence a four-phase contact line is formed for a brief period. However this quadruple contact line is not stable, leading to a 'droplet splitting' effect and eventually expulsion of the oil droplet from the water drop. We then show that the interfacial tension between the different phases and the viscosity of the oil droplet dictate the splitting dynamics. More viscous oils display higher resistance to the extreme deformations of the droplet induced by the instability of the quadruple contact line and no droplet expulsion is observed in such cases

Toward Superhydrophobic and Durable Coatings: Effect of Needle vs Crater Surface Architecture

Practical application of sol–gel derived superhydrophobic films is limited by the fragility of “needlelike” surface roughness. An efficient one step procedure is developed to prepare robust thin films with “craterlike” surface roughness from a methyltrimethoxysilane matrix and polymer sphere templates. The films could be readily spray coated to produce roughened surface textures, which are governed by template concentration and geometry. The effect of this on the wettability and robustness of thin films was examined in detail, revealing a rapid trade-off between the two characteristics due to variations in coating porosity

Flow-induced dissolution of femtoliter surface droplet arrays

The dissolution of liquid nanodroplets is a crucial step in many applied processes, such as separation and dispersion in the food industry, crystal formation of pharmaceutical products, concentrating and analysis in medical diagnosis, and drug delivery in aerosols. In this work, using both experiments and numerical simulations, we quantitatively study the dissolution dynamics of femtoliter surface droplets in a highly ordered array under a uniform flow. Our results show that the dissolution of femtoliter droplets strongly depends on their spatial positions relative to the flow direction, drop-to-drop spacing in the array, and the imposed flow rate. In some particular cases, the droplet at the edge of the array can dissolve about 30% faster than the ones located near the centre. The dissolution rate of the droplet increases by 60% as the inter-droplet spacing is increased from 2.5 μm to 20 μm. Moreover, the droplets close to the front of the flow commence to shrink earlier than those droplets in the center of the array. The average dissolution rate is faster for the faster flow. As a result, the dissolution time (Ti) decreases with the Reynolds number (Re) of the flow as Ti ∝ Re-3/4. The experimental results are in good agreement with the numerical simulations where the advection-diffusion equation for the concentration field is solved and the concentration gradient on the surface of the drop is computed. The findings suggest potential approaches to manipulate nanodroplet sizes in droplet arrays simply by dissolution controlled by an external flow. The obtained droplets with varying curvatures may serve as templates for generating multifocal microlenses in one array

Surface Nanodroplet‐Confined Engineering of Gold (I) ‐Thiolate Nanostructures

Abstract Gold(I)‐thiolate complexes have served as primary building blocks for diverse Au nanostructure synthesis strategies. A delicate approach to characterize and control Au(I)‐thiolate motif formation and assembly on the surface is needed as it can potentially solve challenges associated with utilizing gold nanomaterials in many applications. Here, the controllable generation of flower‐shaped surface gold nanostructures (FSGNs) is demonstrated by manipulating the formation‐assembly process of Au(I)‐dodecanethiolate motifs within nanoscale surface droplets. The morphology and structure of the resulting Au nanostructures are governed by internal convection flows and interfacial energy, modulated by the nanodroplet composition and substrate wettability. The obtained FSGNs are proven to act as versatile scaffolds for the selective generation of Au spiky nanostars. These FSGNs can also be utilized to functionalize nanodroplet‐based reactors, boosting the fluorescent intensity of Nile red (NR) fluorophores and decomposing NR via catalytic reaction. Remarkably, with FSGN functionalized droplets smaller than a radius of 500 nm, the decomposition rate of NR can reach ≈0.01 s−1. These results highlight a miniaturized, controllable, and automated method for the in situ production of 3D gold nanostructures on substrates, offering prospects for fast surface nanostructure fabrication and efficient environmental pollutant treatment

An indirect generation of 1D M^II-2,5-dihydroxybenzoquinone coordination polymers, their structural rearrangements and generation of materials with a high affinity for H₂, CO₂ and CH₄

A series of solid-state structural transformations are found to accompany desolvation of relatively simple coordination polymers to yield materials that exhibit unexpected gas sorbing properties. Reaction of 1,2,4,5-tetrahydroxybenzene with MII salts (M = Mg, or Zn) in an alcohol/water solution in the presence of air affords cis-MII(C6H2O4-II)(H2O)2·2H2O·xROH, (M = Mg, or Zn), crankshaft-like chains in which the absolute configurations of the chiral metal centres follow the pattern ⋯Δ Δ Λ Λ Δ Δ Λ Λ⋯, and are hydrogen bonded together to generate spacious channels. When crystals of the crankshaft chain are air dried the crystals undergo a single crystal-to-powder rearrangement to form linear trans-MII(C6H2O4-II)(H2O)2 chains. Further dehydration yields microporous solids that reversibly sorb H2, CH4 and CO2 with high sorption enthalpies.</p