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1.  Control of initiation, rate, and routing of spontaneous capillary-driven flow of liquid droplets through microfluidic channels on SlipChip 
Langmuir  2012;28(3):1931-1941.
This paper describes the use of capillary pressure to initiate and control the rate of spontaneous liquid-liquid flow through microfluidic channels. In contrast to flow driven by external pressure, flow driven by capillary pressure is dominated by interfacial phenomena and is exquisitely sensitive to the chemical composition and geometry of the fluids and channels. A step-wise change in capillary force was initiated on a hydrophobic SlipChip by slipping a shallow channel containing an aqueous droplet into contact with a slightly deeper channel filled with immiscible oil. This action induced spontaneous flow of the droplet into the deeper channel. A model predicting the rate of spontaneous flow was developed based on the balance of net capillary force with viscous flow resistance, using as inputs the liquid-liquid surface tension, the advancing and receding contact angles at the three-phase aqueous-oil-surface contact line, and the geometry of the devices. The impact of contact angle hysteresis, the presence or absence of a lubricating oil layer, and adsorption of surface-active compounds at liquid-liquid or liquid-solid interfaces were quantified. Two regimes of flow spanning a 104-fold range of flow rates were obtained and modeled quantitatively, with faster (mm/s) flow obtained when oil could escape through connected channels as it was displaced by flowing aqueous solution, and slower (micrometer/s) flow obtained when oil escape was mostly restricted to a μm-scale gap between the plates of the SlipChip (“dead-end flow”). Rupture of the lubricating oil layer (reminiscent of a Cassie-Wenzel transition) was proposed as a cause of discrepancy between the model and the experiment. Both dilute salt solutions and complex biological solutions such as human blood plasma could be flowed using this approach. We anticipate that flow driven by capillary pressure will be useful for design and operation of flow in microfluidic applications that do not require external power, valves, or pumps, including on SlipChip and other droplet- or plug-based microfluidic devices. In addition, this approach may be used as a sensitive method of evaluating interfacial tension, contact angles and wetting phenomena on chip.
doi:10.1021/la204399m
PMCID: PMC3271727  PMID: 22233156
2.  Influence of Cuticle Nanostructuring on the Wetting Behaviour/States on Cicada Wings 
PLoS ONE  2012;7(4):e35056.
The nanoscale protrusions of different morphologies on wing surfaces of four cicada species were examined under an environmental scanning electron microscope (ESEM). The water contact angles (CAs) of the wing surfaces were measured along with droplet adhesion values using a high-sensitivity microelectromechanical balance system. The water CA and adhesive force measurements obtained were found to relate to the nanostructuring differences of the four species. The adhesive forces in combination with the Cassie-Baxter and Wenzel approximations were used to predict wetting states of the insect wing cuticles. The more disordered and inhomogeneous surface of the species Leptopsalta bifuscata demonstrated a Wenzel type wetting state or an intermediate state of spreading and imbibition with a CA of 81.3° and high adhesive force of 149.5 µN. Three other species (Cryptotympana atrata, Meimuna opalifer and Aola bindusara) exhibited nanostructuring of the form of conically shaped protrusions, which were spherically capped. These surfaces presented a range of high adhesional values; however, the CAs were highly hydrophobic (C. atrata and A. bindusara) and in some cases close to superhydrophobic (M. opalifer). The wetting states of A. bindusara, C. atrata and M. opalifer (based on adhesion and CAs) are most likely represented by the transitional region between the Cassie-Baxter and Wenzel approximations to varying degrees.
doi:10.1371/journal.pone.0035056
PMCID: PMC3335046  PMID: 22536351
3.  Hierarchically structured superhydrophobic flowers with low hysteresis of the wild pansy (Viola tricolor) – new design principles for biomimetic materials 
Summary
Hierarchically structured flower leaves (petals) of many plants are superhydrophobic, but water droplets do not roll-off when the surfaces are tilted. On such surfaces water droplets are in the “Cassie impregnating wetting state”, which is also known as the “petal effect”. By analyzing the petal surfaces of different species, we discovered interesting new wetting characteristics of the surface of the flower of the wild pansy (Viola tricolor). This surface is superhydrophobic with a static contact angle of 169° and very low hysteresis, i.e., the petal effect does not exist and water droplets roll-off as from a lotus (Nelumbo nucifera) leaf. However, the surface of the wild pansy petal does not possess the wax crystals of the lotus leaf. Its petals exhibit high cone-shaped cells (average size 40 µm) with a high aspect ratio (2.1) and a very fine cuticular folding (width 260 nm) on top. The applied water droplets are in the Cassie–Baxter wetting state and roll-off at inclination angles below 5°. Fabricated hydrophobic polymer replicas of the wild pansy were prepared in an easy two-step moulding process and possess the same wetting characteristics as the original flowers. In this work we present a technical surface with a new superhydrophobic, low adhesive surface design, which combines the hierarchical structuring of petals with a wetting behavior similar to that of the lotus leaf.
doi:10.3762/bjnano.2.27
PMCID: PMC3148064  PMID: 21977435
anti-adhesive; petal effect; petal structures; polymer replication; superhydrophobic
4.  Under-water superoleophobic Glass: Unexplored role of the surfactant-rich solvent 
Scientific Reports  2013;3:1862.
Preparing low energy liquid-repellant surfaces (superhydrophobic or superoleophobic) have attracted tremendous attention of late. In all these studies, the necessary liquid repellency is achieved by irreversible micro-nano texturing of the surfaces. Here we show for the first time that a glass surface, placed under water, can be made superoleophobic (with unprecedented contact angles close to 180 degrees and roll off angles only a few fractions of 1 degree) by merely changing the surfactant content of the water medium in which the oil (immiscible in water) has been dispersed. Therefore, we propose a paradigm shift in efforts to achieve liquid-repellant systems, namely, altering the solvent characteristics instead of engineering the surfaces. The effect occurs for a surfactant concentration much larger than the critical micelle concentration, and is associated to strong adsorption of surfactant molecules at the solid surface, triggering an extremely stable Cassie-Baxter like conformation of the oil droplets.
doi:10.1038/srep01862
PMCID: PMC3659319  PMID: 23689477
5.  Immobilization of Polymer-Decorated Liquid Crystal Droplets on Chemically Tailored Surfaces 
We demonstrate that the assembly of an amphiphilic polyamine on the interfaces of micrometer-sized droplets of a thermotropic liquid crystal (LC) dispersed in aqueous solutions can be used to facilitate the immobilization of LC droplets on chemically functionalized surfaces. Polymer 1 was designed to contain both hydrophobic (alkyl-functionalized) and hydrophilic (primary and tertiary amine-functionalized) side chain functionality. The assembly of this polymer at the interfaces of aqueous dispersions of LC droplets was achieved by spontaneous adsorption of polymer from aqueous solution. Polymer adsorption triggered transitions in the orientational ordering of the LCs, as observed by polarized light and bright-field microscopy. We demonstrate that the presence of polymer 1 on the interfaces of these droplets can be exploited to immobilize LC droplets on planar solid surfaces through covalent bond formation (e.g., for surfaces coated with polymer multilayers containing reactive azlactone functionality) or through electrostatic interactions (e.g., for surfaces coated with multilayers containing hydrolyzed azlactone functionality). Characterization of immobilized LC droplets by polarized, fluorescence, and laser scanning confocal microscopy revealed the general spherical shape of the polymer-coated LC droplets to be maintained after immobilization, and that immobilization led to additional ordering transitions within the droplets that was dependent on the nature of the surfaces with which they were in contact. Polymer 1-functionalized LC droplets were not immobilized on polymer multilayers treated with poly(ethylene imine) (PEI). We demonstrate that the ability to design surfaces that promote or prevent the immobilization of polymer-functionalized LC droplets can exploited to pattern the immobilization of LC droplets on surfaces. The results of this investigation provide the basis of an approach that could be used to tailor the properties of dispersed LC emulsions and to immobilize these droplets on functional surfaces of interest in a broad range of fundamental and applied contexts.
doi:10.1021/la100376u
PMCID: PMC2883006  PMID: 20405867
6.  Superhydrophobic Surface Based on a Coral-Like Hierarchical Structure of ZnO 
PLoS ONE  2010;5(12):e14475.
Background
Fabrication of superhydrophobic surfaces has attracted much interest in the past decade. The fabrication methods that have been studied are chemical vapour deposition, the sol-gel method, etching technique, electrochemical deposition, the layer-by-layer deposition, and so on. Simple and inexpensive methods for manufacturing environmentally stable superhydrophobic surfaces have also been proposed lately. However, work referring to the influence of special structures on the wettability, such as hierarchical ZnO nanostructures, is rare.
Methodology
This study presents a simple and reproducible method to fabricate a superhydrophobic surface with micro-scale roughness based on zinc oxide (ZnO) hierarchical structure, which is grown by the hydrothermal method with an alkaline aqueous solution. Coral-like structures of ZnO were fabricated on a glass substrate with a micro-scale roughness, while the antennas of the coral formed the nano-scale roughness. The fresh ZnO films exhibited excellent superhydrophilicity (the apparent contact angle for water droplet was about 0°), while the ability to be wet could be changed to superhydrophobicity after spin-coating Teflon (the apparent contact angle greater than 168°). The procedure reported here can be applied to substrates consisting of other materials and having various shapes.
Results
The new process is convenient and environmentally friendly compared to conventional methods. Furthermore, the hierarchical structure generates the extraordinary solid/gas/liquid three-phase contact interface, which is the essential characteristic for a superhydrophobic surface.
doi:10.1371/journal.pone.0014475
PMCID: PMC3012683  PMID: 21209931
7.  Non-Contaminating Camouflage: Multifunctional Skin Microornamentation in the West African Gaboon Viper (Bitis rhinoceros) 
PLoS ONE  2014;9(3):e91087.
The West African Gaboon viper (Bitis rhinoceros) has an extraordinary coloration of pale brown and velvety black markings. The velvety black appearance is caused by a unique hierarchical surface structures which was not found on the pale brown scales. In the present study we examined the wettability of the vipeŕs scales by measuring contact angles of water droplets. Velvet black scale surfaces had high static contact angles beyond 160° and low roll-off angles below 20° indicating an outstanding superhydrophobicity. Our calculations showed that the Cassie-Baxter model describes well wettability effects for these surfaces. Self-cleaning capabilities were determined by contaminating the scales with particles and fogging them until droplets formed. Black scales were clean after fogging, while pale scales stayed contaminated. Black scales feature multifunctional structures providing not only water-repellent but also self-cleaning properties. The pattern of nanoridges can be used as a model for surface-active technical surfaces.
doi:10.1371/journal.pone.0091087
PMCID: PMC3944882  PMID: 24599379
8.  Spontaneous Formation of Water Droplets at Oil-Solid Interfaces 
We report observations of spontaneous formation of micrometer-sized water droplets within micrometer-thick films of a range of different oils (isotropic and nematic 4-cyano-4’-pentylbiphenyl (5CB), and silicone, olive and corn oil) that are supported on glass substrates treated with octadecyltrichlorosilane (OTS) and immersed under water. Confocal imaging was used to determine that the water droplets nucleate and grow at the interface between the oils and OTS-treated glass with a contact angle of ~130°. A simple thermodynamic model based on macroscopic interfacial energetic arguments consistent with the contact angle of 130°, however, fails to account for the spontaneous formation of the water droplets. ζ-potential measurements performed with OTS-treated glass (− 59.0 ± 16.4 mV) and hydrophobic monolayers formed on gold films (2.0 ± 0.7 mV), when combined with the observed absence of droplet formation under films of oil supported on the latter surfaces, suggest that the charge of the oil-solid interface promotes partitioning of water to the interfacial region. The hydrophobic nature of the OTS-treated glass promotes dewetting of water accumulated in the interfacial region into droplets (a thin film of water is seen to form on bare glass). The inhibitory effect on droplet formation of both salt (NaCl) and sucrose (0.1mM to 500mM) added to the aqueous phase was similar, indicating that both solutes lower the chemical potential of the bulk water (osmotic effect) sufficiently to prevent partitioning of the water to the interface between the oil and supporting substrates. These results suggest that charged, hydrophobic surfaces can provide routes to spontaneous formation of surface-supported, water-in-oil emulsions.
doi:10.1021/la101740p
PMCID: PMC2951552  PMID: 20712383
emulsions; interfaces; spontaneous emulsification; water droplets; interfacial droplets; octadecyltrichlorosilane (OTS); monolayers; liquid crystal; isotropic oil
9.  Sorting of droplets by migration on structured surfaces 
Summary
Background: Controlled transport of microdroplets is a topic of interest for various applications. It is well known that liquid droplets move towards areas of minimum contact angle if placed on a flat solid surface exhibiting a gradient of contact angle. This effect can be utilised for droplet manipulation. In this contribution we describe how controlled droplet movement can be achieved by a surface pattern consisting of cones and funnels whose length scales are comparable to the droplet diameter.
Results: The surface energy of a droplet attached to a cone in a symmetry-preserving way can be smaller than the surface energy of a freely floating droplet. If the value of the contact angle is fixed and lies within a certain interval, then droplets sitting initially on a cone can gain energy by moving to adjacent cones.
Conclusion: Surfaces covered with cone-shaped protrusions or cavities may be devised for constructing “band-conveyors” for droplets. In our approach, it is essentially the surface structure which is varied, not the contact angle. It may be speculated that suitably patterned surfaces are also utilised in biological surfaces where a large variety of ornamentations and surface structuring are often observed.
doi:10.3762/bjnano.2.25
PMCID: PMC3148036  PMID: 21977433
microdroplets; microfluidics; surface; surface energy; surface structures
10.  Understanding the wetting properties of nanostructured selenium coatings: the role of nanostructured surface roughness and air-pocket formation 
Wetting properties of biomaterials, in particular nanomaterials, play an important role, as these influence interactions with biological elements, such as proteins, bacteria, and cells. In this study, the wetting phenomenon of titanium substrates coated with selenium nanoparticles was studied using experimental and mathematical modeling tools. Importantly, these selenium-coated titanium substrates were previously reported to increase select protein adsorption (such as vitronectin and fibronectin), to decrease bacteria growth, and increase bone cell growth. Increased selenium nanoparticle coating density resulted in higher contact angles but remained within the hydrophilic regime. This trend was found in disagreement with the Wenzel model, which is widely used to understand the wetting properties of rough surfaces. The trend also did not fit well with the Cassie–Baxter model, which was developed to understand the wetting properties of composite surfaces. A modified wetting model was thus proposed in this study, to understand the contributing factors of material properties to the hydrophilicity/hydrophobicity of these nanostructured selenium-coated surfaces. The analysis and model created in this study can be useful in designing and/or understanding the wetting behavior of numerous biomedical materials and in turn, biological events (such as protein adsorption as well as bacteria and mammalian cell functions).
doi:10.2147/IJN.S42970
PMCID: PMC3669097  PMID: 23737667
hydrophilicity, hydrophobicity, Wenzel model, Cassie; Baxter model, free energy, implant material, proteins, cells, bacteria
11.  Minimal Size of Coffee Ring Structure 
The journal of physical chemistry. B  2010;114(16):5269-5274.
A macroscopic evaporating water droplet with suspended particles on a solid surface will form a ring-like structure at the pinned contact line due to induced capillary flow. As the droplet size shrinks, the competition between the time scales of the liquid evaporation and the particle movement may influence the resulting ring formation. When the liquid evaporates much faster than the particle movement, coffee ring formation may cease. Here, we experimentally show that there exists a lower limit of droplet size, Dc, for the successful formation of a coffee ring structure. When the particle concentration is above a threshold value, Dc can be estimated by considering the collective effects of the liquid evaporation and the particle diffusive motion within the droplet. For suspended particles of size ~100 nm, the minimum diameter of the coffee ring structure is found to be ~10 µm.
doi:10.1021/jp912190v
PMCID: PMC2902562  PMID: 20353247
12.  Probing droplets on superhydrophobic surfaces by synchrotron radiation scattering techniques 
Journal of Synchrotron Radiation  2014;21(Pt 4):643-653.
A comprehensive review about the use of micro- and nanostructured superhydrophobic surfaces as a tool for in situ X-ray scattering investigations of soft matter and biological materials.
Droplets on artificially structured superhydrophobic surfaces represent quasi contact-free sample environments which can be probed by X-ray microbeams and nanobeams in the absence of obstructing walls. This review will discuss basic surface wettability concepts and introduce the technology of structuring surfaces. Quasi contact-free droplets are compared with contact-free droplets; processes related to deposition and evaporation on solid surfaces are discussed. Droplet coalescence based on the electrowetting effect allows the probing of short-time mixing and reaction processes. The review will show for several materials of biological interest that structural processes related to conformational changes, nucleation and assembly during droplet evaporation can be spatially and temporally resolved by raster-scan diffraction techniques. Orientational ordering of anisotropic materials deposited during solidification at pinning sites facilitates the interpretation of structural data.
doi:10.1107/S1600577514009849
PMCID: PMC4073955  PMID: 24971957
superhydrophobic surface; nanotechnology; biological matter; synchrotron radiation micro- and nanodiffraction
13.  Morphing and vectoring impacting droplets by means of wettability-engineered surfaces 
Scientific Reports  2014;4:7029.
Driven by its importance in nature and technology, droplet impact on solid surfaces has been studied for decades. To date, research on control of droplet impact outcome has focused on optimizing pre-impact parameters, e.g., droplet size and velocity. Here we follow a different, post-impact, surface engineering approach yielding controlled vectoring and morphing of droplets during and after impact. Surfaces with patterned domains of extreme wettability (high or low) are fabricated and implemented for controlling the impact process during and even after rebound —a previously neglected aspect of impact studies on non-wetting surfaces. For non-rebound cases, droplets can be morphed from spheres to complex shapes —without unwanted loss of liquid. The procedure relies on competition between surface tension and fluid inertial forces, and harnesses the naturally occurring contact-line pinning mechanisms at sharp wettability changes to create viable dry regions in the spread liquid volume. Utilizing the same forces central to morphing, we demonstrate the ability to rebound orthogonally-impacting droplets with an additional non-orthogonal velocity component. We theoretically analyze this capability and derive a We−.25 dependence of the lateral restitution coefficient. This study offers wettability-engineered surfaces as a new approach to manipulate impacting droplet microvolumes, with ramifications for surface microfluidics and fluid-assisted templating applications.
doi:10.1038/srep07029
PMCID: PMC4229684  PMID: 25392084
14.  Preparation and characterization of superhydrophobic surfaces based on hexamethyldisilazane-modified nanoporous alumina 
Nanoscale Research Letters  2011;6(1):487.
Superhydrophobic nanoporous anodic aluminum oxide (alumina) surfaces were prepared using treatment with vapor-phase hexamethyldisilazane (HMDS). Nanoporous alumina substrates were first made using a two-step anodization process. Subsequently, a repeated modification procedure was employed for efficient incorporation of the terminal methyl groups of HMDS to the alumina surface. Morphology of the surfaces was characterized by scanning electron microscopy, showing hexagonally ordered circular nanopores with approximately 250 nm in diameter and 300 nm of interpore distances. Fourier transform infrared spectroscopy-attenuated total reflectance analysis showed the presence of chemically bound methyl groups on the HMDS-modified nanoporous alumina surfaces. Wetting properties of these surfaces were characterized by measurements of the water contact angle which was found to reach 153.2 ± 2°. The contact angle values on HMDS-modified nanoporous alumina surfaces were found to be significantly larger than the average water contact angle of 82.9 ± 3° on smooth thin film alumina surfaces that underwent the same HMDS modification steps. The difference between the two cases was explained by the Cassie-Baxter theory of rough surface wetting.
doi:10.1186/1556-276X-6-487
PMCID: PMC3212001  PMID: 21827683
superhydrophobic surfaces; surface modification; hexamethyldisilazane; nanoporous alumina
15.  The ultrastructure of fibronectin fibers pulled from a protein monolayer at the air-liquid interface and the mechanism of the sheet-to-fiber transition 
Biomaterials  2015;36:66-79.
Fibronectin is a globular protein that circulates in the blood and undergoes fibrillogenesis if stretched or under other partially denaturing conditions, even in the absence of cells. Stretch assays made by pulling fibers from droplets of solutions containing high concentrations of fibronectin have previously been introduced in mechanobiology, particularly to ask how bacteria and cells exploit the stretching of fibronectin fibers within extracellular matrix to mechano-regulate its chemical display. Our electron microscopy analysis of their ultrastructure now reveals that the manually pulled fibronectin fibers are composed of densely packed lamellar spirals, whose interlamellar distances are dictated by ion-tunable electrostatic interactions. Our findings suggest that fibrillogenesis proceeds via an irreversible sheet-to-fiber transition as the fibronectin sheet formed at the air-liquid interface of the droplet is pulled off by a sharp tip. This far from equilibrium process is driven by the externally applied force, interfacial surface tension, shear-induced fibronectin self-association, and capillary force-induced buffer drainage. The ultrastructural characterization is then contrasted with previous FRET studies that characterized the molecular strain within these manually pulled fibers. Particularly relevant for stretch-dependent binding studies is the finding that the interior fiber surfaces are accessible to nanoparticles smaller than 10 nm. In summary, our study discovers the underpinning mechanism by which highly hierarchically structured fibers can be generated with unique mechanical and mechano-chemical properties, a concept that might be extended to other bio- or biomimetic polymers.
doi:10.1016/j.biomaterials.2014.08.012
PMCID: PMC4234482  PMID: 25442805
Fibronectin; Fibrillogenesis; Sheet-to-fiber transition; Monolayer-to-lamella transition; Electron microscopy; Kinetically trapped supramolecular system; FRET, Förster resonance energy transfer; MEMS, micro-electro-mechanical system; PBS, phosphate buffer solution; PDMS, polydimethylsiloxane; SEM, scanning electron microscopy; TEM, transmission electron microscopy
16.  Hydrophobic-induced Surface Reorganization: Molecular Dynamics Simulations of Water Nanodroplet on Perfluorocarbon Self-Assembled Monolayers 
Soft matter  2010;6(8):1644-1654.
We carried out molecular dynamics simulations of water droplets on self-assembled monolayers of perfluorocarbon molecules. The interactions between the water droplet and the hydrophobic fluorocarbon surface were studied by systematically changing the molecular surface coverage and the mobility of the tethered head groups of the surface chain molecules. The microscopic contact angles were determined for different fluorocarbon surface densities. The contact angle at a nanometer length scale does not show a large change with the surface density. The structure of the droplets was studied by looking at the water density profiles and water penetration near the hydrophobic surface. At surface densities near close packed coverage of fluorocarbons, the water density shows an oscillating pattern near the boundary with a robust layered structure. As the surface density decreased and more water molecules penetrated into the fluorocarbon surface, the ordering of the water molecules at the boundary became less pronounced and the layered density structure became diffuse. The water droplet is found to induce the interfacial surface molecules to rearrange and form unique topological structures that minimize the unfavorable water-surface contacts. The local density of the fluorocarbon molecules right below the water droplet is measured to be higher than the density outside the droplet. The density difference increases as the overall surface density decreases. Two different surface morphologies emerge from the water-induced surface reorganization over the range of surface coverage explored in the study. For surface densities near closed packed monolayer coverage, the height of the fluorocarbons is maximum at the center of the droplet and minimum at the water-vapor-surface triple junction, generating a convex surface morphology under the droplet. For lower surface densities, on the other hand, the height of the fluorocarbon surface becomes maximal at and right outside the water-vapor-surface contact line and decreases quickly towards the center of the droplet, forming a concave shape of the surface. The interplay between the fluorocarbon packing and the water molecules is found to have profound consequences in many aspects of surface-water interactions, including water depletion and penetration, hydrogen bonding, and surface morphologies.
doi:10.1039/b923392j
PMCID: PMC2877516  PMID: 20514368
17.  Superhydrophobic Photosensitizers. Mechanistic Studies of 1O2 Generation in the Plastron and Solid/Liquid Droplet Interface 
Journal of the American Chemical Society  2013;135(50):18990-18998.
We describe here a physical-organic study of the first triphasic superhydrophobic sensitizer for photooxidations in water droplets. Control of synthetic parameters enables the mechanistic study of “borderline” two- and three-phase superhydrophobic sensitizer surfaces where 1O2 is generated in compartments that are wetted, partially wetted, or remain dry in the plastron (i.e., air layer beneath the droplet). The superhydrophobic surface is synthesized by partially embedding silicon phthalocyanine (Pc) sensitizing particles to specific locations on polydimethylsiloxane (PDMS) posts printed in a square array (1 mm tall posts on 0.5 mm pitch). In the presence of red light and oxygen, singlet oxygen is formed on the superhydrophobic surface and reacts with 9,10-anthracene dipropionate dianion (1) within a freestanding water droplet to produce an endoperoxide in 54–72% yields. Control of the 1O2 chemistry was achieved by the synthesis of superhydrophobic surfaces enriched with Pc particles either at the PDMS end-tips or at PDMS post bases. Much of the 1O2 that reacts with anthracene 1 in the droplets was generated by the sensitizer “wetted” at the Pc particle/water droplet interface and gave the highest endoperoxide yields. About 20% of the 1O2 can be introduced into the droplet from the plastron. The results indicate that the superhydrophobic sensitizer surface offers a unique system to study 1O2 transfer routes where a balance of gas and liquid contributions of 1O2 is tunable within the same superhydrophobic surface.
doi:10.1021/ja410529q
PMCID: PMC3930608  PMID: 24295210
18.  Regulation of RNA granule dynamics by phosphorylation of serine-rich, intrinsically disordered proteins in C. elegans 
eLife  null;3:e04591.
RNA granules have been likened to liquid droplets whose dynamics depend on the controlled dissolution and condensation of internal components. The molecules and reactions that drive these dynamics in vivo are not well understood. In this study, we present evidence that a group of intrinsically disordered, serine-rich proteins regulate the dynamics of P granules in C. elegans embryos. The MEG (maternal-effect germline defective) proteins are germ plasm components that are required redundantly for fertility. We demonstrate that MEG-1 and MEG-3 are substrates of the kinase MBK-2/DYRK and the phosphatase PP2APPTR−½. Phosphorylation of the MEGs promotes granule disassembly and dephosphorylation promotes granule assembly. Using lattice light sheet microscopy on live embryos, we show that GFP-tagged MEG-3 localizes to a dynamic domain that surrounds and penetrates each granule. We conclude that, despite their liquid-like behavior, P granules are non-homogeneous structures whose assembly in embryos is regulated by phosphorylation.
DOI: http://dx.doi.org/10.7554/eLife.04591.001
eLife digest
For a gene to be expressed as a protein, its DNA is first used as a template to make a molecule of RNA, which is then translated to make the protein. In most cells, RNA molecules concentrate into aggregates called RNA granules. These granules contain both RNA and proteins that bind to RNA and are used to transport, store, and regulate the translation and breakdown of RNA molecules. Unlike many other structures within cells, RNA granules are not surrounded by a membrane; and the molecules that hold RNA granules together are not known.
P granules are a type of RNA granule that is found in the germ cells (the cells that go on to form eggs and sperm) of a microscopic worm called C. elegans. When a C. elegans embryo is still a single cell, P granules move throughout the cell and the P granules at the front of the cell dissolve, while those at the back condense. As such, when the single-celled embryo divides, the front forms a cell without P granules (that will go on to form the tissues of the worm's body) and the back becomes a P granule-containing germ cell.
Two proteins called MBK-2 and PPTR-1 have opposite effects on P granules: MBK-2 causes P granules to dissolve, while PPTR-1 makes them form. MBK-2 is an enzyme that adds phosphate groups onto other proteins, whereas PPTR-1 is part of an enzyme that removes such groups. Wang et al. have now searched for proteins that interact with MBK-2 and PPTR-1 in order to identify the molecules that regulate the assembly of P granules. They found that a group of proteins, known as MEG proteins, are acted upon by both of these proteins. Wang et al. found that MBK-2 adds phosphate groups to MEG proteins, which encourages granules to disassemble, while PPTR-1 removes these groups to promote granule assembly.
Wang et al. generated mutant worms that lacked each of the MEG proteins. These mutant worms had fewer and smaller P granules than normal worms. Without MEG proteins, P granules failed to assemble or disassemble normally and the worms were infertile. Using high resolution microscopy, Wang et al. observed that the MEG proteins wrap around the P granules and that one of the MEG proteins—called MEG-3—follows an almost ribbon-like path that surrounds and enters each granule. These observations suggest that the MEG proteins stabilize RNA granules by forming a cage-like scaffold around each granule. How the MEG proteins—which are predicted to lack a fixed or ordered three-dimensional structure and show no similarity to proteins with known functions—assemble into a scaffold will be the focus of future studies.
DOI: http://dx.doi.org/10.7554/eLife.04591.002
doi:10.7554/eLife.04591
PMCID: PMC4296509  PMID: 25535836
RNA granules; intrinsically disordered proteins; germ plasm; C. elegans
19.  SURFACTANT INFLUENCE ON RIVULET DROPLET FLOW IN MINITUBES AND CAPILLARIES AND ITS DOWNSTREAM EVOLUTION* 
During our investigations of two-phase flow in long hydrophobic minitubes and capillaries, we have observed transformation of the main rivulet into different new hydrodynamic modes with the use of different kinds of surfactants. The destabilization of rivulet flow at air velocities <80 m/sec occurs primarily due to the strong branching off of sub-rivulets from the main rivulet during the downstream flow in the tube. The addition of some surfactants of not-so-high surface activity was found to increase the frequency of sub-rivulet formation and to suppress the Rayleigh and sinuous instabilities of the formed sub-rivulets. Such instabilities result in subsequent fragmentation of the sub-rivulets and in the formation of linear or sinuous arrays of sub-rivulet fragments (SRFs), which later transform into random arrays of SRFs. In the downstream flow, SRFs further transform into large sliding cornered droplets and linear droplet arrays (LDAs), a phenomenon which agrees with recent theories. At higher surface activity, suppression of the Rayleigh instability of sub-rivulets with surfactants becomes significant, which prevents sub-rivulet fragmentation, and only the rivulet and sub-rivulets can be visualized in the tube. At the highest surface activity, the bottom rivulet transforms rapidly into an annular liquid film. The surfactant influence on the behavior of the rivulets in minitubes is incomparably stronger than the classic example of the known surfactant stabilizing influence on a free jet. The evolution of a rivulet in the downstream flow inside a long minitube includes the following sequence of hydrodynamic modes/patterns: i) single rivulet; ii) rivulet and sub-rivulets; and iii) rivulet, sub-rivulets, sub-rivulet fragments, cornered droplets, linear droplet arrays, linear arrays of sub-rivulet fragments and annular film. The formation of these many different hydrodynamic patterns downstream is in drastic contrast with the known characteristics of two-phase flow, which demonstrates one mode for the entire tube length. Recent achievements in fluid mechanics regarding the stability of sliding thin films and in wetting dynamics have allowed us to interpret many of our findings. However, the most important phenomenon of the surfactant influence on sub-rivulet formation remains poorly understood. To achieve further progress in this new area, an interdisciplinary approach based on the use of methods of two-phase flow, wetting dynamics and interfacial rheology will be necessary.
doi:10.1016/j.cis.2011.05.004
PMCID: PMC3133662  PMID: 21652020
Surfactant; Marangoni stress; wetting dynamics; interfacial rheology; two-phase flow; rivulet; sub-rivulet; sub-rivulet fragment; sliding droplet; cornered droplet; linear droplet array; Rayleigh instability; sinuous instability; minitube cleaning; meandering; two-phase flow maps
20.  Theoretical Model of Droplet Wettability on a Low-Surface-Energy Solid under the Influence of Gravity 
The Scientific World Journal  2014;2014:647694.
The wettability of droplets on a low surface energy solid is evaluated experimentally and theoretically. Water-ethanol binary mixture drops of several volumes are used. In the experiment, the droplet radius, height, and contact angle are measured. Analytical equations are derived that incorporate the effect of gravity for the relationships between the droplet radius and height, radius and contact angle, and radius and liquid surface energy. All the analytical equations display good agreement with the experimental data. It is found that the fundamental wetting behavior of the droplet on the low surface energy solid can be predicted by our model which gives geometrical information of the droplet such as the contact angle, droplet radius, and height from physical values of liquid and solid.
doi:10.1155/2014/647694
PMCID: PMC3910366  PMID: 24511297
21.  Atomistics of vapour–liquid–solid nanowire growth 
Nature Communications  2013;4:1956.
Vapour–liquid–solid route and its variants are routinely used for scalable synthesis of semiconducting nanowires, yet the fundamental growth processes remain unknown. Here we employ atomic-scale computations based on model potentials to study the stability and growth of gold-catalysed silicon nanowires. Equilibrium studies uncover segregation at the solid-like surface of the catalyst particle, a liquid AuSi droplet, and a silicon-rich droplet–nanowire interface enveloped by heterogeneous truncating facets. Supersaturation of the droplets leads to rapid one-dimensional growth on the truncating facets and much slower nucleation-controlled two-dimensional growth on the main facet. Surface diffusion is suppressed and the excess Si flux occurs through the droplet bulk which, together with the Si-rich interface and contact line, lowers the nucleation barrier on the main facet. The ensuing step flow is modified by Au diffusion away from the step edges. Our study highlights key interfacial characteristics for morphological and compositional control of semiconducting nanowire arrays.
The vapour–liquid–solid method is used to produce semiconducting nanowires but the fundamental processes involved are poorly understood. Wang et al. use atomic-scale simulations to elucidate the mechanisms involved in the growth and stability of gold-catalysed silicon nanowires.
doi:10.1038/ncomms2956
PMCID: PMC3709494  PMID: 23752586
22.  Electrically Controlled Membranes Exploiting Cassie-Wenzel Wetting Transitions 
Scientific Reports  2013;3:3028.
We report electrically controlled membranes which become permeable when an electrical field is exerted on a droplet deposited on the membrane. Micro-porous polycarbonate membranes are obtained with the breath-figures assembly technique, using micro-scaled stainless steel gauzes as supports. The membranes demonstrate pronounced Cassie-Baxter wetting. Air cushions trapped by the droplet prevent water penetration through the membrane. We demonstrate two possibilities for controlling the permeability of the membrane, namely contact and non-contact scenarios. When an electrical field is exerted on a droplet deposited on the membrane, the triple-line is de-pinned and the wetting transition occurs in the non-contact scheme. Thus, the membrane becomes permeable. The contact scheme of the permeability control is based on the electrowetting phenomenon.
doi:10.1038/srep03028
PMCID: PMC3805972  PMID: 24149769
23.  Droplet centrifugation, droplet DNA extraction, and rapid droplet thermocycling for simpler and faster PCR assay using wire-guided manipulations 
A computer numerical control (CNC) apparatus was used to perform droplet centrifugation, droplet DNA extraction, and rapid droplet thermocycling on a single superhydrophobic surface and a multi-chambered PCB heater. Droplets were manipulated using “wire-guided” method (a pipette tip was used in this study). This methodology can be easily adapted to existing commercial robotic pipetting system, while demonstrated added capabilities such as vibrational mixing, high-speed centrifuging of droplets, simple DNA extraction utilizing the hydrophobicity difference between the tip and the superhydrophobic surface, and rapid thermocycling with a moving droplet, all with wire-guided droplet manipulations on a superhydrophobic surface and a multi-chambered PCB heater (i.e., not on a 96-well plate). Serial dilutions were demonstrated for diluting sample matrix. Centrifuging was demonstrated by rotating a 10 μL droplet at 2300 round per minute, concentrating E. coli by more than 3-fold within 3 min. DNA extraction was demonstrated from E. coli sample utilizing the disposable pipette tip to cleverly attract the extracted DNA from the droplet residing on a superhydrophobic surface, which took less than 10 min. Following extraction, the 1500 bp sequence of Peptidase D from E. coli was amplified using rapid droplet thermocycling, which took 10 min for 30 cycles. The total assay time was 23 min, including droplet centrifugation, droplet DNA extraction and rapid droplet thermocycling. Evaporation from of 10 μL droplets was not significant during these procedures, since the longest time exposure to air and the vibrations was less than 5 min (during DNA extraction). The results of these sequentially executed processes were analyzed using gel electrophoresis. Thus, this work demonstrates the adaptability of the system to replace many common laboratory tasks on a single platform (through re-programmability), in rapid succession (using droplets), and with a high level of accuracy and automation.
doi:10.1186/1754-1611-6-15
PMCID: PMC3526397  PMID: 22947281
Droplet manipulations; Escherichia coli; Peptidase D; Droplet PCR; Rapid PCR
24.  Rapid Analysis of the Internal Configurations of Droplets of Liquid Crystal using Flow Cytometry 
Analytical chemistry  2013;85(21):10296-10303.
We report the use of flow cytometry to identify the internal ordering (director configurations) of micrometer-sized droplets of thermotropic liquid crystals (LCs) dispersed in aqueous solutions of adsorbates (surfactants and phospholipids). We reveal that changes in the configurations of the LC droplets induced by the adsorbates generate distinct changes in light scattering plots (side versus forward scattering). Specifically, when compared to bipolar droplets, radial droplets generate a narrower distribution of side scattering intensities (SSC, large angle light scattering) for a given intensity of forward scattering (FSC, small angle light scattering). This difference is shown to arise from the rotational symmetry of a radial LC droplet which is absent for the bipolar configuration of the LC droplet. In addition, the scatter plots for radial droplets possess a characteristic “S-shape”, with two or more SSC intensities observed for each intensity of FSC. The origin of the experimentally observed S-shape is investigated via calculation of form factors and established to be due to size-dependent interference effects that differ for the forward and side scattered light. Finally, by analyzing emulsions comprised of mixtures of bipolar and radial droplets at rates of up to 10,000 droplets per second, we demonstrate that flow cytometry permits precise determination of the percentage of radial droplets within the mixture with a coefficient of determination of 0.98 (as validated by optical microscopy). Overall, the results presented in this paper demonstrate that flow cytometry provides a promising approach for high throughput quantification of the internal configurations of LC emulsion microdroplets. Because large numbers of droplets can be characterized, it enables statistically robust analyses of LC droplets. The methodology also appears promising for quantification of chemical and biological assays based on adsorbate-induced ordering transitions within LC droplets.
doi:10.1021/ac4021193
PMCID: PMC4025942  PMID: 24079265
Flow cytometry; liquid crystal droplets; ordering transition; amphiphile; light scattering; interference effects
25.  Co-Fabrication: A Strategy for Building Multi-Component Microsystems 
Accounts of chemical research  2010;43(4):518-528.
Conspectus
Whitesides Conspectus ar-2009-00178k.R2 edited and approved
In this Account, we describe a strategy for fabricating multicomponent microsystems in which the structures of essentially all of the components are formed in a single step of micromolding. This strategy—which we call “co-fabrication”—is an alternative to multilayer microfabrication, in which multiple layers of components are sequentially aligned (“registered”) and deposited on a substrate by photolithography.
Co-fabrication has several characteristics that make it a particularly useful approach for building multicomponent microsystems. It rapidly and inexpensively generates correctly aligned components (for example, wires, heaters, magnetic field generators, optical waveguides, and microfluidic channels)—and over very large surface areas. By avoiding registration, the technique does not impose the size limitations of common registration tools, such as steppers and contact aligners, on substrates. We have demonstrated multicomponent microsystems with surface areas exceeding 100 cm2, but in principle device size is only limited by the requirements of generating the original master.
Co-fabrication can also serve as a low-cost and minimal-equipment strategy for building microsystems. The technique is amenable to a variety of laboratory settings and uses fabrication tools that are less expensive than those used for multistep microfabrication. The process also requires only small amounts of solvent and photoresist—a costly chemical required for photolithography. In co-fabrication, photoresist is applied and developed only once to produce a master, which is then used to produce multiple copies of molds containing the microfluidic channels.
Co-fabrication represents a new processing paradigm in which the exterior (or shell) of the desired structures are produced before the interior (or core). This approach—generating the insulation or packaging structure first, and injecting materials that provide function in channels in liquid phase—makes it possible to design and build microsystems with component materials that cannot be easily manipulated conventionally (such as solid materials with low melting points, liquid metals, liquid crystals, fused salts, foams, emulsions, gases, polymers, biomaterials, and fragile organics). Moreover, materials can be altered, removed, or replaced after the manufacturing stage. For example, co-fabrication allows one to build devices in which a liquid flows through the device during use (or is replaced before use). Metal wires can be melted and re-set by heating (in principle, repairing a break). This method leads to certain kinds of structures—such as integrated metallic wires with large cross-sectional areas, or optical waveguides aligned in the same plane as microfluidic channels—that would be difficult or impossible to make with techniques such as sputter deposition or evaporation.
This Account outlines the strategy of co-fabrication, describing several co-fabricated microsystems that combine microfluidics with (i) electrical wires for microheaters, electromagnets, and organic electrodes; (ii) fluidic optical components, such as optical waveguides, lenses, and light sources; (iii) gels for biological cell cultures; and (iv) droplets for compartmentalized chemical reactions, such as protein crystallization.
doi:10.1021/ar900178k
PMCID: PMC2857577  PMID: 20088528

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