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1.  Porous Organic Nanolayers for Coating of Solid-state Devices 
Highly hydrophobic surfaces can have very low surface energy and such low surface energy biological interfaces can be obtained using fluorinated coatings on surfaces. Deposition of biocompatible organic films on solid-state surfaces is attained with techniques like plasma polymerization, biomineralization and chemical vapor deposition. All these require special equipment or harsh chemicals. This paper presents a simple vapor-phase approach to directly coat solid-state surfaces with biocompatible films without any harsh chemical or plasma treatment. Hydrophilic and hydrophobic monomers were used for reaction and deposition of nanolayer films. The monomers were characterized and showed a very consistent coating of 3D micropore structures.
The coating showed nano-textured surface morphology which can aid cell growth and provide rich molecular functionalization. The surface properties of the obtained film were regulated by varying monomer concentrations, reaction time and the vacuum pressure in a simple reaction chamber. Films were characterized by contact angle analysis for surface energy and with profilometer to measure the thickness. Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed the chemical composition of the coated films. Variations in the FTIR results with respect to different concentrations of monomers showed the chemical composition of the resulting films.
The presented approach of vapor-phase coating of solid-state structures is important and applicable in many areas of bio-nano interface development. The exposure of coatings to the solutions of different pH showed the stability of the coatings in chemical surroundings. The organic nanocoating of films can be used in bio-implants and many medical devices.
PMCID: PMC3125257  PMID: 21569579
2.  Asymmetric Glyoxylate-Ene Reactions Catalyzed by Chiral Pd(II) Complexes in the Ionic Liquid [bmim][PF6] 
The room temperature ionic liquid [bmim][PF6] was employed as the reaction medium in the asymmetric glyoxylate-ene reaction of α-methyl styrene (4a) with ethyl glyoxylate using chiral palladium(II) complexes as the catalysts. [Pd(S-BINAP)(3,5-CF3-PhCN)2](SbF6)2 (1b) showed the highest catalytic activity. Under the reaction conditions of 40 °C, 0.5 h, and 1b/4a molar ratio of 0.05, ethyl α-hydroxy-4-phenyl-4-pentenoate was obtained in excellent chemical yield (94 %) with high enantioselectivity (70 %). Other α-hydroxy esters can also be obtained in high chemical yields and enantioselectities through the glyoxylate-ene reactions of alkenes with glyoxylates catalyzed by 1b in [bmim][PF6]. Moreover, the ionic liquid [bmim][PF6] which contained the palladium(II) complex could be recycled and reused several times without significant loss of the catalytic activity.
PMCID: PMC3714615
Ionic liquid; glyoxylate-ene reaction; palladium; chiral; 1-n-butyl-3-methylimidazolium hexafluorophosphate
3.  Quasi-Immiscible Spreading of Aqueous Surfactant Solutions on Entangled Aqueous Polymer Solution Subphases 
ACS applied materials & interfaces  2013;5(12):5542-5549.
Motivated by the possibility of enhancing aerosol drug delivery to mucus-obstructed lungs, the spreading of a drop of aqueous surfactant solution on a physically entangled aqueous poly(acrylamide) solution subphase that mimics lung airway surface liquid was investigated. Sodium dodecyl sulfate was used as the surfactant. To visualize spreading of the drop and mimic the inclusion of a drug substance, fluorescein, a hydrophilic and non-surface active dye, was added to the surfactant solution. The spreading progresses through a series of events. Marangoni stresses initiate the convective spreading of the drop. Simultaneously, surfactant escapes across the drop’s contact line within a second of deposition and causes a change in subphase surface tension outside the drop on the order of 1 mN/m. Convective spreading of the drop ends within 2–3 seconds of drop deposition, when a new interfacial tension balance is achieved. Surfactant escape depletes the drop of surfactant and the residual drop takes the form of a static lens of non-zero contact angle. On longer time scales, the surfactant dissolves into the subphase. The lens formed by the water in the deposited drop persists for as long as 3 minutes after the convective spreading process ends due to the long diffusional timescales associated with the underlying entangled polymer solution. The persistence of the lens suggests that the drop phase behaves as if it were immiscible with the subphase during this time period. Whereas surfactant escapes the spreading drop and advances on the subphase/vapor interface, hydrophilic dye molecules in the drop do not escape, but remain with the drop throughout the convective spreading. The quasi-immiscible nature of the spreading event suggests that the chemical properties of the surfactant and subphase are much less important than their physical properties, consistent with prior qualitative studies of spreading of different types of surfactants on entangled polymer subphases: the selection of surfactant for pulmonary delivery applications may be limited only by physical and toxicological considerations. Further, the escape of surfactant from individual drops may provide an additional spreading mechanism in the lung as hydrodynamic and/or surface pressure repulsions may drive individual droplets apart after deposition.
PMCID: PMC3959907  PMID: 23705869
Marangoni flow; surfactant spreading; surfactant transport; pulmonary drug delivery
4.  Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers 
A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1].
PMCID: PMC3458608  PMID: 23019558
breath figure; nanopatterned template; polymer blend lithography (PBL); self-assembled monolayer (SAM); self assembly; spin coating; vapor phase
5.  DNA–Based Asymmetric Catalysis: Role of Ionic Solvents and Glymes 
RSC advances  2014;4(96):54051-54059.
Recently, DNA has been evaluated as a chiral scaffold for metal complexes to construct so called ‘DNA-based hybrid catalysts’, a robust and inexpensive alternative to enzymes. The unique chiral structure of DNA allows the hybrid catalysts to catalyze various asymmetric synthesis reactions. However, most current studies used aqueous buffers as solvents for these asymmetric reactions, where substrates/products are typically suspended in the solutions. The mass transfer limitation usually requires a long reaction time. To overcome this hurdle and to advance DNA-based asymmetric catalysis, we evaluated a series of ionic liquids (ILs), inorganic salts, deep eutectic solvents (DES), glymes, glycols, acetonitrile and methanol as co-solvents/additives for the DNA-based asymmetric Michael addition. In general, these additives induce indistinguishable changes to the DNA B-form duplex conformation as suggested by circular dichroism (CD) spectroscopy, but impose a significant influence on the catalytic efficiency of the DNA-based hybrid catalyst. Conventional organic solvents (e.g. acetonitrile and methanol) led to poor product yields and/or low enantioselectivities. Most ILs and inorganic salts cause the deactivation of the hybrid catalyst except 0.2 M [BMIM][CF3COO] (95.4% ee and 93% yield) and 0.2 M [BMIM]Cl (93.7% ee and 89% yield). Several other additives have also been found to improve the catalytic efficiency of the DNA-based hybrid catalyst (control reaction without additive gives >99% ee and 87% yield): 0.4 M glycerol (>99% ee and 96% yield at 5 °C or 96.2% ee and 83% yield at room temperature), 0.2 M choline chloride/glycerol (1:2) (92.4% ee and 90% yield at 5 °C or 94.0% ee and 88% yield at room temperature), and 0.5 M dipropylene glycol dimethyl ether (>99% ee and 87% yield at room temperature). The use of some co-solvents/additives allows the Michael addition to be performed at a higher temperature (e.g. room temperature vs 5 °C) and a shorter reaction time (24 h vs 3 days). In addition, we found that a brief pre-sonication (5 min) of DNA in MOPS buffer prior to the reaction could improve the performance of the DNA-based hybrid catalyst. We have also shown that this DNA-based catalysis method is suitable for a variety of different substrates and relatively large-scale reactions. In conclusion, a judicious selection of benign co-solvents/additives could improve the catalytic efficiency of DNA-based hybrid catalyst.
PMCID: PMC4224305  PMID: 25386337
DNA; asymmetric synthesis; hybrid catalyst; ionic liquid; deep eutectic solvent; glyme
6.  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.
PMCID: PMC2883006  PMID: 20405867
7.  The role of biocompatible coatings of biomaterials for creation of direct and appropriate chemical bounding between bioimplant and bone tissue 
Journal of Injury and Violence Research  2012;4(3 Suppl 1): Paper No. 39.
Nowadays, the surface modification of biomaterials to increase biocompatibility and improve other aspects of environmental performance is widely prevalent and is developing. Biological host response depends on the primary interactions of biological and biomaterials systems at the molecular surfaces. Therefore, the surface properties at the atomic scale influence on compatibility and optimal performance of the material in body. The present study aims to survey the most common surface modification techniques of biomaterials focusing on the surface coating techniques and their applications in bone tissue engineering and tissue repairing field. Furthermore, the process and features of biomaterial surface coating in complex superficial modification of biomaterials as a representation of biomaterials interfaces with the biological environment are discussed. Finally, the potential applications and advantages of these techniques in repairing damaged tissues in neurosurgery and orthopedic surgery are presented.
In this review article, the most common and important methods of surface modification of biomaterials (thermal spray, electrophoresis, pulsed laser deposition, electrochemical, biomimetic, sputtering, Chemical Vapor Deposition (CVD), and, Sol–Gel techniques) which the reputable manufacture companies of biomaterial are applying and many published articles in the biomaterial field (since 2004 up to now). Furthermore, the potential applications and current positions of these methods in bone tissue engineering and effective factors for an optimal tissue repairing using biomaterial surface coating are presented.
The Sol-gel method is suitable for obtaining nanoscale structures. Plasma spraying method has a high-speed balance and is the only commercially available method. The pulsed laser coating method can be used in multilayer coatings and structures with a fixed Stoichiometric.
The electrophoresis coating methods are able to coat relatively complex shapes with precise control over coating thickness.In recent years, several coating methods such as electrochemical, biomimetic, sputtering, and CVD have been proposed and used by researchers some of them with good satisfactory results.
Findings of our survey show that surface modification of biomaterials can keep the crucial physical properties of the biomaterials unchanged which is an important feature in biological reactions. The main advantages of biomaterial surface modification including surface coating can be presented as follows:
Reducing protein adsorption:Biomaterials sometimes need to have the lowest protein adsorption, otherwise, will cause uncontrolled immune responses.
Lack of cellular coherency
Cellular absorption:Biomaterials that are used as replacement tissue cells must have high capability for cell absorption and also should facilitate their growth process.
Reducing Clot formation:Biomaterials that are used as blood implants should have the lowest capacity of clot formation.
High coherency to bacteria
Reducing friction and grinding
Biomaterials, Coating, Biocompatibility, Grinding, Bounding, Implant
PMCID: PMC3571565
8.  Gold-ionic liquid nanofluids with preferably tribological properties and thermal conductivity 
Nanoscale Research Letters  2011;6(1):259.
Gold/1-butyl-3-methylimidazolium hexafluorophosphate (Au/[Bmim][PF6]) nanofluids containing different stabilizing agents were fabricated by a facile one-step chemical reduction method, of which the nanofluids stabilized by cetyltrimethylammonium bromide (CTABr) exhibited ultrahighly thermodynamic stability. The transmission electron microscopy, UV-visible absorption, Fourier transform infrared, and X-ray photoelectron characterizations were conducted to reveal the stable mechanism. Then, the tribological properties of these ionic liquid (IL)-based gold nanofluids were first investigated in more detail. In comparison with pure [Bmim][PF6] and the nanofluids possessing poor stability, the nanofluids with high stability exhibited much better friction-reduction and anti-wear properties. For instance, the friction coefficient and wear volume lubricated by the nanofluid with rather low volumetric concentration (1.02 × 10-3%) stabilized by CTABr under 800 N are 13.8 and 45.4% lower than that of pure [Bmim][PF6], confirming that soft Au nanoparticles (Au NPs) also can be excellent additives for high performance lubricants especially under high loads. Moreover, the thermal conductivity (TC) of the stable nanofluids with three volumetric fraction (2.55 × 10-4, 5.1 × 10-4, and 1.02 × 10-3%) was also measured by a transient hot wire method as a function of temperature (33 to 81°C). The results indicate that the TC of the nanofluid (1.02 × 10-3%) is 13.1% higher than that of [Bmim][PF6] at 81°C but no obvious variation at 33°C. The conspicuously temperature-dependent and greatly enhanced TC of Au/[Bmim][PF6] nanofluids stabilized by CTABr could be attributed to micro-convection caused by the Brownian motion of Au NPs. Our results should open new avenues to utilize Au NPs and ILs in tribology and the high-temperature heat transfer field.
PMCID: PMC3211321  PMID: 21711789
9.  Vehicle Exhaust Gas Clearance by Low Temperature Plasma-Driven Nano-Titanium Dioxide Film Prepared by Radiofrequency Magnetron Sputtering 
PLoS ONE  2013;8(4):e59974.
A novel plasma-driven catalysis (PDC) reactor with special structure was proposed to remove vehicle exhaust gas. The PDC reactor which consisted of three quartz tubes and two copper electrodes was a coaxial dielectric barrier discharge (DBD) reactor. The inner and outer electrodes firmly surrounded the outer surface of the corresponding dielectric barrier layer in a spiral way, respectively. Nano-titanium dioxide (TiO2) film prepared by radiofrequency (RF) magnetron sputtering was coated on the outer wall of the middle quartz tube, separating the catalyst from the high voltage electrode. The spiral electrodes were designed to avoid overheating of microdischarges inside the PDC reactor. Continuous operation tests indicated that stable performance without deterioration of catalytic activity could last for more than 25 h. To verify the effectiveness of the PDC reactor, a non-thermal plasma(NTP) reactor was employed, which has the same structure as the PDC reactor but without the catalyst. The real vehicle exhaust gas was introduced into the PDC reactor and NTP reactor, respectively. After the treatment, compared with the result from NTP, the concentration of HC in the vehicle exhaust gas treated by PDC reactor reduced far more obviously while that of NO decreased only a little. Moreover, this result was explained through optical emission spectrum. The O emission lines can be observed between 870 nm and 960 nm for wavelength in PDC reactor. Together with previous studies, it could be hypothesized that O derived from catalytically O3 destruction by catalyst might make a significant contribution to the much higher HC removal efficiency by PDC reactor. A series of complex chemical reactions caused by the multi-components mixture in real vehicle exhaust reduced NO removal efficiency. A controllable system with a real-time feedback module for the PDC reactor was proposed to further improve the ability of removing real vehicle exhaust gas.
PMCID: PMC3616156  PMID: 23560062
10.  X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water 
ACS Nano  2015;10(1):1224-1230.
Films of colloidal CsPbX3 (X = I, Br or Cl) nanocrystals, prepared by solution drop-casting or spin-coating on a silicon substrate, were exposed to a low flux of X-rays from an X-ray photoelectron spectrometer source, causing intermolecular C=C bonding of the organic ligands that coat the surface of the nanocrystals. This transformation of the ligand shell resulted in a greater stability of the film, which translated into the following features: (i) Insolubility of the exposed regions in organic solvents which caused instead complete dissolution of the unexposed regions. This enabled the fabrication of stable and strongly fluorescent patterns over millimeter scale areas. (ii) Inhibition of the irradiated regions toward halide anion exchange reactions, when the films were exposed either to halide anions in solution or to hydrohalic vapors. This feature was exploited to create patterned regions of different CsPbIxBryClz compositions, starting from a film with homogeneous CsPbX3 composition. (iii) Resistance of the films to degradation caused by exposure to air and moisture, which represents one of the major drawbacks for the integration of these materials in devices. (iv) Stability of the film in water and biological buffer, which can open interesting perspectives for applications of halide perovskite nanocrystals in aqueous environments.
PMCID: PMC4734608  PMID: 26617344
perovskite; nanocrystals; X-ray; anion-exchange; patterning
11.  Green chemistry and nanofabrication in a levitated Leidenfrost drop 
Nature Communications  2013;4:2400.
Green nanotechnology focuses on the development of new and sustainable methods of creating nanoparticles, their localized assembly and integration into useful systems and devices in a cost-effective, simple and eco-friendly manner. Here we present our experimental findings on the use of the Leidenfrost drop as an overheated and charged green chemical reactor. Employing a droplet of aqueous solution on hot substrates, this method is capable of fabricating nanoparticles, creating nanoscale coatings on complex objects and designing porous metal in suspension and foam form, all in a levitated Leidenfrost drop. As examples of the potential applications of the Leidenfrost drop, fabrication of nanoporous black gold as a plasmonic wideband superabsorber, and synthesis of superhydrophilic and thermal resistive metal–polymer hybrid foams are demonstrated. We believe that the presented nanofabrication method may be a promising strategy towards the sustainable production of functional nanomaterials.
Droplets of water on very hot surfaces form levitating droplets, according to the Leidenfrost effect. Here, the authors show that green chemistry can be performed in these charged droplets, demonstrated by the synthesis of a range of nanoparticles, nanoscale coatings and porous metallic materials.
PMCID: PMC3826638  PMID: 24169567
12.  Self-assembly of octadecyltrichlorosilane: Surface structures formed using different protocols of particle lithography 
Particle lithography offers generic capabilities for the high-throughput fabrication of nanopatterns from organosilane self-assembled monolayers, which offers the opportunity to study surface-based chemical reactions at the molecular level. Nanopatterns of octadecyltrichlorosilane (OTS) were prepared on surfaces of Si(111) using designed protocols of particle lithography combined with either vapor deposition, immersion, or contact printing. Changing the physical approaches for applying molecules to masked surfaces produced OTS nanostructures with different shapes and heights. Ring nanostructures, nanodots and uncovered pores of OTS were prepared using three protocols, with OTS surface coverage ranging from 10% to 85%. Thickness measurements from AFM cursor profiles were used to evaluate the orientation and density of the OTS nanostructures. Differences in the thickness and morphology of the OTS nanostructures are disclosed based on atomic force microscopy (AFM) images. Images of OTS nanostructures prepared on Si(111) that were generated by the different approaches provide insight into the self-assembly mechanism of OTS, and particularly into the role of water and solvents in hydrolysis and silanation.
PMCID: PMC3304319  PMID: 22428102
atomic force microscopy; nanopatterning; nanostructures; octadecyltrichlorosilane; particle lithography; self-assembled monolayer; self-assembly
13.  Fabrication of porous silicon by metal-assisted etching using highly ordered gold nanoparticle arrays 
Nanoscale Research Letters  2012;7(1):450.
A simple method for the fabrication of porous silicon (Si) by metal-assisted etching was developed using gold nanoparticles as catalytic sites. The etching masks were prepared by spin-coating of colloidal gold nanoparticles onto Si. An appropriate functionalization of the gold nanoparticle surface prior to the deposition step enabled the formation of quasi-hexagonally ordered arrays by self-assembly which were translated into an array of pores by subsequent etching in HF solution containing H2O2. The quality of the pattern transfer depended on the chosen preparation conditions for the gold nanoparticle etching mask. The influence of the Si surface properties was investigated by using either hydrophilic or hydrophobic Si substrates resulting from piranha solution or HF treatment, respectively. The polymer-coated gold nanoparticles had to be thermally treated in order to provide a direct contact at the metal/Si interface which is required for the following metal-assisted etching. Plasma treatment as well as flame annealing was successfully applied. The best results were obtained for Si substrates which were flame annealed in order to remove the polymer matrix - independent of the substrate surface properties prior to spin-coating (hydrophilic or hydrophobic). The presented method opens up new resources for the fabrication of porous silicon by metal-assisted etching. Here, a vast variety of metal nanoparticles accessible by well-established wet-chemical synthesis can be employed for the fabrication of the etching masks.
PMCID: PMC3463426  PMID: 22876790
Porous silicon; Nanolithography; Gold nanoparticles; Self-assembly; Metal-assisted etching; 81.05.Rm; 81.16.Nd; 81.65.Cf
14.  Elucidation of the effect of ionic liquid pretreatment on rice husk via structural analyses 
In the present study, three ionic liquids, namely 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc), and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM]DEP), were used to partially dissolve rice husk, after which the cellulose were regenerated by the addition of water. The aim of the investigation is to examine the implications of the ionic liquid pretreatments on rice husk composition and structure.
From the attenuated total reflectance Fourier transform-infrared (ATR FT-IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) results, the regenerated cellulose were more amorphous, less crystalline, and possessed higher structural disruption compared with untreated rice husk. The major component of regenerated cellulose from [BMIM]Cl and [EMIM]DEP pretreatments was cellulose-rich material, while cellulose regenerated from [EMIM]OAc was a matrix of cellulose and lignin. Cellulose regenerated from ionic pretreatments could be saccharified via enzymatic hydrolysis, and resulted in relatively high reducing sugars yields, whereas enzymatic hydrolysis of untreated rice husk did not yield reducing sugars. Rice husk residues generated from the ionic liquid pretreatments had similar chemical composition and amorphousity to that of untreated rice husk, but with varying extent of surface disruption and swelling.
The structural architecture of the regenerated cellulose and rice husk residues showed that they could be used for subsequent fermentation or derivation of cellulosic compounds. Therefore, ionic liquid pretreatment is an alternative in the pretreatment of lignocellulosic biomass in addition to the conventional chemical pretreatments.
PMCID: PMC3499433  PMID: 22958710
Rice husk; Ionic liquid; Dissolution; Pretreatment; Regenerated cellulose; Structural analysis
15.  Autophobing on Liquid Subphases Driven by Interfacial Transport of Amphiphilic Molecules 
We investigated the phenomenon of incomplete wetting of a high energy liquid subphase by drops of pure amphiphilic molecules as well as drops of amphiphile solutions which are immiscible with the subphase. We show that amphiphiles escape across the contact line of the drop, move on the subphase/vapor interface and form a submonolayer or full monolayer external to the drop. If this monolayer is sufficiently dense, it can reduce the surface tension of the subphase, raise the contact angle of the drop and prevent the drop from fully wetting the subphase. This phenomenon is called autophobing and has been extensively studied on solid substrates. For the liquid subphase studied here, we measure the surface tensions of the three relevant interfaces before and after the drop is deposited. The measured surface tension external to the drop shows that amphiphiles can move across the contact line and form a monolayer outside of the drop. In some cases, at equilibrium, the monolayer is in a sufficiently packed state to create the nonwetting condition. In other cases, at equilibrium the monolayer density is insufficient to lower the surface tension enough to achieve the nonwetting condition. Unlike on solid substrates where the formation of the monolayer external to the drop is kinetically hindered, the amphiphiles can move rapidly across the liquid subphase by Marangoni driven surface transport and local equilbirum is achieved. However, because the amphiphile inventory and subphase area are limited, the achievement of autophobing on a liquid subphase depends not only on the instrinsic subphase/amphiphile interaction but also on the total amphiphile inventory and area of the liquid subphase.
PMCID: PMC3523312  PMID: 23039250
16.  Improving Blood Compatibility of Intravascular Oxygen Sensors Via Catalytic Decomposition of S-Nitrosothiols to Generate Nitric Oxide In Situ 
Reliable, real-time, in vivo sensing (intravascular) of blood gases and electrolytes remains a difficult challenge owing to biocompatibility issues that occur when chemical sensors are implanted into the blood stream. Recently, local release of nitric oxide (NO) at the sensor/blood interface has been suggested as a potential solution to this problem. However, the lifetime of NO release from thin polymer films coated on implanted sensors is limited by the reservoir of NO donor loaded within the polymeric coating. To continuously produce NO at the sensor/blood interface, a novel approach to catalytically decompose endogenous S-nitrosothiols (RSNOs) in blood to generate NO in situ is reported herein. Metallic copper particles of two different sizes (3 μm and 80 nm) are embedded as catalysts in thin polymer coatings on the surface intravascular electrochemical oxygen sensing catheters. Oxygen levels (partial pressure of oxygen; PO2) provided by the copper particle/polymer coated sensors are, on average, more accurate than values obtained from non-NO generating control sensors when both types of sensors are implanted in porcine arteries for 19–20 h. Upon termination of each in vivo study, catheters were explanted and examined for surface thrombosis via both visual image and lactate dehydrogenase (LDH) assay. The results indicate that the Cu0-catalyst coatings significantly reduce the occurrence of surface thrombosis, likely from the ability to generate NO from endogenous RSNO species at the sensor/blood interface.
PMCID: PMC1805711  PMID: 17330157
nitric oxide generation; S-nitrosothiols; copper catalyst; intravascular electrochemical oxygen sensor
17.  Encapsulation of gold nanoparticles into self-assembling protein nanoparticles 
Gold nanoparticles are useful tools for biological applications due to their attractive physical and chemical properties. Their applications can be further expanded when they are functionalized with biological molecules. The biological molecules not only provide the interfaces for interactions between nanoparticles and biological environment, but also contribute their biological functions to the nanoparticles. Therefore, we used self-assembling protein nanoparticles (SAPNs) to encapsulate gold nanoparticles. The protein nanoparticles are formed upon self-assembly of a protein chain that is composed of a pentameric coiled-coil domain at the N-terminus and trimeric coiled-coil domain at the C-terminus. The self-assembling protein nanoparticles form a central cavity of about 10 nm in size, which is ideal for the encapsulation of gold nanoparticles with similar sizes.
We have used SAPNs to encapsulate several commercially available gold nanoparticles. The hydrodynamic size and the surface coating of gold nanoparticles are two important factors influencing successful encapsulation by the SAPNs. Gold nanoparticles with a hydrodynamic size of less than 15 nm can successfully be encapsulated. Gold nanoparticles with citrate coating appear to have stronger interactions with the proteins, which can interfere with the formation of regular protein nanoparticles. Upon encapsulation gold nanoparticles with polymer coating interfere less strongly with the ability of the SAPNs to assemble into nanoparticles. Although the central cavity of the SAPNs carries an overall charge, the electrostatic interaction appears to be less critical for the efficient encapsulation of gold nanoparticles into the protein nanoparticles.
The SAPNs can be used to encapsulate gold nanoparticles. The SAPNs can be further functionalized by engineering functional peptides or proteins to either their N- or C-termini. Therefore encapsulation of gold nanoparticles into SAPNs can provide a useful platform to generate a multifunctional biodevices.
PMCID: PMC3502577  PMID: 23114058
18.  Electroformation of Janus and patchy capsules 
Nature Communications  2014;5:3945.
Janus and patchy particles have designed heterogeneous surfaces that consist of two or several patches with different materials properties. These particles are emerging as building blocks for a new class of soft matter and functional materials. Here we introduce a route for forming heterogeneous capsules by producing highly ordered jammed colloidal shells of various shapes with domains of controlled size and composition. These structures combine the functionalities offered by Janus or patchy particles, and those given by permeable shells such as colloidosomes. The simple assembly route involves the synergetic action of electro-hydrodynamic flow and electro-coalescence. We demonstrate that the method is robust and straightforwardly extendable to production of multi-patchy capsules. This forms a starting point for producing patchy colloidosomes with domains of anisotropic chemical surface properties, permeability or mixed liquid–solid phase domains, which could be exploited to produce functional emulsions, light and hollow supra-colloidosome structures, or scaffolds.
Colloidal self-assembly at liquid interfaces has important emulsion applications, for food, household or personal care products, and drug encapsulation. Here, the authors develop a method of forming patchy heterogeneous capsules by electro-coalescence of multiple liquid drops.
PMCID: PMC4050235  PMID: 24853057
19.  How to Prepare Reproducible, Homogeneous, and Hydrolytically Stable Aminosilane-derived Layers on Silica 
Langmuir  2011;28(1):416-423.
Five functional silanes, 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), N-(2-aminoethyl)-3-aminopropyltriethoxysilane (AEAPTES), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS), and N-(6-aminohexyl)aminomethyltriethoxysilane (AHAMTES) were assessed for the preparation of hydrolytically stable amine-functionalized silica substrates. These can be categorized into three groups (G1, G2, and G3) based on the intra-molecular coordinating ability of the amine functionality to the silicon center. Silanizations were carried out in anhydrous toluene as well as in the vapor phase at elevated temperatures. Aminosilane-derived layers prepared in solution are multilayers in nature and those produced in the vapor phase have monolayer characteristics. In general, vapor-phase reactions are much less sensitive to variations in humidity and reagent purity, are more practical than solution-phase method, and generate more reproducible results. Intra-molecular catalysis by the amine functionality is found to be important for both silanizaton and hydrolysis. The primary amine group in the G1 silanes (APTES and APTMS) can readily catalyze siloxane bond formation and hydrolysis to render their silane layers unstable toward hydrolysis. The amine functionality in the G3 silane (AHAMTES) is incapable of intra-molecular catalysis of silanization so that stable siloxane bonds between the silane molecules and surface silanols do not form easily. The secondary amine group in the G2 silanes (AEAPTES and AEAPTMS), on the other hand, can catalyze siloxane bond formation, but the intra-molecular catalysis of bond detachment is sterically hindered. The G2 silanes are the best candidates for preparing stable amine-functionalized surfaces. Between the two G2 aminosilanes, AEAPTES results in more reproducible silane layers than AEAPTMS in the vapor phase due to its lower sensitivity to water content in the reaction systems.
PMCID: PMC3243110  PMID: 22128807
20.  An Efficient Approach to Surface-Initiated Ring-Opening Metathesis Polymerization of Cyclooctadiene 
Surface-initiated ring-opening metathesis polymerization of cyclooctadiene (COD), a low ring-strain olefin, is reported for the first time. Polymerization was carried out in the vapor phase, which is advantageous compared to conventional solution methods in terms of minimizing chain transfer by reducing polymer chain mobility at the vapor/solid interface. Attachments of a norbornenyl-containing silane and a Grubbs catalyst to silicon substrates were carried out before samples were exposed to COD vapor. The thickness of grafted 1,4-polybutadiene films was controlled by reaction time and reached ~40 nm after 7 h. The polymer films were further chemically modified to afford a new polymer, head-to-head poly(vinyl alcohol).
PMCID: PMC2515563  PMID: 17241005
21.  Hydrogel coated monoliths for enzymatic hydrolysis of penicillin G 
The objective of this work was to develop a hydrogel-coated monolith for the entrapment of penicillin G acylase (E. coli, PGA). After screening of different hydrogels, chitosan was chosen as the carrier material for the preparation of monolithic biocatalysts. This protocol leads to active immobilized biocatalysts for the enzymatic hydrolysis of penicillin G (PenG). The monolithic biocatalyst was tested in a monolith loop reactor (MLR) and compared with conventional reactor systems using free PGA, and a commercially available immobilized PGA. The optimal immobilization protocol was found to be 5 g l−1 PGA, 1% chitosan, 1.1% glutaraldehyde and pH 7. Final PGA loading on glass plates was 29 mg ml−1 gel. For 400 cpsi monoliths, the final PGA loading on functionalized monoliths was 36 mg ml−1 gel. The observed volumetric reaction rate in the MLR was 0.79 mol s−1 m−3monolith. Apart from an initial drop in activity due to wash out of PGA at higher ionic strength, no decrease in activity was observed after five subsequent activity test runs. The storage stability of the biocatalysts is at least a month without loss of activity. Although the monolithic biocatalyst as used in the MLR is still outperformed by the current industrial catalyst (immobilized preparation of PGA, 4.5 mol s−1 m−3catalyst), the rate per gel volume is slightly higher for monolithic catalysts. Good activity and improved mechanical strength make the monolithic bioreactor an interesting alternative that deserves further investigation for this application. Although moderate internal diffusion limitations have been observed inside the gel beads and in the gel layer on the monolith channel, this is not the main reason for the large differences in reactor performance that were observed. The pH drop over the reactor as a result of the chosen method for pH control results in a decreased performance of both the MLR and the packed bed reactor compared to the batch system. A different reactor configuration including an optimal pH profile is required to increase the reactor performance. The monolithic stirrer reactor would be an interesting alternative to improve the performance of the monolith-PGA combination.
PMCID: PMC2493519  PMID: 18427849
Monolith; Chitosan; Entrapment; PenicillinG; Bioreactor
22.  Organic electrode coatings for next-generation neural interfaces 
Traditional neuronal interfaces utilize metallic electrodes which in recent years have reached a plateau in terms of the ability to provide safe stimulation at high resolution or rather with high densities of microelectrodes with improved spatial selectivity. To achieve higher resolution it has become clear that reducing the size of electrodes is required to enable higher electrode counts from the implant device. The limitations of interfacing electrodes including low charge injection limits, mechanical mismatch and foreign body response can be addressed through the use of organic electrode coatings which typically provide a softer, more roughened surface to enable both improved charge transfer and lower mechanical mismatch with neural tissue. Coating electrodes with conductive polymers or carbon nanotubes offers a substantial increase in charge transfer area compared to conventional platinum electrodes. These organic conductors provide safe electrical stimulation of tissue while avoiding undesirable chemical reactions and cell damage. However, the mechanical properties of conductive polymers are not ideal, as they are quite brittle. Hydrogel polymers present a versatile coating option for electrodes as they can be chemically modified to provide a soft and conductive scaffold. However, the in vivo chronic inflammatory response of these conductive hydrogels remains unknown. A more recent approach proposes tissue engineering the electrode interface through the use of encapsulated neurons within hydrogel coatings. This approach may provide a method for activating tissue at the cellular scale, however, several technological challenges must be addressed to demonstrate feasibility of this innovative idea. The review focuses on the various organic coatings which have been investigated to improve neural interface electrodes.
PMCID: PMC4034607  PMID: 24904405
coatings; carbon nanotubes; conductive polymers; hydrogels; living electrodes; material properties
23.  Modification of Hydrophilic and Hydrophobic Surfaces Using an Ionic-Complementary Peptide 
PLoS ONE  2007;2(12):e1325.
Ionic-complementary peptides are novel nano-biomaterials with a variety of biomedical applications including potential biosurface engineering. This study presents evidence that a model ionic-complementary peptide EAK16-II is capable of assembling/coating on hydrophilic mica as well as hydrophobic highly ordered pyrolytic graphite (HOPG) surfaces with different nano-patterns. EAK16-II forms randomly oriented nanofibers or nanofiber networks on mica, while ordered nanofibers parallel or oriented 60° or 120° to each other on HOPG, reflecting the crystallographic symmetry of graphite (0001). The density of coated nanofibers on both surfaces can be controlled by adjusting the peptide concentration and the contact time of the peptide solution with the surface. The coated EAK16-II nanofibers alter the wettability of the two surfaces differently: the water contact angle of bare mica surface is measured to be <10°, while it increases to 20.3±2.9° upon 2 h modification of the surface using a 29 µM EAK16-II solution. In contrast, the water contact angle decreases significantly from 71.2±11.1° to 39.4±4.3° after the HOPG surface is coated with a 29 µM peptide solution for 2 h. The stability of the EAK16-II nanofibers on both surfaces is further evaluated by immersing the surface into acidic and basic solutions and analyzing the changes in the nanofiber surface coverage. The EAK16-II nanofibers on mica remain stable in acidic solution but not in alkaline solution, while they are stable on the HOPG surface regardless of the solution pH. This work demonstrates the possibility of using self-assembling peptides for surface modification applications.
PMCID: PMC2117347  PMID: 18091996
24.  Enhancement of lipase activity in non-aqueous media upon immobilization on multi-walled carbon nanotubes 
Immobilization of biologically active proteins on nanosized surfaces is a key process in bionanofabrication. Carbon nanotubes with their high surface areas, as well as useful electronic, thermal and mechanical properties, constitute important building blocks in the fabrication of novel functional materials.
Lipases from Candida rugosa (CRL) were found to be adsorbed on the multiwalled carbon nanotubes with very high retention of their biological activity (97%). The immobilized biocatalyst showed 2.2- and 14-fold increases in the initial rates of transesterification activity in nearly anhydrous hexane and water immiscible ionic liquid [Bmim] [PF6] respectively, as compared to the lyophilized powdered enzyme. It is presumed that the interaction with the hydrophobic surface of the nanotubes resulted in conformational changes leading to the 'open lid' structure of CRL. The immobilized enzyme was found to give 64% conversion over 24 h (as opposed to 14% with free enzyme) in the formation of butylbutyrate in nearly anhydrous hexane. Similarly, with ionic liquid [Bmim] [PF6], the immobilized enzyme allowed 71% conversion as compared to 16% with the free enzyme. The immobilized lipase also showed high enantioselectivity as determined by kinetic resolution of (±) 1-phenylethanol in [Bmim] [PF6]. While free CRL gave only 5% conversion after 36 h, the immobilized enzyme resulted in 37% conversion with > 99% enantiomeric excess. TEM studies on the immobilized biocatalyst showed that the enzyme is attached to the multiwalled nanotubes.
Successful immobilization of enzymes on nanosized carriers could pave the way for reduced reactor volumes required for biotransformations, as well as having a use in the construction of miniaturized biosensensor devices.
PMCID: PMC2211749  PMID: 18047656
25.  Polysaccharide Ecocomposite Materials: Synthesis, Characterization and Application for Removal of Pollutants and Bacteria 
ECS transactions  2013;50(11):573-594.
A novel, simple and totally recyclable method has been developed for the synthesis of nontoxic, biocompatible and biodegradable composite materials from cellulose and chitosan. In this method, [BMIm+Cl−], an ionic liquid (IL), was used as a solvent to dissolve and synthesize the [CEL+CS] composite materials. Since the IL can be removed from the materials by washing them with water, and recovered from the washed solution, the method is totally recyclable. XRD, FTIR, NIR and SEM were used to characterize the materials and to confirm that CEL and CS were successfully regenerated by the method without any chemical transformation. More importantly, we have successfully demonstrated that [CEL+CS] material can serve as an effective adsorbent for removal of various endocrine disruptors including polychlorophenols and bisphenol A. This is because the composites have combined advantages of their components, namely superior chemical stability and mechanical stability (from CEL) and excellent adsorption capability for pollutants (from CS).
PMCID: PMC4508029  PMID: 26203313

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