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1.  Controlled synthesis and tunable properties of ultrathin silica nanotubes through spontaneous polycondensation on polyamine fibrils 
This paper describes a facile approach to a biomimetic rapid fabrication of ultrathin silica nanotubes with a highly uniform diameter of 10 nm and inner hollow of around 3 nm. The synthesis is carried out through a spontaneous polycondensation of alkoxysilane on polyamine crystalline fibrils that were conveniently produced from the neutralization of a solution of protonated linear polyethyleneimine (LPEI–H+) by alkali compounds. A simple mixing the fibrils with alkoxysilane in aqueous solution allowed for the rapid formation of silica to produce LPEI@silica hybrid nanotubes. These 10-nm nanotubes were hierarchically organized in a mat-like morphology with a typical size of 1–2 micrometers. The subsequent removal of organic LPEI via calcination resulted in silica nanotubes that keep this morphology. The morphology, the structure, the pore properties and the formation mechanism of the silica nanotubes were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller measurements (BET), and X-ray diffraction (XRD). Detailed studies demonstrated that the formation of the nanotubes depends on the molar ratio of [OH]/[CH2CH2NH] during the neutralization as well as on the basicity of the alkali compound and on the concentration of the silica source. The synthesis of silica nanotubes established here could be easily applied to a fabrication on the kilogram scale. Silica nanotubes that were obtained from the calcination of hybrid nanotubes of LPEI@silica in an N2 atmosphere showed a distinct photoluminescence centered at 540 nm with a maximum excitation wavelength of 320 nm. Furthermore, LPEI@silica hybrid nanotubes were applied to create silica–carbon composite nanotubes by alternative adsorption of ionic polymers and subsequent carbonization.
PMCID: PMC3869340  PMID: 24367748
biomimetic silicification; polyethyleneimine; silica–carbon nanocomposite; silica nanotubes; template synthesis
2.  Characterization of Nanoscale Transformations in Polyelectrolyte Multilayers Fabricated from Plasmid DNA Using Laser Scanning Confocal Microscopy in Combination with Atomic Force Microscopy 
Microscopy research and technique  2010;73(9):834-844.
Laser scanning confocal microscopy (LSCM) and atomic force microscopy (AFM) were used to characterize changes in nanoscale structure that occur when ultrathin polyelectrolyte multilayers (PEMs) are incubated in aqueous media. The PEMs investigated here were fabricated by the deposition of alternating layers of plasmid DNA and a hydrolytically degradable polyamine onto a precursor film composed of alternating layers of linear poly(ethylene imine) (LPEI) and sodium poly(styrene sulfonate) (SPS). Past studies of these materials in the context of gene delivery revealed transformations from a morphology that is smooth and uniform to one characterized by the formation of nanometer-scale particulate structures. We demonstrate that in-plane registration of LSCM and AFM images acquired from the same locations of films fabricated using fluorescently labeled polyelectrolytes allows the spatial distribution of individual polyelectrolyte species to be determined relative to the locations of topographic features that form during this transformation. Our results suggest that this physical transformation leads to a morphology consisting of a relatively less disturbed portion of film composed of polyamine and DNA juxtaposed over an array of particulate structures composed predominantly of LPEI and SPS. Characterization by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) microanalysis provides additional support for this interpretation. The combination of these different microscopy techniques provides insight into the structures and dynamics of these multicomponent thin films that cannot be achieved using any one method alone, and that could prove useful for the further development of these assemblies as platforms for the surface-mediated delivery of DNA.
PMCID: PMC2889202  PMID: 20155860
Thin Films; Nanostructure; Polymers; Layer-by-Layer; DNA Delivery
3.  Nanoscale Roughness and Morphology Affect the IsoElectric Point of Titania Surfaces 
PLoS ONE  2013;8(7):e68655.
We report on the systematic investigation of the role of surface nanoscale roughness and morphology on the charging behaviour of nanostructured titania (TiO2) surfaces in aqueous solutions. IsoElectric Points (IEPs) of surfaces have been characterized by direct measurement of the electrostatic double layer interactions between titania surfaces and the micrometer-sized spherical silica probe of an atomic force microscope in NaCl aqueous electrolyte. The use of a colloidal probe provides well-defined interaction geometry and allows effectively probing the overall effect of nanoscale morphology. By using supersonic cluster beam deposition to fabricate nanostructured titania films, we achieved a quantitative control over the surface morphological parameters. We performed a systematical exploration of the electrical double layer properties in different interaction regimes characterized by different ratios of characteristic nanometric lengths of the system: the surface rms roughness Rq, the correlation length ξ and the Debye length λD. We observed a remarkable reduction by several pH units of IEP on rough nanostructured surfaces, with respect to flat crystalline rutile TiO2. In order to explain the observed behavior of IEP, we consider the roughness-induced self-overlap of the electrical double layers as a potential source of deviation from the trend expected for flat surfaces.
PMCID: PMC3712945  PMID: 23874708
4.  Mapping the Complex Morphology of Cell Interactions with Nanowire Substrates Using FIB-SEM 
PLoS ONE  2013;8(1):e53307.
Using high resolution focused ion beam scanning electron microscopy (FIB-SEM) we study the details of cell-nanostructure interactions using serial block face imaging. 3T3 Fibroblast cellular monolayers are cultured on flat glass as a control surface and on two types of nanostructured scaffold substrates made from silicon black (Nanograss) with low- and high nanowire density. After culturing for 72 hours the cells were fixed, heavy metal stained, embedded in resin, and processed with FIB-SEM block face imaging without removing the substrate. The sample preparation procedure, image acquisition and image post-processing were specifically optimised for cellular monolayers cultured on nanostructured substrates. Cells display a wide range of interactions with the nanostructures depending on the surface morphology, but also greatly varying from one cell to another on the same substrate, illustrating a wide phenotypic variability. Depending on the substrate and cell, we observe that cells could for instance: break the nanowires and engulf them, flatten the nanowires or simply reside on top of them. Given the complexity of interactions, we have categorised our observations and created an overview map. The results demonstrate that detailed nanoscale resolution images are required to begin understanding the wide variety of individual cells’ interactions with a structured substrate. The map will provide a framework for light microscopy studies of such interactions indicating what modes of interactions must be considered.
PMCID: PMC3541134  PMID: 23326412
5.  Electrochemical DNA biosensor based on the BDD nanograss array electrode 
The development of DNA biosensor has attracted considerable attention due to their potential applications, including gene analysis, clinical diagnostics, forensic study and more medical applications. Using electroactive daunomycin as an indicator, the hybridization detection was measured by differential pulse voltammetry in this study.
Electrochemical DNA biosensor was developed based on the BDD film electrode (fBDD) and BDD nanograss array electrode (nBDD). In comparison with fBDD and AuNPs/CA/fBDD electrode, the lower semicircle diameter of electrochemical impedance spectroscopy obtained on nBDD and AuNPs/CA/nBDD electrode indicated that the presence of nanograss array improved the reactive site, reduced the interfacial resistance, and made the electron transfer easier. Using electroactive daunomycin as an indicator, the hybridization detection was measured by differential pulse voltammetry.
The experimental results demonstrated that the prepared AuNPs/CA/nBDD electrode was suitable for DNA hybridization with favorable performance of faster response, higher sensitivity, lower detection limit and satisfactory selectivity, reproducibility and stability.
PMCID: PMC3637572  PMID: 23575250
DNA biosensor; AuNPs/CA/nBDD; AuNPs/CA/fBDD
6.  Nanoscale control of silica particle formation via silk-silica fusion proteins for bone regeneration 
The biomimetic design of silk/silica fusion proteins was carried out, combining the self assembling domains of spider dragline silk (Nephila clavipes) and silaffin derived R5 peptide of Cylindrotheca fusiformis that is responsible for silica mineralization. Genetic engineering was used to generate the protein-based biomaterials incorporating the physical properties of both components. With genetic control over the nanodomain sizes and chemistry, as well as modification of synthetic conditions for silica formation, controlled mineralized silk films with different silica morphologies and distributions were successfully generated; generating 3D porous networks, clustered silica nanoparticles (SNPs), or single SNPs. Silk serves as the organic scaffolding to control the material stability and multiprocessing makes silk/silica biomaterials suitable for different tissue regenerative applications. The influence of these new silk-silica composite systems on osteogenesis was evaluated with human mesenchymal stem cells (hMSCs) subjected to osteogenic differentiation. hMSCs adhered, proliferated, and differentiated towards osteogenic lineages on the silk/silica films. The presence of the silica in the silk films influenced osteogenic gene expression, with the upregulation of alkaline phosphatase (ALP), bone sialoprotein (BSP), and collagen type 1 (Col 1) markers. Evidence for early bone formation as calcium deposits was observed on silk films with silica. These results indicate the potential utility of these new silk/silica systems towards bone regeneration.
PMCID: PMC2956983  PMID: 20976116
7.  Understanding the protonation behavior of linear polyethylenimine in solutions through Monte Carlo simulations 
Biomacromolecules  2010;11(1):29.
The success of polyethyleneimine (PEI) as a non-viral based gene delivery vector has been attributed to its proton buffering capacity. Despite the great interest in PEI for its use in non-viral based gene delivery, the protonation behavior of PEI in solution is not well understood. Earlier experimental studies have reported inconsistent values of the protonation state of PEI. In this work, we report our investigation of the protonation behavior of a realistic linear PEI (lPEI) with computational approaches. Reported experimental pKa values of several diamine compounds are first examined. A screened coulombic interaction with a distance dependence dielectric is shown to reproduce the shifted pKa values of the model diamine compounds. Then atomistic molecular dynamics simulations of lPEI chain with 20 repeating units are performed and the results are used to provide parameters for a coarse-grained polyamine model. The screened coulombic interaction is then incorporated in the coarse-grained lPEI chain and computational titrations are performed. The obtained computational titration curves of lPEI in solutions were found to be in best agreement with experimental results by Smits et al, but the computational titration curves have too strong of a dependence on salt concentration compared to the experimental results by Smits et al. Disregarding the discrepancy in the salt dependence, our computational titrations reveal that approximately 55% of the lPEI amine groups are protonated under physiological conditions in solution with a nearly alternating arrangement of protonated and non-protonated amines. Titrations of lPEI in the presence of a polyanion are also performed to determine how the charge state of lPEI could be affected by complexation with DNA in gene therapy preparations. While the presence of the polyanion increases the degree of protonation of the PEI, many of PEI amines remain unprotonated under physiological conditions, providing evidence that PEI complexed with DNA could still have proton buffering capacity. Potential sources of error that have resulted in the inconsistency of previously reported protonation states of PEI were also discussed.
PMCID: PMC2821107  PMID: 19954222
linear polyethyleneimine; protonation behavior; Monte Carlo titration; gene delivery
8.  Multilayer mediated forward and patterned siRNA transfection using linear-PEI at extended N/P ratios 
Acta biomaterialia  2009;5(5):1474-1488.
Gene delivery from a substrate depends, in part, on the vector-nucleic acid complex that is bound to the surface and the cell adhesive properties of the surface. Here, we present a method to deliver patterns of small interfering RNA (siRNA) that capitalize on a forward transfection method (transfection by introducing siRNA-transfection reagent complexes onto plated cells); herein denoted as multilayer mediated forward transfection (MFT). This method separates the substrate-mediated delivery from the cell adhesive properties of the surface. pH responsive layer-by-layer (LbL) assembled multilayers were used as the delivery platform and microcontact printing technique (μCP) was used to pattern nanoparticles of transfection reagent-siRNA complexes onto degradable multilayers. Efficient MFT depend on optimal formulation of the nanoparticles. 25 kDa linear polyethylenimine (LPEI) was optimized as the siRNA transfection reagent for normal forward transfection (NFT) of the nanoparticles. A broad range of LPEI-siRNA nitrogen/phosphate (N/P) ratios (ranging from 5 to 90) was evaluated for the relative amounts of siRNA incorporated into the nanoparticles, nanoparticle size and NFT efficiencies. All the siRNA was incorporated into the nanoparticles at N/P ratio near 90. Increasing the amount of siRNA incorporated into the nanoparticles, with increasing N/P ratio correlated with a linear blue-shift in the ultraviolet/visible (UV/vis) absorbance spectrum of the LPEI-siRNA nanoparticles. NFT efficiency greater than 80% was achieved with minimal cytotoxicity at N/P ratio of 30 and siRNA concentration of 200 nM. Similarly, MFT efficiency ≥ 60% was achieved for LPEI-siRNA nanoparticles at N/P ratios greater than 30.
PMCID: PMC2677632  PMID: 19217360
Patterned siRNA transfection; Forward transfection; Layer-by-layer (LbL) assembly; Linear polyethylenimine (LPEI)-siRNA nanoparticles; N/P ratio; UV/vis blue shift
9.  Superhydrophobic surfaces of the water bug Notonecta glauca: a model for friction reduction and air retention 
Superhydrophobic surfaces of plants and animals are of great interest for biomimetic applications. Whereas the self-cleaning properties of superhydrophobic surfaces have been extensively investigated, their ability to retain an air film while submerged under water has not, in the past, received much attention. Nevertheless, air retaining surfaces are of great economic and ecological interest because an air film can reduce friction of solid bodies sliding through the water. This opens perspectives for biomimetic applications such as low friction fluid transport or friction reduction on ship hulls. For such applications the durability of the air film is most important. While the air film on most superhydrophobic surfaces usually lasts no longer than a few days, a few semi-aquatic plants and insects are able to hold an air film over a longer time period. Currently, we found high air film persistence under hydrostatic conditions for the elytra of the backswimmer Notonecta glauca which we therefore have chosen for further investigations. In this study, we compare the micro- and nanostructure of selected body parts (sternites, upper side of elytra, underside of elytra) in reference to their air retaining properties. Our investigations demonstrate outstanding air film persistence of the upper side of the elytra of Notonecta glauca under hydrostatic and hydrodynamic conditions. This hierarchically structured surface was able to hold a complete air film under hydrostatic conditions for longer than 130 days while on other body parts with simple structures the air film showed gaps (underside of elytra) or even vanished completely after a few days (sternites). Moreover, the upper side of the elytra was able to keep an air film up to flow velocities of 5 m/s. Obviously the complex surface structure with tiny dense microtrichia and two types of larger specially shaped setae is relevant for this outstanding ability. Besides high air film persistence, the observation of a considerable fluid velocity directly at the air–water interface indicates the ability to reduce friction significantly. The combination of these two abilities makes these hierarchically structured surfaces extremely interesting as a biomimetic model for low friction fluid transport or drag reduction on ship hulls.
PMCID: PMC3148060  PMID: 21977425
air film; aquatic insects; backswimmer; drag reduction; superhydrophobic surfaces
10.  Addition of ‘Charge-Shifting’ Side Chains to Linear Poly(ethyleneimine) Enhances Cell Transfection Efficiency 
Biomacromolecules  2008;9(7):2063-2071.
We reported recently that the addition of ester-functionalized, ‘charge-shifting’ side chains to linear poly(ethyleneimine) (LPEI) can be used to design polyamines that promote both self-assembly and self-disassembly with DNA in aqueous environments. This investigation sought to characterize the influence of charge-shifting side chains on the ability of LPEI to mediate cell transfection and understand the extent to which increases (or decreases) in levels of transfection could be understood in terms of time-dependent changes in the net charges of these polymers. We report that the addition of ‘charge-shifting’ side chains to LPEI leads to significant increases in levels of LPEI-mediated transfection. In particular, polymer 1e, functionalized with 20 mol% ester-functionalized side chains, mediates levels of transgene expression in vitro up to eight-fold higher than LPEI. Experiments using an amide-functionalized analog of polymer 1e demonstrated that the esters in polymer 1e play an important role in promoting increased levels of transfection. These results, in combination with the results of additional gel electrophoresis experiments, provide support for the view that increases in transfection result from time-dependent changes in the net charge of polymer 1e and the disruption of ionic interactions in polyplexes. Additional support for this view is provided by the results of confocal microscopy experiments and measurements of fluorescence resonance energy transfer, which suggest that polymer 1e promotes the disruption of polyplexes in intracellular environments effectively. The approach reported here provides a means of addressing one important ‘late-stage’ obstacle to polyplex-mediated transfection (polyplex unpackaging). If integrated successfully with methods that have been developed to address other important barriers to transfection, this general approach could lead to the development of multifunctional polyplexes that mimic more effectively the range of functions of viruses as agents for the delivery of DNA.
PMCID: PMC2556208  PMID: 18564876
11.  Quantitative Characterization of the Influence of the Nanoscale Morphology of Nanostructured Surfaces on Bacterial Adhesion and Biofilm Formation 
PLoS ONE  2011;6(9):e25029.
Bacterial infection of implants and prosthetic devices is one of the most common causes of implant failure. The nanostructured surface of biocompatible materials strongly influences the adhesion and proliferation of mammalian cells on solid substrates. The observation of this phenomenon has led to an increased effort to develop new strategies to prevent bacterial adhesion and biofilm formation, primarily through nanoengineering the topology of the materials used in implantable devices. While several studies have demonstrated the influence of nanoscale surface morphology on prokaryotic cell attachment, none have provided a quantitative understanding of this phenomenon. Using supersonic cluster beam deposition, we produced nanostructured titania thin films with controlled and reproducible nanoscale morphology respectively. We characterized the surface morphology; composition and wettability by means of atomic force microscopy, X-ray photoemission spectroscopy and contact angle measurements. We studied how protein adsorption is influenced by the physico-chemical surface parameters. Lastly, we characterized Escherichia coli and Staphylococcus aureus adhesion on nanostructured titania surfaces. Our results show that the increase in surface pore aspect ratio and volume, related to the increase of surface roughness, improves protein adsorption, which in turn downplays bacterial adhesion and biofilm formation. As roughness increases up to about 20 nm, bacterial adhesion and biofilm formation are enhanced; the further increase of roughness causes a significant decrease of bacterial adhesion and inhibits biofilm formation. We interpret the observed trend in bacterial adhesion as the combined effect of passivation and flattening effects induced by morphology-dependent protein adsorption. Our findings demonstrate that bacterial adhesion and biofilm formation on nanostructured titanium oxide surfaces are significantly influenced by nanoscale morphological features. The quantitative information, provided by this study about the relation between surface nanoscale morphology and bacterial adhesion points towards the rational design of implant surfaces that control or inhibit bacterial adhesion and biofilm formation.
PMCID: PMC3180288  PMID: 21966403
12.  Morphology-controlled synthesis of silica nanotubes through pH- and sequence-responsive morphological change of bacterial flagellar biotemplates 
Journal of materials chemistry  2012;22:15702-15709.
Bacterial flagella are naturally-occurring self-assembling protein nanofibers protruding from the bacterial surface to assist the swimming of bacteria. They are rigid and exhibit diverse morphologies depending on the ionic strength, the pH values, temperature, and subunit sequences. Here, the silica nanotubes (SNTs) with controllable morphologies were synthesized using flagella as biological templates in aqueous solution under mild conditions. The morphologies and surface features of flagella-templated SNTs can be simply tuned by adjusting the pH value or surface chemistry of flagella by peptide display. A variety of different morphologies (coiled, straight, and curly with different wavelengths) and surface features (smooth, rough, granular and pear-necklace-like) of SNTs were obtained. When pH varies from acidic to alkaline conditions, in general, SNTs varied from bundled coiled, to characteristic sinusoidal waves, helical, and straight morphology. Under genetic control, flagella displaying negatively-charged peptides exhibited thinner layer of silica condensation but rough surface. However, flagella with positively-charged peptide inserts induced the deposition of thicker silica shell with smooth surface. Incorporation of hydroxyl bearing amino acid residues such as Ser into the peptide displayed on flagella highly enhanced the biotemplated deposition of silica. This work suggests that bacterial flagella are promising biotemplates for developing an environmentally-benign and cost-efficient approach to morphology-controlled synthesis of nanotubes. Moreover, the dependency of the thickness of the silica shell on the peptides displayed on flagella helps us to further understand the mechanism of biomimetic nucleation of silica on biological templates.
PMCID: PMC3409586  PMID: 22865955
13.  Characterization of localized surface plasmon resonance transducers produced from Au25 nanoparticle multilayers 
This article reports the preparation of gold plasmonic transducers using a nanoparticle self-assembly/heating method and the characterization of the films using scattering-type scanning near-field optical microscopy (s-SNOM). Nanoparticle-polymer multilayer films were prepared by the layer-by-layer assembly on glass slides by alternating exposures to monodisperse Au25 nanoparticles and ionic polymer linkers. Thermal evaporation of organic matters from the nanoparticle-polymer multilayer films at 600 °C allowed the nanoparticles to coalescence and form nanostructured films. Characterization of the nanostructured films generated from Au25 nanoparticles using atomic force microscopy (AFM) showed that the films have rounded, small, island-like morphologies (d: 30-50 nm) with a pit in the center of many islands. However, further characterizations with s-SNOM revealed that the produced nanoislands contain a single gold cluster in a pit surrounded by donut-shaped dielectric species. Formation of such a structure is thought to be resulted from the embedding of gold clusters under the reorganized polysiloxane binder coatings and glass surfaces during heat treatment of the Au25 nanoparticle multilayer films. The nanostructured films displayed strong surface plasmon resonance bands in UV-vis spectra with a peak absorbance occurring at ~545-550 nm. The optical sensing capability of the films was examined using D-glucose-functionalized gold island films with the interaction of Concanavalin A (ConA). The result showed that the adsorption of ConA on island films causes a large change in the LSPR band intensity.
PMCID: PMC3398733  PMID: 22822292
Nanoislands; Nanoparticle; Self-Assembly; Plasmonics; Sensor; Gold
14.  Growth of Optically Active Chiral Inorganic Films through DNA Self-Assembly and Silica Mineralisation 
Scientific Reports  2014;4:4866.
The circularly polarized reflection of nature is due to their distinct azimuthally twisted or helical character in the nanostructure of the surface films. Although many chiral inorganic powders have been successfully synthesised, the artificial synthesis of chiral inorganic films is rare. Herein, we reported a facile synthetic route for the growth of monolayered chiral film on the quaternary ammonium-modified silicon substrate. The films grew on the substrate surface because of the strong electrostatic interaction between positively charged quaternary ammonium groups and negatively charged phosphate groups of DNA, with subsequent growth to right-handed, vertically aligned, impeller-like helical architectures with left-handed two-dimensional square p4mm-structured DNA chiral packing. The DNA–silica composite films exhibited strong optical activity at 295 nm and in the range of 400–800 nm, corresponding to DNA chiral packing (absorption) and to the helical blade in the impeller (scattering), respectively. Upon removal of DNA templates, the pure inorganic impeller-like helical morphology was maintained; consequently, the scattering-based optical response was blue-shifted approximately 200 nm as a result of a decrease in the effective average refractive index. The hierarchical structures were reflected from the surfaces by cross-polarised light, which confirmed that the films were strongly birefringent, with long-range anisotropy.
PMCID: PMC4007082  PMID: 24784912
15.  Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size 
This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.
PMCID: PMC3102539  PMID: 21625329
Nanoislands; Nanoparticles; Self-Assembly; Plasmonics; Au
16.  Superhydrophobic Surface Based on a Coral-Like Hierarchical Structure of ZnO 
PLoS ONE  2010;5(12):e14475.
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.
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.
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.
PMCID: PMC3012683  PMID: 21209931
17.  Subtleties of biomineralisation revealed by manipulation of the eggshell membrane 
Biomaterials  2011;32(34):8743-8752.
Biocalcification of collagen matrices with calcium phosphate and biosilicification of diatom frustules with amorphous silica are two discrete processes that have intrigued biologists and materials scientists for decades. Recent advancements in the understanding of the mechanisms involved in these two biomineralisation processes have resulted in the use of biomimetic strategies to replicate these processes separately using polyanionic, polycationic or zwitterionic analogues of extracellular matrix proteins to stabilise amorphous mineral precursor phases. To date, there is a lack of a universal model that enables the subtleties of these two apparently dissimilar biomineralisation processes to be studied together. Here, we utilise the eggshell membrane as a universal model for differential biomimetic calcification and silicification. By manipulating the eggshell membrane to render it permeable to stabilised mineral precursors, it is possible to introduce nanostructured calcium phosphate or silica into eggshell membrane fibre cores or mantles. We provide a model for infiltrating the two compartmental niches of a biopolymer membrane with different intrafibre minerals to obtain materials with potentially improved structure-property relationships.
PMCID: PMC3183170  PMID: 21864897
apatite; biomineralisation; silica; membrane
18.  Formation of Asymmetrical Structured Silica Controlled by a Phase Separation Process and Implication for Biosilicification 
PLoS ONE  2013;8(4):e61164.
Biogenetic silica displays intricate patterns assembling from nano- to microsize level and interesting non-spherical structures differentiating in specific directions. Several model systems have been proposed to explain the formation of biosilica nanostructures. Of them, phase separation based on the physicochemical properties of organic amines was considered to be responsible for the pattern formation of biosilica. In this paper, using tetraethyl orthosilicate (TEOS, Si(OCH2CH3)4) as silica precursor, phospholipid (PL) and dodecylamine (DA) were introduced to initiate phase separation of organic components and influence silica precipitation. Morphology, structure and composition of the mineralized products were characterized using a range of techniques including field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), infrared spectra (IR), and nitrogen physisorption. The results demonstrate that the phase separation process of the organic components leads to the formation of asymmetrically non-spherical silica structures, and the aspect ratios of the asymmetrical structures can be well controlled by varying the concentration of PL and DA. On the basis of the time-dependent experiments, a tentative mechanism is also proposed to illustrate the asymmetrical morphogenesis. Therefore, our results imply that in addition to explaining the hierarchical porous nanopatterning of biosilica, the phase separation process may also be responsible for the growth differentiation of siliceous structures in specific directions. Because organic amine (e.g., long-chair polyamines), phospholipids (e.g., silicalemma) and the phase separation process are associated with the biosilicification of diatoms, our results may provide a new insight into the mechanism of biosilicification.
PMCID: PMC3621999  PMID: 23585878
19.  Asymmetric Free-Standing Film with Multifunctional Anti-Bacterial and Self-Cleaning Properties 
ACS applied materials & interfaces  2012;4(9):4476-4483.
A superhydrophobic/hydrophilic asymmetric free-standing film has been created using layer-by-layer assembly technique. Poly(ethylene-imine)-Ag+ complex (PEI-Ag+) at pH 9.0 was assembled with poly(acrylic acid) (PAA) at pH 3.2 on a Teflon substrate to yield a micro-nanostructured surface that can be turned to be superhydrophobic after being coated with a low surface energy compound. Silver nanoparticle loaded free-standing film with one surface being superhydrophobic while the other surface is hydrophilic was then obtained after detachment from the substrate. The superhydrophobicity enabled the upper surface with anti adhesion and self-cleaning properties and the hydrophilic bottom surface can release silver ions as antibiotic agent. The broad-spectrum antimicrobial capability of silver ions released from the bottom surface coupled with superhydrophobic barrier protection of the upper surface may make the free-standing film a new therapy for open wound.
PMCID: PMC4111538  PMID: 22947922
Asymmetric; superhydrophobic; free-standing films; anti adhesion; drug release; layer-by-layer assembly
20.  Characterization of Lipid-Templated Silica and Hybrid Thin Film Mesophases by Grazing Incidence Small-Angle X-ray Scattering 
The nanostructure of silica and hybrid thin film mesophases templated by phospholipids via an evaporation-induced self-assembly (EISA) process was investigated by grazing-incidence small-angle X-ray scattering (GISAXS). Diacyl phosphatidylcholines with two tails of 6 or 8 carbons were found to template 2D hexagonal mesophases, with the removal of lipid from these lipid/silica films by thermal or UV/O3 processing resulting in a complete collapse of the pore volume. Monoacyl phosphatidylcholines with single tails of 10–14 carbons formed 3D micellular mesophases; the lipid was found to be extractable from these 3D materials, yielding a porous material. In contrast to pure lipid/silica thin film mesophases, films formed from the hybrid bridged silsesquioxane precursor bis(triethoxysilyl)ethane exhibited greater stability toward (both diacyl and monoacyl) lipid removal. Ellipsometric, FTIR, and NMR studies show that the presence of phospholipid suppresses siloxane network formation, while actually promoting condensation reactions in the hybrid material. 1D X-ray scattering and FTIR data were found to be consistent with strong interactions between lipid headgroups and the silica framework.
PMCID: PMC2736351  PMID: 19496546
21.  Two-Dimensional Nanostructure- Reinforced Biodegradable Polymeric Nanocomposites for Bone Tissue Engineering 
Biomacromolecules  2013;14(3):900-909.
This study investigates the efficacy of two dimensional (2D) carbon and inorganic nanostructures as reinforcing agents of crosslinked composites of the biodegradable and biocompatible polymer polypropylene fumarate (PPF) as a function of nanostructure concentration. PPF composites were reinforced using various 2D nanostructures: single- and multi-walled graphene oxide nanoribbons (SWGONRs, MWGONRs), graphene oxide nanoplatelets (GONPs), and molybdenum di-sulfite nanoplatelets (MSNPs) at 0.01–0.2 weight% concentrations. Cross-linked PPF was used as the baseline control, and PPF composites reinforced with single- or multi-walled carbon nanotubes (SWCNT, MWCNT) were used as positive controls. Compression and flexural testing show a significant enhancement (i.e., compressive modulus = 35–108%, compressive yield strength = 26–93%, flexural modulus = 15–53%, and flexural yield strength = 101–262% greater than the baseline control) in the mechanical properties of the 2D-reinforced PPF nanocomposites. MSNPs nanocomposites consistently showed the highest values among the experimental or control groups in all the mechanical measurements. In general, the inorganic nanoparticle MSNPs showed a better or equivalent mechanical reinforcement compared to carbon nanomaterials, and 2-D nanostructures (GONP, MSNP) are better reinforcing agents compared to 1-D nanostructures (e.g. SWCNTs). The results also indicate that the extent of mechanical reinforcement is closely dependent on the nanostructure morphology and follows the trend nanoplatelets > nanoribbons > nanotubes. Transmission electron microscopy of the cross-linked nanocomposites indicates good dispersion of nanomaterials in the polymer matrix without the use of a surfactant. The sol-fraction analysis showed significant changes in the polymer cross-linking in the presence of MSNP (0.01–0.2 wt %) and higher loading concentrations of GONP and MWGONR (0.1–0.2 wt%). The analysis of surface area and aspect ratio of the nanostructures taken together with the above results indicates differences in nanostructure architecture (2D vs. 1D nanostructures), as well as the chemical compositions (inorganic vs. carbon nanostructures), number of functional groups, and structural defects for the 2D nanostructures maybe key properties that affect the mechanical properties of 2D nanostructure-reinforced PPF nanocomposites, and the reason for the enhanced mechanical properties compared to the controls.
PMCID: PMC3601907  PMID: 23405887
22.  Microwave-Assisted Synthesis of Titania Nanocubes, Nanospheres and Nanorods for Photocatalytic Dye Degradation 
Nanoscale Research Letters  2008;4(2):144-152.
TiO2 nanostructures with fascinating morphologies like cubes, spheres, and rods were synthesized by a simple microwave irradiation technique. Tuning of different morphologies was achieved by changing the pH and the nature of the medium or the precipitating agent. As-synthesized titania nanostructures were characterized by X-ray diffraction (XRD), UV–visible spectroscopy, infrared spectroscopy (IR), BET surface area, photoluminescence (PL), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and atomic force microscopy (AFM) techniques. Photocatalytic dye degradation studies were conducted using methylene blue under ultraviolet light irradiation. Dye degradation ability for nanocubes was found to be superior to the spheres and the rods and can be attributed to the observed high surface area of nanocubes. As-synthesized titania nanostructures have shown higher photocatalytic activity than the commercial photocatalyst Degussa P25 TiO2.
PMCID: PMC2894357  PMID: 20596288
Nanocubes; Nanorods; Nanospheres; Photocatalytic activity; Microwave irradiation; Dye degradation
23.  Microwave-Assisted Synthesis of Titania Nanocubes, Nanospheres and Nanorods for Photocatalytic Dye Degradation 
Nanoscale Research Letters  2008;4(2):144-152.
TiO2nanostructures with fascinating morphologies like cubes, spheres, and rods were synthesized by a simple microwave irradiation technique. Tuning of different morphologies was achieved by changing the pH and the nature of the medium or the precipitating agent. As-synthesized titania nanostructures were characterized by X-ray diffraction (XRD), UV–visible spectroscopy, infrared spectroscopy (IR), BET surface area, photoluminescence (PL), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and atomic force microscopy (AFM) techniques. Photocatalytic dye degradation studies were conducted using methylene blue under ultraviolet light irradiation. Dye degradation ability for nanocubes was found to be superior to the spheres and the rods and can be attributed to the observed high surface area of nanocubes. As-synthesized titania nanostructures have shown higher photocatalytic activity than the commercial photocatalyst Degussa P25 TiO2.
PMCID: PMC2894357  PMID: 20596288
Nanocubes; Nanorods; Nanospheres; Photocatalytic activity; Microwave irradiation; Dye degradation
24.  Bactericidal Performance of Visible-Light Responsive Titania Photocatalyst with Silver Nanostructures 
PLoS ONE  2010;5(4):e10394.
Titania dioxide (TiO2) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO2 photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved.
Methodology/Principal Findings
Using thermal reduction method, here we synthesized silver-nanostructures coated TiO2 thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO2, carbon-doped TiO2 [TiO2 (C)] and nitrogen-doped TiO2 [TiO2 (N)], TiO2 (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO2 (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials.
Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.
PMCID: PMC2861596  PMID: 20454454
25.  Functionalized, Biodegradable Hydrogels for Control over Sustained and Localized siRNA Delivery to Incorporated and Surrounding Cells 
Acta biomaterialia  2012;9(1):4487-4495.
Currently, the most severe limitation to applying RNA interference (RNAi) technology is delivery, including localizing the molecules to a specific site of interest to target a specific cell population and sustaining the presentation of these molecules for a controlled period of time. In this study, we engineered a functionalized, biodegradable system created by covalent incorporation of cationic linear polyethyleneimine (LPEI) into photocrosslinked dextran (DEX) hydrogels through a biodegradable ester linkage. The key innovation of this system is that control over the sustained release of short interference RNA (siRNA) was achieved, as LPEI could electrostatically interact with siRNA to maintain siRNA within the hydrogels and degradation of the covalent ester linkages between the LPEI and the hydrogels led to tunable release of LPEI/siRNA complexes over time. The covalent conjugation of LPEI did not affect the swelling or degradation properties of the hydrogels, and the addition of siRNA and LPEI had minimal effect on their mechanical properties. These hydrogels exhibited low cytotoxicity against human embryonic kidney 293 cells (HEK293). The release profiles could be tailored by varying DEX (8 and 12 %w/w) and LPEI (0, 5, 10 μg/ 100 μl gel) concentrations with nearly 100% cumulative release achieved at day 9 (8 %w/w gel) and day 17 (12 %w/w gel). The released siRNA exhibited high bioactivity with cells surrounding and inside the hydrogels over an extended time period. This controllable and sustained siRNA delivery hydrogel system that permits tailored siRNA release profiles may be valuable to guide cell fate for regenerative medicine and other therapeutic applications such as cancer.
PMCID: PMC3508156  PMID: 22902819
dextran; injectable biomaterials; controlled delivery; photopolymerization; siRNA interference

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