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Bacteria killing behavior based on physical effects is preferred for biomedical implants because of the negligible associated side effects. However, our current understanding of the antibacterial activity of nanostructures remains limited and, in practice, nanoarchitectures that are created on orthopedics should also promote osteogenesis simultaneously. In this study, tilted and vertical nanolamellar structures are fabricated on semi-crystalline polyether-ether-ketone (PEEK) via argon plasma treatment with or without pre-annealing. The two types of nanolamellae can physically kill the bacteria that come into contact with them, but the antibacterial mechanisms between the two are different. Specifically, the sharp edges of the vertically aligned nanolamellae can penetrate and damage the bacterial membrane, whereas bacteria are stuck on the tilted nanostructures and are stretched, leading to eventual destruction. The tilted nanolamellae are more desirable than the vertically aligned ones from the perspective of peri-implant bone regeneration. Our study not only reveals the role of the arrangement of nanostructures in orthopedic applications but also provides new information about different mechanisms of physical antibacterial activity.

A tantalum/tantalum nitride (Ta/TaN) multilayered coating is deposited on plasma-nitridedAZ91 Mg alloy. The top TaN layer undergoes O 2 + Ar plasma etching to improve the antibacterial properties and Mg plasma immersion ion implantation (MgPIII) is performed to enhance the biocompatibility and wound healing capability. A uniform, compact, homogeneous, and columnar nanostructured MgPIII and plasma-etched TaN layer with a cluster size of about 17 nm, surface roughness of 0.28 nm, and needle morphology is observed. Although, plasma etching increases the corrosion current density ( i corr ) from 0.02 to 0.19 µA cm -2 due to larger surface roughness and different potentials between sharp points and smooth points, MgPIII decreases i corr from 0.19 to 0.02 µA cm -2 besides a more positive corrosion potential. The amounts of Mg +2 released to the simulated body fluid (SBF) diminishes from 89.63 ± 0.54 to 60.30 ± 0.47 mg l -1 cm -2 indicating improved corrosion resistance. Under fever conditions (40 °C), i corr decreases by 63%, but the open circuit potential does not change due to the constant chemical composition of the surface as well as thicker double layer and less defects, as confirmed by the larger amount of Mg +2 of 71.49 ± 0.22 mg l -1 cm -2 leached to the SBF. In the self-healing process which occurs via the reactions between the tantalum intermediate layer and electrolytes and penetrating ions through the defects as well as formation of oxide compounds, creation and propagation of defects are deterred as shown the 24 h destructive polarization test in SBF. The combination of plasma etching and MgPIII enhance not only the bacterial resistance and biocompatibility of the super-hard TaN layer by providing the rougher surface on TaN-P-Mg, but also the nano-mechanical properties and anticorrosion properties. As a result, the hardness increases by 7%, elastic modulus decreases by 19%, and the stiffness increases by 21%., (© 2021 IOP Publishing Ltd.)

2D silicon nanosheets (SiNSs) are promising materials for biomedicine but facile synthesis of SiNSs remains a challenge. Herein, by means of a sulfur-iodine co-assisted chemical vapor transport method, octahedron silicon (oct-Si) crystals with fully exposed {111} planes are prepared as precursors for efficient synthesis of SiNSs by facet-selective exfoliation. The 13 nm thick SiNSs have good biocompatibility and the sharp Raman scattering signal facilitates intracellular Raman imaging upon exposure to a near-infrared (NIR) laser. Furthermore, the SiNSs have excellent NIR photothermal characteristics such as a large extinction coefficient of 11.3 L g -1 cm -1 and high photothermal conversion efficiency of 21.4% at 1064 nm. In vitro experiments demonstrate superior NIR-II photothermal therapeutic effects in killing cancer cells. Comparing to conventional methods, the novel facet-selective cleavage strategy is more controllable and environmentally friendly boding well for the fabrication of non-van der Waals 2D materials. The multimodal photonic behavior also suggests large potential of the SiNSs pertaining to integrated multi-NIR biophotonic techniques using single nanomaterials., (© 2020 Wiley-VCH GmbH.)

Background and Purpose : Although inorganic nanomaterials have been widely used in multimodal cancer therapies, the intrinsic contributions of the materials are not well understood and sometimes underestimated. In this work, bioactive phospho-therapy with black phosphorus nanosheets (BPs) for in vivo tumor suppression is studied. Methods : Orthotopic liver tumor and acute myeloid leukemia are chosen as the models for the solid tumor and hematological tumor, respectively. BPs are injected into mice through the tail vein and tumor growth is monitored by IVIS bioluminescence imaging. Tumor tissues and serum samples are collected to determine the suppression effect and biosafety of BPs after treatment. Results : The in vitro studies show that BPs with high intracellular uptake produce apoptosis- and autophagy-mediated programmed cell death of human liver carcinoma cells but do not affect normal cells. BPs passively accumulate in the tumor site at a high concentration and inhibit tumor growth. The tumor weight is much less than that observed from the doxorubicin (DOX)-treated group. The average survival time is extended by at least two months and the survival rate is 100% after 120 days. Western bolt analysis confirms that BPs suppress carcinoma growth via the apoptosis and autophagy pathways. In addition, administration of BPs into mice suffering from leukemia results in tumor suppression and long survival. Conclusions : This study reveals that BPs constitute a type of bioactive anti-cancer agents and provides insights into the application of inorganic nanomaterials to cancer therapy., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

Low-dimensional nanomaterials (LDNs) are receiving increasing attention in cancer therapy owing to their unique properties, especially the large surface area-to-volume ratio. LDNs such as metallic nanoparticles (NPs), hydroxyapatite NPs, graphene derivatives, and black phosphorus (BP) nanosheets have been proposed for drug delivery, photothermal/photodynamic therapies, and multimodal theranostic treatments. The therapeutic effectiveness is mainly based on the physical characteristics of LDNs, but their inherent bioactivity has not been fully capitalized. In this Minireview, recent advances in the anti-cancer effects of various types of LDNs with inherent chemotherapeutic bioactivity are described and the bioactivity mechanisms are discussed on the cellular and molecular levels. BP, one of the newest and exciting members of the LDN family, is highlighted owing to the excellent inherent bioactivity, selectivity, and biocompatibility in cancer therapy. LDNs and related derivatives possess inherent bioactivity and selective chemotherapeutic effects suggesting large potential as nanostructured anti-cancer agents in cancer therapy., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Black phosphorus nanosheets (BPs) are demonstrated to be highly bioactive anti-cancer agents because of their inherent and selective chemotherapeutic effects. Fast intracellular biodegradation of BPs and acute elevation of phosphate anions were observed from different types of cancer cells due to the stronger intracellular oxidative stress and accelerated energy metabolism, but normal cells are not affected. Selective biodegradation of BPs induced G2/M phase arrest and subsequent apoptosis- and autophagy-mediated cell death in cancer cells but not normal cells. The selectivity was superior to that of the traditional chemotherapeutic agent, doxorubicin (DOX). In vivo assessment confirmed the efficiency of BPs in suppressing tumor growth. This study provides insights into nanostructured bioactive anti-cancer agents and reveals a new direction for nanomedicine research., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Interfacial characteristics play an important role in infection prevention and osteointegration of artificial bone implants. In this work, both Ag nanoparticles (AgNPs) and ZnO NPs are incorporated into hydroxyapatite (HA) nanopowders and deposited onto Ti6Al4V (Ti6) implants by laser cladding. The composite coatings possess a hierarchical surface structure with homogeneous distributions of Ag and ZnO. The Ag and ZnO NPs that are immobilized by laser cladding ensure long-term and gradual release of Ag and Zn ions at low cumulative concentrations of 36.2 and 56.4 μg/L after immersion for 21 days. A large concentration of Ag released initially increases the cytotoxicity but the large initial ZnO content enhances the cell viability and osteogenetic ability. The nano Ag/ZnO-embedded HA coating (Ag/ZnO/HA = 7:3:90 wt %, namely Ag7ZnO3HA) exhibits optimal antibacterial efficacy and osteogenetic capability, as exemplified by the broad spectrum antibacterial efficacy of 96.5 and 85.8% against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), respectively, together with enhanced osteoinductivity with higher alkaline phosphatase (ALP) activity of 134.60 U/g protein compared to 70.79 U/g protein for the untreated implants after culturing for 7 days. The rabbit femoral implant model further confirms that the optimized composite coating accelerates the formation of new bone tissues indicating 87.15% of the newly formed bone area and osteointegration showing 83.75% of the bone-implant contact area even in the presence of injected S. aureus. The laser-cladded Ag7ZnO3HA composite coatings are promising metallic implants with excellent intrinsic antibacterial activity and osteointegration ability.

Silver nanoparticles (AgNPs) enwrapped in the biologically safe tannic acid (TA)/Fe 3+ nanofilm are synthesized by an ultrafast, green, simple, and universal method. The physical antibacterial activity and photodynamic antibacterial therapy (PAT) efficacy of the TA/Fe 3+ /AgNPs nanofilm were investigated for the first time, which exhibited a strong physical antibacterial activity as well as great biocompatibility, through in vitro and in vivo studies. The results disclosed that this hybrid coating could possess high PAT capabilities upon irradiation under a visible light of 660 nm, which is longer than those of previously reported green and blue sensitization light, thus allowing deeper light penetration into biological tissues. Electron spin resonance (ESR) spectra proved that the PAT efficacy of the TA/Fe 3+ /AgNPs nanofilm was associated with the yields of singlet oxygen ( 1 O 2 ) under the irradiation of visible light (660 nm). A higher PAT efficiency of 100 and 94% against Escherichia coli and Staphylococcus aureus could be achieved within 20 min of illumination under 660 nm visible light, whereas the innate physical antibacterial activity of AgNPs could endow the implants with long-term prevention of bacterial infection. The mechanism of PAT may be associated with the formation of oxidative stress and oxidative damage to key biomolecules (proteins and lipids) in bacteria. Our results reveal that the synergistic action of both PAT and physical action of AgNPs in this hybrid nanofilm is an effective way to inactivate bacteria, with minimal side effects.

Two of the challenges for clinical implementation of nano-therapeutic strategies are optimization of tumor targeting and clearance of the nanoagents in vivo. Herein, a cell-mediated therapy by transporting 2D Bi 2 Se 3 nanosheets within macrophage vehicles is described. The Bi 2 Se 3 nanosheets with excellent near-infrared photothermal performance exhibit high macrophage uptake and negligible cytotoxicity thus facilitating the fabrication of Bi 2 Se 3 -laden-macrophages. Compared with bare Bi 2 Se 3 , the Bi 2 Se 3 -laden-macrophages after intravenous injection show prolonged blood circulation and can overcome the hypoxia-associated drug delivery barrier to target the tumor efficiently and dramatically enhance the efficiency of photothermal cancer therapy. The Bi 2 Se 3 -laden-macrophages possess good biocompatibility as demonstrated by the biochemical and histological analyses and furthermore, most of the materials are excreted from the body within 25 days. Our findings reveal a desirable system for highly efficient near-infrared photothermal cancer therapy., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Because of the excellent mechanical properties and good biocompatibility, titanium-based metals are widely used in hard tissue repair, especially load-bearing orthopedic applications. However, bacterial infection and complication during and after surgery often causes failure of the metallic implants. To endow titanium-based implants with antibacterial properties, surface modification is one of the effective strategies. Possessing the unique organic structure composed of molecular and functional groups resembling those of natural organisms, functionalized polymeric nanoarchitectures enhance not only the antibacterial performance but also other biological functions that are difficult to accomplish on many conventional bioinert metallic implants. In this review, recent advance in functionalized polymeric nanoarchitectures and the associated antimicrobial mechanisms are reviewed.

As an implantable material, carbon-fiber-reinforced polyetheretherketone (CFRPEEK) possesses an adjustable elastic modulus similar to that of cortical bone and is a prime candidate to replace metallic surgical implants. However, the bioinertness and poor osteogenic properties of CFRPEEK limit its clinical application as orthopedic implants. In this work, titanium ions are introduced energetically into CFRPEEK by plasma immersion ion implantation (PIII). Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) reveal the formation of nanopores with the side wall and bottom embedded with ∼20 nm TiO2 nanoparticles on the CFRPEEK surface. Nanoindentation measurements confirm the stability and improved elastic resistance of the structured surfaces. In vitro cell adhesion, viability assay, and real-time PCR analyses disclose enhanced adhesion, proliferation, and osteo-differentiation of rat bone mesenchymal stem cells (bMSCs). The multilevel structures on CFRPEEK also exhibit partial antibacterial activity to Staphylococcus aureus and Escherichia coli. Our results indicate that a surface with multifunctional biological properties can be produced by multilevel surface engineering and application of CFRPEEK to orthopedic and dental implants can be broadened and expedited based on this scheme., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Ultra-sensitive colorimetric determination of H2O2 is accomplished based on the intrinsic peroxidase-like activity of Au nanoclusters (AuNCs) stabilized by glutathione (GSH). The color change of 3,3,5,5-tetramethylbenzidine (TMB) catalyzed by AuNCs offers an indirect method to measure glucose. This sensing platform makes use of a dual optical signal change, including the color change in an aqueous solution under visible light illumination and an ultra-sensitive fluorescent assay arising from efficient fluorescence resonance energy transfer (FRET) between the AuNCs and oxidized TMB. The detection limits of H2O2 and glucose are 4.9 × 10(-13) M and 1.0 × 10(-11) M, respectively. In addition, enhanced fluorescence is observed from the AuNCs due to the use of ethanol which produces clear changes in the quantum yield and lifetime of the AuNCs. The quantum yield of AuNCs is enhanced from ∼12.5% as an isolated fluorophore to 38.9% in an AuNCs-ethanol complex. The enhanced fluorescence lowers the detection limits of H2O2 and glucose by 2 orders of magnitude compared to those attained from the original AuNCs.

Nitrogen fertilizer unabsorbed by crops eventually discharges into the environment through runoff, leaching and volatilization, resulting in three-dimensional (3D) pollution spanning from underground into space. Here we describe an approach for controlling nitrogen loss, developed using loss control fertilizer (LCF) prepared by adding modified natural nanoclay (attapulgite) to traditional fertilizer. In the aqueous phase, LCF self-assembles to form 3D micro/nano networks via hydrogen bonds and other weak interactions, obtaining a higher nitrogen spatial scale so that it is retained by a soil filtering layer. Thus nitrogen loss is reduced and sufficient nutrition for crops is supplied, while the pollution risk of the fertilizer is substantially lowered. As such, self-fabrication of nano-material was used to manipulate the nitrogen spatial scale, which provides a novel and promising approach for the research and control of the migration of other micro-scaled pollutants in environmental medium.

Porous biomaterials with the proper three-dimensional (3D) surface network can enhance biological functionalities especially in tissue engineering, but it has been difficult to accomplish this on an important biopolymer, polyetheretherketone (PEEK), due to its inherent chemical inertness. In this study, a 3D porous and nanostructured network with bio-functional groups is produced on PEEK by sulfonation and subsequent water immersion. Two kinds of sulfonation-treated PEEK (SPEEK) samples, SPEEK-W (water immersion and rinsing after sulfonation) and SPEEK-WA (SPEEK-W with further acetone rinsing) are prepared. The surface characteristics, in vitro cellular behavior, in vivo osseointegration, and apatite-forming ability are systematically investigated by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, cell adhesion and cell proliferation assay, real-time RT-PCR analysis, micro-CT evaluation, push-out tests, and immersion tests. SPEEK-WA induces pre-osteoblast functions including initial cell adhesion, proliferation, and osteogenic differentiation in vitro as well as substantially enhanced osseointegration and bone-implant bonding strength in vivo and apatite-forming ability. Although SPEEK-W has a similar surface morphology and chemical composition as SPEEK-WA, its cytocompatibility is inferior due to residual sulfuric acid. Our results reveal that the pre-osteoblast functions, bone growth, and apatite formation on the SPEEK surfaces are affected by many factors, including positive effects introduced by the 3D porous structure and SO3H groups as well as negative ones due to the low pH environment. Surface functionalization broadens the use of PEEK in orthopedic implants., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A new class of ratiometric fluorescence sensors composed of rare-earth (RE) compound nanotubes is described. Polyethylenimine-coated yttrium hydroxide fluoride nanotubes (YHF NTs) that were synthesized hydrothermally exhibit highly efficient fluorescence when doped with RE ions. The polyethylenimine on the NTs facilitates the incorporation of phosphors such as quantum dots or organic dyes onto the NT surface to produce dual-emitting nanocomposites which are excellent ratiometric fluorescence sensors. The phosphor layer and underlying tubes in the nanocomposites act as the indicator and reference probes, respectively. This ratiometric fluorescence method which can be applied to the detection of heavy metals in solutions, temperature sensing, and pH sensing boasts high sensitivity and selectivity as well as better accuracy than traditional intensity-based fluorescence methods.

Micro/nano-texturing is a promising approach to produce biomaterials with better tissue integration properties, but the underlying mechanisms are only partially understood. We propose that the integrin-linked kinase (ILK)/β-catenin pathway may play a role in mediating the signals of topographical cues to cells. To confirm the hypothesis, human MG63 osteoblasts are cultured on the micro/nano-textured topographies (MNTs) to assess the cell differentiation in terms of collagen secretion, extracellular matrix mineralization, and osteogenesis-related gene expression. The expression of β-catenin, ILK and integrin β1 and β3 is assayed by real-time polymerase chain reaction and the protein levels of β-catenin, phosphorylated glycogen synthase kinase 3β (p-GSK3β) and ILK are determined by western blot. The ILK silenced MG63 induced by small interfering RNA is cultured on the samples and the cell functions and the levels of β-catenin, GSK3β and p-GSK3β are determined. The results show that the MNTs enhance MG63 differentiation and it is related to the higher expression of integrin β1 and β3 and ILK, which activate the β-catenin signaling by initiating β-catenin expression and inhibiting its degradation by phosphorylating GSK3β. ILK silencing attenuates the β-catenin signaling activation and the enhanced MG63 differentiation by the MNTs. Our results explicitly demonstrate the role of the ILK/β-catenin pathway in mediating the signals from topographical cues to osteoblasts to tailor differentiation and provide new target points for biomaterials modification and biofunctionalization to attain better clinical performance., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Good understanding of the reaction mechanism in the electrochemical reduction of water to hydrogen is crucial to renewable energy technologies. Although previous studies have revealed that the surface properties of materials affect the catalytic reactivity, the effects of a catalytic surface on the hydrogen evolution reaction (HER) on the molecular level are still not well understood. Contrary to general belief, water molecules do not adsorb onto the surfaces of 3C-SiC nanocrystals (NCs), but rather spontaneously dissociate via a surface autocatalytic process forming a complex consisting of -H and -OH fragments. In this study, we show that ultrathin 3C-SiC NCs possess superior electrocatalytic activity in the HER. This arises from the large reduction in the activation barrier on the NC surface enabling efficient dissociation of H(2)O molecules. Furthermore, the ultrathin 3C-SiC NCs show enhanced HER activity in photoelectrochemical cells and are very promising to the water splitting based on the synergistic electrocatalytic and photoelectrochemical actions. This study provides a molecular-level understanding of the HER mechanism and reveals that NCs with surface autocatalytic effects can be used to split water with high efficiency thereby enabling renewable and economical production of hydrogen., (© 2012 American Chemical Society)

Magnetic manganese oxide nanostructures are fabricated at room temperature by mixing a KMnO(4) solution and oleic acid capped Fe(3)O(4) particles. Oleic acid molecules capped Fe(3)O(4) particles are oxidized by potassium permanganate (KMnO(4)) in an aqueous solution to produce porous magnetic manganese oxide nanostructures. The synthesis technique can be extended to other MnO(x) structures with composition of different nanocrystals, such as quantum dots, noble metal crystals which may have important applications as catalysts, adsorbents, electrodes and advanced materials in many scientific disciplines. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption measurements are employed to characterize the structures. As an adsorbent in water treatment, the nanostructures possess a large adsorption capability and high organic pollutant removal rates due to the large surface area and pore volume. The nanostructures are recyclable as their adsorption capability can be recovered by combustion. Furthermore, the strong magnetism exhibited by the structures provides an easy and efficient separation means in wastewater treatment under an external magnetic field., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The discovery of efficient sources of terahertz radiation has been exploited in imaging applications, and developing a nanoscale terahertz source could lead to additional applications. High-frequency mechanical vibrations of charged nanostructures can lead to radiative emission, and vibrations at frequencies of hundreds of kilohertz have been observed from a ZnO nanobelt under the influence of an alternating electric field. Here, we observe mechanical resonance and radiative emission at ∼ 0.36 THz from core-shell ZnO mesocrystal microspheres excited by a continuous green-wavelength laser. We find that ∼ 0.016% of the incident power is converted into terahertz radiation, which corresponds to a quantum efficiency of ∼ 33%, making the ZnO microspheres competitive with existing terahertz-emitting materials. The mechanical resonance and radiation stem from the coherent photo-induced vibration of the hexagonal ZnO nanoplates that make up the microsphere shells. The ZnO microspheres are formed by means of a nonclassical, self-organized crystallization process, and represent a straightforward route to terahertz radiation at the nanoscale.

Monodisperse, uniform, and hierarchically mesostructured silica particles with a thin shell have been fabricated via one-step synthesis using dodecanethiol (C(12)-SH) and CTAB as dual templates. A series of hierarchically mesostructured silica particles with a morphology similar to that of pomegranate can be obtained by simply adjusting the mass ratio of C(12)-SH to CTAB. When the mass ratio is increased, a mesophase transformation occurs from an ordered 2D hexagonal structure to a mesostructured cellular foam in the core of the hierarchically mesoporous silica particles. These unique silica particles are characterized by small-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and nitrogen adsorption-desorption measurements. The formation mechanism of the hierarchically mesostructured silica particles with a thin shell is proposed according to the experimental results. Synergistic self-assembly of C(12)-SH and CTAB in the solution is believed to play a key role in mediating the formation of these hierarchical silica mesostructures, and the hydrophobic dodecanethiol can act as both the swelling agent for CTAB micelles and coagent for the formation of a microemulsion with CTAB micelles. This synthesis method is simple, straightforward, and suitable for the preparation of the other biomineral nanostructures that are unique scaffolds in biological, medical, and catalytic applications.

We have produced glycerol-bonded 3C-SiC nanocrystal (NC) films, which when excited by photons of different wavelengths, produce strong and tunable violet to blue-green (360-540 nm) emission as a result of the quantum confinement effects rendered by the 3C-SiC NCs. The emission is so intense that the emission spots are visible to the naked eyes. The light emission is very stable and even after storing in air for more than six months, no intensity degradation can be observed. X-ray photoelectron spectroscopy and absorption fine structure measurements indicate that the Si-terminated NC surfaces are completely bonded to glycerol molecules. Calculations of geometry optimization and electron structures based on the density functional theory for 3C-SiC NCs with attached glycerol molecules show that these molecules are bonded on the NCs causing strong surface structural change, while the isolated levels in the conduction band of the bare 3C-SiC NCs are replaced with quasi-continuous bands that provide continuous tunability of the emitted light by changing the frequencies of exciting laser. As an application, we demonstrate the potential of using 3C-SiC NCs to fabricate full-color emitting solid films by incorporating porous silicon.

A monoclinic zirconia coating with a nanostructural surface was prepared on the Ti-6Al-4V substrate by an atmospheric plasma-spraying technique, and its microstructure and composition, as well as mechanical and biological properties, were investigated to explore potential application as a bioactive coating on bone implants. X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Raman spectroscopy revealed that the zirconia coating was composed of monoclinic zirconia which was stable at low temperature, and its surface consists of nano-size grains 30-50 nm in size. The bond strength between the coating and the Ti-6Al-4V substrate was 48.4 + or - 6.1 MPa, which is higher than that of plasma-sprayed HA coatings. Hydrothermal experiments indicated that the coating was stable in a water environment and the phase composition and Vickers hardness were independent of the hydrothermal treatment time. Bone-like apatite is observed to precipitate on the surface of the coating after soaking in simulated body fluid for 6 days, indicating excellent bioactivity in vitro. The nanostructured surface composed of monoclinic zirconia is believed to be crucial to its bioactivity. Morphological observation and the cell proliferation test demonstrated that osteoblast-like MG63 cells could attach to, adhere to and proliferate well on the surface of the monoclinic zirconia coating, suggesting possible applications in hard tissue replacements., (Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

SiC nanocrystals (NCs) exhibit unique surface chemistry and possess special properties. This provides the opportunity to design suitable surface structures by terminating the surface dangling bonds with different atoms thereby boding well for practical applications. In this article, we report the photoluminescence properties of 3C-SiC NCs in water suspensions with different pH values. Besides a blue band stemming from the quantum confinement effect, the 3C-SiC NCs show an additional photoluminescence band at 510 nm when the excitation wavelengths are longer than 350 nm. Its intensity relative to the blue band increases with the excitation wavelength. The 510 nm band appears only in acidic suspensions but not in alkaline ones. Fourier transform infrared, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure analyses clearly reveal that the 3C-SiC NCs in the water suspension have Si-H and Si-OH bonds on their surface, implying that water molecules only react with a Si-terminated surface. First-principle calculations suggest that the additional 510 nm band arises from structures induced by H(+) and OH(-) dissociated from water and attached to Si dimers on the modified (001) Si-terminated portion of the NCs. The size requirement is consistent with the observation that the 510 nm band can only be observed when the excitation wavelengths are relatively large, that is, excitation of bigger NCs.

A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost-efficient surface-enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub-10-nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite-difference time-domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.

An inorganic nano-network of attapulgite is formed from rigid nanorods using ion beam bombardment. The structure of the nano-networks depends on the ion beam fluence for the same ion energy. Scanning electron microscopy reveals that ion beam bombardment improves the dispersion of the attapulgite particles and the change in the shape of the rod-shaped attapulgite particles stems from the thermal stress induced by ion beam bombardment. This phenomenon is more obvious for higher ion fluences. The bent or twisted rod-shaped attapulgite particles cross-link to form a network structure, which is stable in water, and when the ion fluence is increased further, the cross-linked points are permanently sealed. The improved materials are more useful than clava attapulgite particles.

Surface-enhanced Raman scattering (SERS) is recognized as one of the most sensitive spectroscopic tools offering highly sensitive chemical and biological detection. The fact that particle plasmon allows direct coupling of light to resonant electron plasmon oscillation has spurred tremendous efforts in the design and fabrication of highly SERS-active substrates in nanostructured films and metallic nanoparticles. Theoretical studies have shown that symmetry breaking allows for more complex plasmon propagation, potentially leading to more intense electromagnetic field generation along the structure and in gaps formed between these materials. Anisotropic metallic nanostructures have all of the characteristics that make them excellent candidates as SERS substrates. Thus, SERS is expected from anisotropic materials. This review focuses on the progress and advances in the design and fabrication of anisotropic nanostructures for SERS, with an emphasis on future challenges.

Nanophase materials are promising alternative implant materials in tissue engineering. Here we report for the first time the large-scale direct growth of nanostructured bioactive titanates on three-dimensional (3D) microporous Ti-based metal (NiTi and Ti) scaffolds via a facile low temperature hydrothermal treatment. The nanostructured titanates show characteristics of 1D nanobelts/nanowires on a nanoskeleton layer. Besides resembling cancelous bone structure on the micro/macroscale, the 1D nanostructured titanate on the exposed surface is similar to the lowest level of hierarchical organization of collagen and hydroxyapatite. The resulting surface displays superhydrophilicity and favors deposition of hydroxyapatite and accelerates cell attachment and proliferation. The remarkable simplicity of this process makes it widely accessible as an enabling technique for applications from engineering materials treatment including energy-absorption materials and pollution-treatment materials to biotechnology.

Titania (TiO2) coatings with nanostructural surface prepared using plasma spraying technology were irradiated by ultraviolet light in simulated body fluids to improve their bioactivity. The in vitro bioactivity of the coatings was evaluated by investigating the formation of apatite on their surfaces in simulated body fluids. Bone-like apatite was observed to precipitate on the UV-irradiated TiO2 coating with nanostructural surface after it was immersed in simulated body fluid for a certain period, but not on the as-sprayed and UV-irradiated TiO2 coatings without nanostructural surface. The results indicate that the nano-TiO2 surface can be activated by UV-irradiation to induce its bioactivity. The ability of apatite formation on the nano-TiO2 surface was improved with the increase of UV-irradiation time. The in vivo results reveal that the as-prepared TiO2 coating with nanostructural surface cannot induce the formation of new bones during the implantation period, but the UV-irradiated TiO2 coating with nanostructural surface could do so during an implantation time longer than 2 months. Our results indicate that the osseointegration ability of the plasma-sprayed TiO2 coating with nanostructural surface can be improved by UV irradiation.

Although some types of TiO(2) powders and gel-derived films can exhibit bioactivity, plasma-sprayed TiO(2) coatings are always bioinert, thereby hampering wider applications in bone implants. We have successfully produced a bioactive nanostructured TiO(2) surface with grain size smaller than 50 nm using nanoparticle plasma spraying followed by hydrogen plasma immersion ion implantation (PIII). The hydrogen PIII nano-TiO(2) coating can induce bone-like apatite formation on its surface after immersion in a simulated body fluid. In contrast, apatite cannot form on either the as-sprayed TiO(2) surfaces (both <50 nm grain size and >50 nm grain size) or hydrogen-implanted TiO(2) with grain size larger than 50 nm. Hence, both a hydrogenated surface that gives rise to negatively charged functional groups on the surface and small grain size (<50 nm) that enhances surface adsorption are crucial to the growth of apatite. Introduction of surface bioactivity to plasma-sprayed TiO(2) coatings, which are generally recognized to have excellent biocompatibility and corrosion resistance as well as high bonding to titanium alloys, makes them more superior than many current biomedical coatings.