Double-stranded DNAs (ds-DNAs) have been identified as efficient templates favoring the formation of fluorescent copper nanoparticles (Cu NPs). Herein, we have tried to synthesize fluorescent Cu NPs using single-stranded DNAs (ss-DNAs) as templates and to identify the critical DNA sequences. By comparing the results using homopolymer DNAs, hairpin DNAs, and pristine ss-DNAs as templates, we found that DNA thymine base plays a dominant role in producing red-emissive fluorescent Cu NPs on ss-DNA templates. The thymine-dependent growth of the fluorescent Cu NPs is confirmed by Hg2+ mediated T-T base pair in comparison with the other non-specific metal ions, which could be developed into a practical sensor for turn-on fluorescence detection of Hg2+ with a high selectivity. The mechanism is briefly discussed according the DNA sequence-dependent formation of fluorescent Cu NPs. This work demonstrates the sequence role in producing fluorescent Cu NPs that could serve as promising fluorescent nanoprobes in biosensing and DNA-hosted Cu nanomaterials.
Cartilage tissue is a nanostructured tissue which is notoriously hard to regenerate due to its extremely poor inherent regenerative capacity and complex stratified architecture. Current treatment methods are highly invasive and may have many complications. Thus, the goal of this work is to use nanomaterials and nano/microfabrication methods to create novel biologically inspired tissue engineered cartilage scaffolds to facilitate human bone marrow mesenchymal stem cell (MSC) chondrogenesis. To this end we utilized electrospinning to design and fabricate a series of novel 3D biomimetic nanostructured scaffolds based on hydrogen (H-2) treated multi-walled carbon nanotubes (MWCNTs) and biocompatible poly(L-lactic acid) (PLLA) polymers. Specifically, a series of electrospun fibrous PLLA scaffolds with controlled fiber dimension were fabricated in this study. In vitro MSC studies showed that stem cells prefer to attach in the scaffolds with smaller fiber diameter. More importantly, the MWCNT embedded scaffolds showed a drastic increase in mechanical strength and a compressive Young's modulus matching to natural cartilage. Furthermore, our MSC differentiation results demonstrated that incorporation of the H2 treated carbon nanotubes and poly-L-lysine coating can induce more chondrogenic differentiations of MSCs than controls. After two weeks of culture, PLLA scaffolds with H2 treated MWCNTs and poly-L-lysine can achieve the highest glycosaminoglycan synthesis, making them promising for further exploration for cartilage regeneration.
A very thin graphene nanoribbon/polyvinyl alcohol (GNR/PVA) composite film has been developed which is light weight and requires a very low concentration of filler to achieve electromagnetic interference (EMI) shielding as high as 60 dB in the X band. Atomic force microscope studies show very well conjugated filler concentration in the PVA matrix for varying concentrations of GNR supported by Raman spectroscopy data. The films show 14 orders of increase in conductivity with a GNR concentration of 0.0075 wt% in PVA. This is possible because of the interconnected GNR network providing a very low percolation threshold as observed from the electrical measurements. Local density of states study of GNR using scanning tunnelling spectroscopy shows the presence of localized states near the Fermi energy. There are multiple advantages of GNR as an EMI shielding material in a polymer matrix. It has good dispersion in water, the conductive network in the composite shows very high electrical conductivity for a very low concentration of GNR and the presence of localized density of states near Fermi energy provides the spin states required for the absorbance of radiation energy in the X band.
Surface plasmon resonance sensors of the nanohole array type provide a promising platform for label-free biosensing on surfaces. For their extensive use, an efficient fabrication procedure to make nanoscale features on metallic films is required. We develop a simple and robust template-transfer approach to structure periodic nanohole arrays in optically thick Au films on poly(dimethylsiloxane) substrates. This technique significantly simplifies the process of sensor fabrication and reduces the cost of the device. A spectral analysis approach is also developed for improving the sensor performance. The sensitivity of the resulting sensor to refractive index change is 522 nm/RIU (refractive index unit) and the resolution is improved to 2 x 10(-5) RIU, which are among the best reported values for localized surface plasmon resonance sensors. We also demonstrate the limit of detection of this sensor for cardiac troponin-I.
The intrinsic interfacial thermal resistance at graphene/organic interfaces, as a result of mismatches in the phonon vibrational spectra of the two materials, diminishes the overall heat transfer performance of graphene/organic nanocomposites. In this paper, we use molecular dynamics (MD) simulations to design alkyl-pyrene molecules that can non-covalently functionalize graphene surfaces in contact with a model organic phase composed of octane. The alkyl-pyrene molecules possess phonon-spectra features of both graphene and octane and, therefore, can serve as phonon-spectra linkers to bridge the vibrational mismatch at the graphene/octane interface. In support of this hypothesis, we find that the best linker candidate can enhance the out-of-plane graphene/organic interfacial thermal conductance by similar to 22%, attributed to its capability to compensate the low-frequency phonon mode of graphene. We also find that the length of the alkyl chain indirectly affects the interfacial thermal conductance through different orientations of these chains because they dictate the contribution of the out-of-plane high-frequency carbon-hydrogen bond vibrations to the overall phonon transport. This study advances our understanding of the less destructive non-covalent functionalization method and design principles of suitable linker molecules to enhance the thermal performance of graphene/organic nanocomposites while retaining the intrinsic chemical, thermal, and mechanical properties of pristine graphene.
A systematic approach for understanding the electron transport mechanisms in resistive strain gauges based on assemblies of gold colloidal nanoparticles (NPs) protected by organic ligands is described. The strain gauges were fabricated from parallel micrometer wide wires made of 14 nm gold (Au) colloidal NPs on polyethylene terephthalate substrates, elaborated by convective self-assembly. Electron transport in such devices occurs by inter-particle electron tunneling through the tunnel barrier imposed by the organic ligands protecting the NPs. This tunnel barrier was varied by changing the nature of organic ligands coating the nanoparticles: citrate (CIT), phosphines (BSPP, TDSP) and thiols (MPA, MUDA). Electro-mechanical tests indicate that only the gold NPs protected by phosphine and thiol ligands yield high gauge sensitivity. Temperature-dependent resistance measurements are explained using the 'regular island array model' that extracts transport parameters, i.e., the tunneling decay constant beta and the Coulomb charging energy E-C. This reveals that the Au@CIT nanoparticle assemblies exhibit a behavior characteristic of a strong-coupling regime, whereas those of Au@BSPP, Au@TDSP, Au@MPA and Au@MUDA nanoparticles manifest a weak-coupling regime. A comparison of the parameters extracted from the two methods indicates that the most sensitive gauges in the weak-coupling regime feature the highest beta. Moreover, the E-C values of these 14 nm NPs cannot be neglected in determining the beta values.
An arrangement of self-assembled GaN nanowires (NWs) grown by plasma-assisted molecular beam epitaxy on a Si(111) substrate is studied as a function of the temperature at which the substrate is nitridized before GaN growth. We show that the NWs grow with the c-axis perpendicular to the substrate surface independently of nitridation temperature with only a slight improvement in tilt coherency for high nitridation temperatures. A much larger influence of the substrate nitridation process on the in-plane arrangement of NWs is found. For high (850 degrees C)and medium (450 degrees C) nitridation temperatures angular twist distributions are relatively narrow and NWs are epitaxially aligned to the substrate in the same way as commonly observed in GaN on Si(111) planar layers with an AlN buffer. However, if the substrate is nitridized at low temperature (similar to 150 degrees C)the epitaxial relationship with the substrate is lost and an almost random in-plane orientation of GaN NWs is observed. These results are correlated with a microstructure of silicon nitride film created on the substrate as the result of the nitridation procedure.
We report the realization of high performance silicon nanowire (SiNW) based solar cells with a conversion efficiency of 17.11% and a large size of 125 x 125 mm(2). The key factor for success lies in an efficient approach of dielectric passivation to greatly enhance the electrical properties while keeping the advantage of excellent light trapping of the SiNW structure. The suppression of carrier recombination has been demonstrated through the combination of the SiO2/SiNx stack, which exhibits a good passivation effect on heavily doped SiNWs via reducing both the Shockley-Read-Hall recombination and near surface Auger recombination. We have examined in detail the effects of different passivations and SiNW lengths on the effective minority carrier lifetime, reflectance and carrier recombination characteristics, as well as cell performance. The proposed passivation techniques can be easily adapted to conventional industrial manufacturing processes, providing a potential prospect of SiNW based solar cells in mass production.
We have studied the photoelectrochemical properties of both undoped and Si-doped GaN nanowire arrays in 1 mol l(-1) solutions of hydrogen bromide and potassium bromide, which were used separately as electrolytes. It is observed that variations of the photocurrent with bias voltage depend strongly on the n-type doping in GaN nanowires in both electrolytes, which are analyzed in the context of GaN surface band bending and its variation with the incorporation of Si-doping. Maximum incident-photon-to-current-conversion efficiencies of similar to 15% and 18% are measured for undoped and Si-doped GaN nanowires under similar to 350 nm light illumination, respectively. Stable hydrogen generation is also observed at a zero bias potential versus the counter-electrode.
The mechanism of action of silver nanoparticles (AgNPs) is unclear due to the particles' strong tendency to agglomerate. Preventing agglomeration could offer precise control of the physicochemical properties that drive biological response to AgNPs. In an attempt to control agglomeration, we exposed zebrafish embryos to AgNPs of 20 or 110 nm core size, and polypyrrolidone (PVP) or citrate surface coatings in media of varying ionic strength. AgNPs remained unagglomerated in 62.5 mu M CaCl2 (CaCl2) and ultrapure water (UP), but not in standard zebrafish embryo medium (EM). Zebrafish embryos developed normally in the low ionic strength environments of CaCl2 and UP. Exposure of embryos to AgNPs suspended in UP and CaCl2 resulted in higher toxicity than suspensions in EM. 20 nm AgNPs were more toxic than 110 nm AgNPs, and the PVP coating was more toxic than the citrate coating at the same particle core size. The silver tissue burden correlated well with observed toxicity but only for those exposures where the AgNPs remained unagglomerated. Our results demonstrate that size-and surface coating-dependent toxicity is a result of AgNPs remaining unagglomerated, and thus a critical-design consideration for experiments to offer meaningful evaluations of AgNP toxicity.
Recently, carbon dots (CDs) have been among the most promising emerging fluorescent labels for cellular imaging. In this work, a new facile synthesis method was developed for fabricating CDs from polystyrene foam waste and common organic solvents. The CDs obtained have tunable emission from blue to orange and are expected to be of use for labeling different cellular structures simultaneously. Transmission electron microscopy, x-ray diffraction, Raman spectra, Fourier transform infrared spectrometry, UV-vis, and fluorescence spectrophotometry (PL) were employed to investigate the structures and luminescence properties of CDs. The highest quantum yield (QY) achieved was 36%. The mechanisms for the formation and luminescence of the CDs are analyzed. The ability of the solvent to disperse the CDs plays a very important role in the origin of PL. The type of organic solvent has an important influence on the position of emission peaks and the QY. Different emissive traps play the dominant role in the luminescence of carbon materials. Furthermore, a hemolysis assay was performed to evaluate the biocompatibility of these CDs in vitro. The biocompatibility of the CDs, even at very high doses, ensures their potential in biomedical applications.
We report single crystal phase and non-tapered wurtzite (WZ) and zincblende twinning superlattice (ZB TSL) InP nanowires (NWs). The NWs are grown in a metalorganic vapor phase epitaxy (MOVPE) reactor using the vapor-liquid-solid (VLS) mechanism and in situ etching with HCl at a high growth temperature. Our stacking fault-free WZ and ZB TSL NWs allow access to the fundamental properties of both NW crystal structures, whose optical and electronic behaviors are often screened by polytypism or incorporated impurities. The WZ NWs show no acceptor-related emission, implying that the VLS-grown NW is almost free of impurities due to sidewall removal by HCl. They only emit light at the free exciton (1.491 eV) and the donor bound exciton transition (1.4855 eV). The ZB NWs exhibit a photoluminescence spectrum being unaffected by the twinning planes. Surprisingly, the acceptor-related emission in the ZB NWs can be almost completely removed by etching away the impurity-contaminated sidewall grown via a vapor-solid mechanism.
Controlling the growth of zinc oxide nanowires is necessary to optimize the performance of nanowire-based devices such as photovoltaic solar cells, nano-generators, or light-emitting diodes. With this in mind, we investigate the nucleation and growth mechanisms of ZnO nanowires grown by metalorganic vapor phase epitaxy either on O-polar ZnO or on sapphire substrates. Whatever the substrate, ZnO nanowires are Zn-polar, as demonstrated by convergent beam electron diffraction. For growth on O-polar ZnO substrate, the nanowires are found to sit on O-polar pyramids. As growth proceeds, the inversion domain boundary moves up in order to remain at the top of the O-polar pyramids. For growth on sapphire substrates, the nanowires may also originate from the sapphire/ZnO interface. The presence of atomic steps and the non-polar character of sapphire could be the cause of the Zn-polar crystal nucleation on sapphire, whereas it is proposed that the segregation of aluminum impurities could account for the nucleation of inverted domains for growth on O-polar ZnO.
The electrochemistry of silver nanoparticles contained in a consumer product has been studied. The redox properties of silver particles in a commercially available disinfectant cleaning spray were investigated via cyclic voltammetry before particle-impact voltammetry was used to detect single particles in both a typical aqueous electrolyte and authentic seawater media. We show that particle- impact voltammetry is a promising method for the detection of nanoparticles that have leached into the environment from consumer products, which is an important development for the determination of risks associated with the incorporation of nanotechnology into everyday products.
Resistive switching and conductance quantization are systematically studied in a Ag/poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester/indium-tin oxide sandwich structure. The observed bipolar switching behavior can be attributed to the formation and dissolution of Ag filaments during positive and negative voltage sweeps, respectively. More importantly, conductance quantization with both integer and half integer multiples of single atomic point contact can be realized by slowing down the voltage sweep speed as well as by pulse measurement. The former may reflect the formed Ag filaments with different atomic point contacts, while the latter probably originates from the interaction between the Ag filaments and the elemental hydrogen provided by the organic storage medium. With appropriate current compliances, low resistance states with desired quantized conductance values are successfully achieved, thus showing the potential for ultrahigh density memory applications. Besides, 100 successive switching cycles with densely distributed resistance values of each resistance state and extrapolated retention properties over ten years are also demonstrated.
A biopsy of the first lymph node to which a tumor drains-the sentinel lymph node (SLN)-is commonly performed to identify micrometastases. Image guidance of the SLN biopsy procedure has the potential to improve its accuracy and decrease its morbidity. We have developed a new stable contrast agent for photoacoustic image-guided SLN biopsy: silica-coated gold nanoplates (Si-AuNPs). The Si-AuNPs exhibit high photothermal stability when exposed to pulsed and continuous wave laser irradiation. This makes them well suited for in vivo photoacoustic imaging. Furthermore, Si-AuNPs are shown to have low cytotoxicity. We tested the Si-AuNPs for SLN mapping in a mouse model where they exhibited a strong, sustained photoacoustic signal. Real-time ultrasound and photoacoustic imaging revealed that the Si-AuNPs quickly drain to the SLN, gradually spreading throughout a large portion of the node.
Defects are generally believed to deteriorate the superlative performance of graphene-based devices but may also be useful when carefully engineered to tailor the local properties and achieve new functionalities. Central to most defect-associated applications is the defect coverage and arrangement. In this work, we investigate, by molecular dynamics simulations, the mechanical properties and fracture dynamics of graphene sheets with randomly distributed vacancies or Stone-Wales defects under tensile deformations over a wide defect coverage range. With defects presented, an sp-sp(2) bonding network and an sp-sp(2)-sp(3) bonding network are observed in vacancy-defected and Stone-Wales-defected graphene, respectively. The ultimate strength degrades gradually with increasing defect coverage and saturates in the high-ratio regime, whereas the fracture strain presents an unusual descending-saturating-improving trend. In the dense vacancy defect situation, the fracture becomes more plastic and super-ductility is observed. Further fracture dynamics analysis reveals that the crack trapping by sp-sp(2) and sp-sp(2)-sp(3) rings and the crack-tip blunting account for the ductile fracture, whereas geometric rearrangement on the entire sheet for vacancy defects and geometric rearrangement on the specific defect sites for Stone-Wales defects account for their distinctive rules of the evolution of the fracture strain.
We demonstrate a reliable fabrication method to produce plasmonic dipole nanoantennas with gap values in the range of 3.5-20 nm. The method combines electron beam lithography to create gold nanorods and helium focused ion beam milling to cut the gaps. Results show a reproducibility within 1 nm. Scattering spectra of antennas show a red shift of resonance wavelengths and an increase of the intensity of resonance peaks with a decrease of the gap size, which is in agreement with finite element simulations. The measured refractive index sensitivity was about 250 nm per refractive index unit for antennas with gap values below 5 nm.
As a result of global energy needs, much research has been devoted to the conversion of solar energy to various usable forms, such as chemical energy in the form of hydrogen via water splitting. To make the conversion methods efficient, economically practical, and industrially scalable, sensitizers capable of utilizing visible and near infrared (IR) light need to be developed. Herein, water-soluble, colloidally stable carbon quantum dots (CQDs) are successfully synthesized by a facile one-step alkali-assisted electrochemical method. Owing to their broad visible light absorption, upconversion luminescence properties and efficient electron injection to TiO2, these CQDs can be used as the sensitizer for photoelectrochemical cells and show an optimized photocurrent of 1.2 mA cm(-2) at 0 V versus Ag/AgCl under 100 mW cm(-2) simulated sunlight. The above results indicate that the elementally abundant and environmentally friendly CQDs, as a novel sensitizer, can surely be employed to make full use of the visible spectrum of sunlight for their application in photovoltaic devices.
Structural, chemical and electronic properties of electroforming in the TiN/HfO2 system are investigated at the nanometre scale. Reversible resistive switching is achieved by biasing the metal oxide using conductive atomic force microscopy. An original method is implemented to localize and investigate the conductive region by combining focused ion beam, scanning spreading resistance microscopy and scanning transmission electron microscopy. Results clearly show the presence of a conductive filament extending over 20 nm. Its size and shape is mainly tuned by the corresponding HfO2 crystalline grain. Oxygen vacancies together with localized states in the HfO2 band gap are highlighted by electron energy loss spectroscopy. Oxygen depletion is seen mainly in the central part of the conductive filament along grain boundaries. This is associated with partial amorphization, in particular at both electrode/oxide interfaces. Our results are a direct confirmation of the filamentary conduction mechanism, showing that oxygen content modulation at the nanometre scale plays a major role in resistive switching.