Gold nanorods core/AgPt alloy nanodots shell: A novel potent antibacterial nanostructure

In the light of the current problems of silver nanoparticles （Ag NPs） in terms of antibacterial performance, we have designed a novel trimetallic corelshell nanostructure with AgPt alloy nanodots epitaxially grown on gold nanorods （Au@PtAg NRs） as a potential antibacterial agent. Both Escherichia coli （E. coli） and Staphylococcus aureus （S. aureus） were studied. The antibacterial activity exhibits an obvious composition-dependence. On increasing the Ag fraction in the alloy shell up to 80%, the antibacterial activity gradually increases, demonstrating a flexible way to tune this activity. At 80% Ag, tile antibacterial activity is better than that of a pure Ag shell. The improved antibacterial ability mainly results from the high exposure of silver on the shell surface due to the dot morphology. We thus demonstrate that forming alloys is an effective way to improve antibacterial activity while retaining high chemical stability for Ag-based nanomaterials. Furthermore, due to the tunable localized surface plasmonic response in the near-infrared （NIR） spectral region, additional control over antibacterial activity using light--such as photothermal killing and photo- triggered silver ion release--is expected. As a demonstration, highly enhanced antibacterial activity is shown by utilizing the NIR photothermal effect of the nanostructures. Our results indicate that such tailored nanostructures will find a role in the future fight against bacteria, including the challenge of the increasing severity of multidrug resistance.     

Site-controlled formation of InGaAs quantum nanostructures-Tailoring the dimensionality and the quantum confinement

We report on InGaAs quantum disks (QDks) controllably formed on the top (001) facet of nano-patterned GaAs pyramidal platforms. The QDks exhibit pyramidal shape with special facets and varied dimensions, depending on the GaAs pyramidal buffer and the amount of InGaAs deposited. The formation of QDks is explained by the overgrowth of an InGaAs layer and thereafter coalescence of small InGaAs islands. Photoluminescence (PL) characteristics of ensemble QDks and exciton features of individual QDks together demonstrate that we may achieve a transition from zero-dimensional (0D) to two-dimensional (2D) quantum structure with increasing QDk size. This transition provides the flexibility to continuously tailor the dimensionality and subsequently the quantum confinement of semiconductor nanostructures via site-controlled self-assembled epitaxy for device applications based on single quantum structures.      

Enhanced and tunable fluorescent quantum dots within a single crystal of protein

The design and synthesis of bio-nano hybrid materials can not only provide new materials with novel properties, but also advance our fundamental understanding of interactions between biomolecules and their abiotic counterparts. Here, we report a new approach to achieving such a goal by growing CdS quantum dots （QDs） within single crystals of lysozyme protein. This bio-nano hybrid emitted much stronger red fluorescence than its counterpart without the crystal, and such fluorescence properties could be either enhanced or suppressed by the addition of Ag（I） or Hg（II）, respectively. The three-dimensional incorporation of CdS QDs within the lysozyme crystals was revealed by scanning transmission electron microscopy with electron tomography. More importantl~ since our approach did not disrupt the crystalline nature of the lysozyme crystals, the metal and protein interactions were able to be studied by X-ray crystallography, thus providing insight into the role of Cd（II） in the CdS QDs formation.     

Curved carbon nanotubes: From unique geometries to novel properties and peculiar applications

Incorporating pentagons and heptagons into the hexagonal networks of pristine carbon nanotubes （CNTs） can form various CNT-based nanostructures, as pentagons and heptagons will bend or twist the CNTs by introducing positive and negative curvature, respectively. Some typical so-made CNT-based nanostructures are reviewed in this article, including zero-dimensional toroidal CNTs, and one-dimensional kinked and coiled CNTs. Due to the presence of non-hexagonal rings and curved geometries, such nanostructures possess rather different structural, physical and chemical properties from their pristine CNT counterparts, which are reviewed comprehensively in this article. Additionally, their synthesis, modelling studies, and potential applications are discussed.     

Two-photon-excited near-infrared emissive carbon dots as multifunctional agents for fluorescence imaging and photothermal therapy

C dots (CDs) have shown great potential in bioimaging and phototherapy. However, it is challenging to manipulate their fluorescent properties and therapeutic efficacy to satisfy the requirements for clinic applications. In this study, we prepared S, Se-codoped CDs via a hydrothermal method and demonstrated that the doping resulted in excitation wavelength-independent near-infrared (NIR) emissions of the CDs, with peaks at 731 and 820 nm. Significantly, the CDs exhibited a photothermal conversion efficiency of ~58.2%, which is the highest reported value for C nanostructures and is comparable to that of Au nanostructures. Moreover, the CDs had a large two-photon absorption cross section (~30,045 GM), which allowed NIR emissions and the photothermal conversion of the CDs through the two-photon excitation (TPE) mechanism. In vitro and in vivo tests suggested that CDs can function as new multifunctional phototheranostic agents for the TPE fluorescence imaging and photothermal therapy of cancer cells.

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Nanoplasmonic colloidal suspensions for the enhancement of the luminescent emission from single-walled carbon nanotubes

Aiming to enhance the luminescence yield of carbon nanotubes, we introduce a new class of hybrid nanoplasmonic colloidal systems （π-hybrids）. Nanotubes dispersed in gold nanorod colloidal suspensions yield hybrid structures exhibiting enhanced luminescence up to a factor of 20. The novelty of the proposed enhancement mechanism relies on including metal proximity effects in addition to its localized surface plasmons. This simple, robust and flexible technique enhances the luminescence of nanotubes with chiralities whose enhancement has never reported before, for example the （8,4） tube.     

Redox-sensitive colorimetric polyaniline nanoprobes synthesized by a solvent-shift process

We have synthesized water-stable polyaniline nanoparticles coated with triarmed polyethylene glycol chains using a solvent-shift method and confirmed their colloidal size and aqueous solubility. Furthermore, we have demonstrated that the polyaniline nanoparticles can be doped with biological dopants to produce distinct color changes allowing the detection of live cancer cells.      

Enhanced π-π interactions between a C60 fullerene and a buckle bend on a double-walled carbon nanotube

In situ low-voltage aberration corrected transmission electron microscopy (TEM) observations of the dynamic entrapment of a C₆₀ molecule in the saddle of a bent double-walled carbon nanotube is presented. The fullerene interaction is non-covalent, suggesting that enhanced π-π interactions (van der Waals forces) are responsible. Classical molecular dynamics calculations confirm that the increased interaction area associated with a buckle is sufficient to trap a fullerene. Moreover, they show hopping behavior in agreement with our experimental observations. Our findings further our understanding of carbon nanostructure interactions, which are important in the rapidly developing field of low-voltage aberration corrected TEM and nano-carbon device fabrication.      

Bi2WO6 quantum dot-intercalated ultrathin montmorillonite nanostructure and its enhanced photocatalytic performance

The kinetic competition between electron-hole recombination and water oxidation is a key limitation for the development of efficient solar water splitting materials. In this study, we present a solution for solving this challenge by constructing a quantum dot-intercalated nanostructure. For the first time, we show the interlayer charge of the intercalated nanostructure can significantly inhibit the electron-hole recombination in photocatalysis. For Bi₂WO₆ quantum dots (QDs) intercalated in a montmorillonite (MMT) nanostructure as an example, the average lifetime of the photogenerated charge carriers was increased from 3.06 μs to 18.8 μs by constructing the intercalated nanostructure. The increased lifetime markedly improved the photocatalytic performance of Bi₂WO₆ both in solar water oxidation and environmental purification. This work not only provides a method to produce QD-intercalated ultrathin nanostructures but also a general route to design efficient semiconductor-based photoconversion materials for solar fuel generation and environmental purification.      

Electron-electron interactions in monolayer graphene quantum capacitors

We demonstrate the effects of electron-electron （e-e） interactions in monolayer graphene quantum capacitors. Ultrathin yttrium oxide showed excellent per-formance as the dielectric layer in top-gate device geometry. The structure and dielectric constant of the yttrium oxide layers have been carefully studied. The inverse compressibility retrieved from the quantum capacitance agreed fairly well with the theoretical predictions for the e--e interactions in monolayer graphene at different temperatures. We found that electron-hole puddles played a significant role in the low-density carrier region in graphene. By considering the temperature-dependent charge fluctuation, we established a model to explain the round-off effect originating from the e-e interactions in monolayer graphene near the Dirac point.     

Linear strain-gradient effect on the energy bandgap in bent CdS nanowires

Although possible non-homogeneous strain effects in semiconductors have been investigated for over a half century and the strain-gradient can be over 1% per micrometer in flexible nanostructures, we still lack an understanding of their influence on energy bands. Here we conduct a systematic cathodoluminescence spectroscopy study of the strain-gradient induced exciton energy shift in elastically curved CdS nanowires at low temperature, and find that the red-shift of the exciton energy in the curved nanowires is proportional to the strain-gradient, an index of lattice distortion. Density functional calculations show the same trend of band gap reduction in curved nanostructures and reveal the underlying mechanism. The significant linear strain-gradient effect on the band gap of semiconductors should shed new light on ways to tune optical-electronic properties in nanoelectronics.      

Anomalous enhancement of fluorescence of carbon dots through lanthanum doping and potential application in intracellular imaging of ferric ion

An anomalous enhancement of fluorescence of carbon dots (CDs) was observed via lanthanum (La) doping. La-doped CDs (La-CDs) were prepared through microwave pyrolysis within 4 min. With La³⁺ doping, the emission band shifted from blue to green although La³⁺ is non-fluorescent. The quantum yield and fluorescence lifetime improved by about 20% and 35%, respectively. All experiment results indicate that La³⁺ doping is an effective way to tune fluorescence and improve the performance of CDs. Another unique attribute of La-CDs is high sensitivity to Fe³⁺. The La-CD-based fluorescence probe was established and used for sensitive and selective detection of Fe³⁺ with a limit of detection of 91 nmol/L. The proposed fluorescence probe also was successfully employed to visualize intracellular Fe³⁺ in live HeLa cells through cell imaging. It was also shown that yttrium exhibited the same fluorescence enhancement effect as La. The results may provide a new route for preparing CDs with special properties.

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A perspective on functionalizing colloidal quantum dots with DNA

This perspective provides an overview of the techniques that have been developed for the conjugation of DNA to colloidal quantum dots (QDs), or semiconductor nanocrystals. Methods described include: ligand exchange at the QD surface, covalent conjugation of DNA to the QD surface ligands, and one-step DNA functionalization on core QDs or during core/shell QD synthesis in aqueous solution, with an emphasis on the most recent progress in our lab. We will also discuss emerging trends in DNA-functionalized QDs for potential applications.      

A green synthesis of carbon nanoparticles from honey and their use in real-time photoacoustic imaging

Imaging sentinel lymph nodes (SLN) could provide us with critical information about the progression of a cancerous disease. Real-time high-resolution intraoperative photoacoustic imaging (PAI) in conjunction with a near-infrared (NIR) probe may offer opportunities for the immediate imaging for direct identification and resection of SLN or collecting tissue samples. In this work a commercially amenable synthetic methodology is revealed for fabricating luminescent carbon nanoparticles with rapid clearance properties. A one-pot “green” technique is pursued, which involved rapid surface passivation of carbon nanoparticles with organic macromolecules (e.g., polysorbate, polyethyleneglycol) in solvent-free conditions. Interestingly, the naked carbon nanoparticles are derived for the first time, from commercial food grade honey. Surface coated particles are markedly smaller (～7 nm) than previously explored particles (gold, single-walled carbon nanotubes, copper) for SLN imaging. The results indicate an exceptionally rapid signal enhancement (～2 min) of the SLN. Owing to their strong optical absorption in the NIR region, tiny size and rapid lymphatic transport, this platform offers great potential for faster resection of SLN and may lower complications caused in axillary investigation by mismarking with dyes or low-resolution imaging techniques.      

Alumina-coated Ag nanocrystal monolayers as surfaceenhanced Raman spectroscopy platforms for the direct spectroscopic detection of water splitting reaction intermediates

A novel Ag-alumina hybrid surface-enhanced Raman spectroscopy （SERS） platform has been designed for the spectroscopic detection of surface reactions in the steady state. Single crystalline and faceted silver （Ag） nanoparticles with strong light scattering were prepared in large quantity, which enables their reproducible self-assembly into large scale monolayers of Raman sensor arrays by the Langrnuir-Blodgett technique. The close packed sensor film contains high density of sub-nm gaps between sharp edges of Ag nanoparticles, which created large local electromagnetic fields that serve as ＂hot spots＂ for SERS enhancement. The SERS substrate was then coated with a thin layer of alumina by atomic layer deposition to prevent charge transfer between Ag and the reaction system. The photocatalytic water splitting reaction on a monolayer of anatase TiO2 nanoplates decorated with Pt co-catalyst nanoparticles was employed as a model reaction system. Reaction intermediates of water photooxidation were observed at the TiO2/solution interface under UV irradiation. The surface-enhanced Raman vibrations corresponding to peroxo, hydroperoxo and hydroxo surface intermediate species were observed on the TiO2 surface, suggesting that the photo-oxidation of water on these anatase TiO2 nanosheets may be initiated by a nucleophilic attack mechanism.     

On-chip isotachophoresis separation of functional DNA origami capture nanoarrays from cell lysate

Scaffolded DNA origami, a versatile method to construct high yield self- assembled DNA nanostructures, has been investigated to develop water-soluble nanoarrays for label free RNA detection, drug delivery, molecular positioning and recognition, and spatially ordered catalysis of single molecule chemical reactions. Its attributes that facilitate these applications suggest DNA origami as a candidate platform for intracellular targeting. After the interaction with targeted proteins in cell lysate, it is critical to separate and concentrate DNA origami nanoarrays from the crude cell lysate for further analysis. The recent development of microchip isotachophoresis （ITP） provides an alternative robust sample preconcentration and electrophoretic separation method. In this study, we present online ITP for stacking, separation and identification of aptamer-functionalized DNA origami and its thrombin complex in a simple cross-channel fused silica microfluidic chip. In particular, the method achieved separation of a binding complex in less than 5 min and 150-fold signal enhancement. We successfully separated and analyzed the thrombin bound origami-aptamer spiked into cell lysate using on-chip ITP. Our results demonstrate that origami/thrombin nanostructures can be effectively separated from cell lysate using this method and that the structural integrity of the concentrated binding complex is maintained as confirmed by atomic force microscopy （AFM）. An ITP-based separation module can be easily coupled to other microchip pre- and post-processing steps to provide an integrated proteomics analysis platform for diagnostic applications.     

Nanocrystal-semiconductor interface: Atomic-resolution cross-sectional transmission electron microscope study of lead sulfide nanocrystal quantum dots on crystalline silicon

We report on a cross-sectional high resolution transmission electron microscope study of lead sulfide nanocrystal quantum dots （NCQDs） dispersed on electron-transparent silicon nanopillars that enables nearly atomically-resolved simultaneous imaging of the entire composite： the quantum dot, the interfacial region, and the silicon substrate. Considerable richness in the nanocrystal shape and orientation with respect to the substrate lattice is observed. The average NCQD-substrate separation is found to be significantly smaller than the length of the ligands on the NCQDs. Complementary photoluminescence measurements show that light emission from PbS NCQDs on silicon is effectively quenched which we attribute to intrinsic mechanisms of energy and charge transfer from PbS NCQDs to Si.     

Graphene-CdSe nanobelt solar cells with tunable configurations

We have combined two planar nanostructures, graphene and CdSe nanobelts, to construct Schottky junction solar cells with open-circuit voltages of about 0.5 V and cell efficiencies on the order of 0.1%. By covering transparent graphene or carbon nanotube (CNT) films on selected positions along macroscopically long CdSe nanobelts, we have demonstrated the fabrication of active solar cells with many different configurations and parallel connections from individual or multiple assembled nanobelts. The graphene-CdSe nanobelt solar cells reported here show a great flexibility in creating diverse device architectures, and might be scaled up for cell integration based on assembled nanobelt arrays and patterned graphene (or CNT) films.      

Large-energy-shift photon upconversion in degenerately doped InP nanowires by direct excitation into the electron gas

Realizing photon upconversion in nanostructures is important for many next- generation applications such as biological labelling, infrared detectors and solar cells. In particular nanowires are attractive for optoelectronics because they can easily be electrically contacted. Here we demonstrate photon upconversion with a large energy shift in highly n-doped InP nanowires. Crucially, the mechanism responsible for the upconversion in our system does not rely on multi-photon absorption via intermediate states, thus eliminating the need for high photon fluxes to achieve upconversion. The demonstrated upconversion paves the way for utilizing nanowires--with their inherent flexibility such as electrical contactability and the ability to position individual nanowires--for photon upconversion devices also at low photon fluxes, possibly down to the single photon level in optimised structures.     

Silicene nanoribbons as carbon monoxide nanosensors with molecular resolution

Applications based on silicene as grown on substrates are of high interest toward actual utilization of this unique material. Here we explore, from first principles, the nature of carbon monoxide adsorption on semiconducting silicene nanoribbons and the resulting quantum conduction modulation with and without silver contacts for sensing applications. We find that quantum conduction is detectably modified by weak chemisorption of a single CO molecule on a pristine silicene nanoribbon. This modification can be attributed to the charge transfer from CO to the silicene nanoribbon and the deformation induced by the CO chemisorption. Moderate binding energies provide an optimal mix of high detectability and recoverability. With Ag contacts attached to a -1 nm silicene nanoribbon, the interface states mask the conductance modulations caused by CO adsorption, emphasizing length effects for sensor applications. The effects of atmospheric gases--nitrogen, oxygen, carbon dioxide, and water--as well as CO adsorption density and edge-dangling bond defects, on sensor functionality are also investigated. Our results reveal pristine silicene nanoribbons as a promising new sensing material with single molecule resolution.