Ultraflat Au nanoplates as a new building block for molecular electronics.

We demonstrate the charge transport properties of a self-assembled organic monolayer on Au nanoplates with conductive probe atomic force microscopy (CP-AFM). Atomically flat Au nanoplates, a few hundred micrometers on each side, that have only (111) surfaces, were synthesized using the chemical vapor transport method; these nanoplates were employed as the substrates for hexadecanethiol (HDT) self-assembled monolayers (SAMs). Atomic-scale high-resolution images show (√3 x √3) R30° molecular periodicity, indicating a well-ordered structure of the HDT on the Au nanoplates. We observed reduced friction and adhesion forces on the HDT SAMs on Au nanoplates, compared with Si substrates, which is consistent with the lubricating nature of HDT SAMs. The electrical properties, such as I-V characteristics and current as a function of load, were measured using CP-AFM. We obtained a tunneling decay constant (ß) of 0.57 Å(-1), including through-bond (ßtb = 0.99 Å(-1)) and through-space (ßts = 1.36 Å(-1)) decay constants for the two-pathway model. This indicates that the charge transport properties of HDT SAMs on Au nanoplates are consistent with those on a Au (111) film, suggesting that SAMs on nanoplates can provide a new building block for molecular electronics.

Remarkably enhanced adhesion of coherently aligned catechol-terminated molecules on ultraclean ultraflat gold nanoplates.

We report the characterization and formation of catechol-terminated molecules immobilized on gold nanoplates (Au NPLs) using N-(3,4-dihydroxyphenethyl)-2-mercaptoacetamide (Cat-EAA-SH). Single-crystalline Au NPLs, synthesized using a one-step chemical vapor transport method, have ultraclean and ultraflat surfaces that make Cat-EAA-SH molecules aligned into a well-ordered network of a large-scale. Topographic study of the catechol-terminated molecules on Au NPLs using atomic force microscopy showed more orderly orientation and higher density, leading to significantly higher adhesion as observed from local force-distance curves than those on other Au surfaces. These coherently aligned catechol-terminated molecules on the atomically smooth gold surface led to significanty more reproducible and thus more physico-chemically meaningful measurements than was possible before by employing rough gold surfaces.

Composition-selective fabrication of ordered intermetallic Au-Cu nanowires and their application to nano-size electrochemical glucose detection.

Bimetallic nanostructures can provide distinct and improved physicochemical properties by the coupling effect of the two metal components, making them promising materials for a variety of applications. Herein, we report composition-selective fabrication of ordered intermetallic Au-Cu nanowires (NWs) by two-step chemical vapor transport method and their application to nano-electrocatalytic glucose detection. Ordered intermetallic Au3Cu and AuCu3 NWs are topotaxially fabricated by supplying Cu-containing chemicals to pre-synthesized single-crystalline Au NW arrays. The composition of fabricated Au-Cu NWs can be selected by changing the concentration of Cu-containing species. Interestingly, Au3Cu NW electrodes show unique electrocatalytic activity for glucose oxidation, allowing us to detect glucose without interference from ascorbic acid. Such interference-free detection of glucose is attributed to the synergistic effect, induced by incorporation of Cu in Au. We anticipate that Au3Cu NWs could show possibility as efficient nano-size electrochemical glucose sensors and the present fabrication method can be employed to fabricate valuable ordered intermetallic nanostructures.

Ultra-specific zeptomole microRNA detection by plasmonic nanowire interstice sensor with Bi-temperature hybridization.

MicroRNAs (miRNAs) are emerging new biomarkers for many human diseases. To fully employ miRNAs as biomarkers for clinical diagnosis, it is most desirable to accurately determine the expression patterns of miRNAs. The optimum miRNA profiling method would feature 1) highest sensitivity with a wide dynamic range for accurate expression patterns, 2) supreme specificity to discriminate single nucleotide polymorphisms (SNPs), and 3) simple sensing processes to minimize measurement variation. Here, an ultra-specific detection method of miRNAs with zeptomole sensitivity is reported by applying bi-temperature hybridizations on single-crystalline plasmonic nanowire interstice (PNI) sensors. This method shows near-perfect accuracy of SNPs and a very low detection limit of 100 am (50 zeptomole) without any amplification or labeling steps. Furthermore, multiplex sensing capability and wide dynamic ranges (100 am-100 pm) of this method allows reliable observation of the expression patterns of miRNAs extracted from human tissues. The PNI sensor offers combination of ultra-specificity and zeptomole sensitivity while requiring two steps of hybridization between short oligonucleotides, which could present the best set of features for optimum miRNA sensing method.

Rainbow radiating single-crystal Ag nanowire nanoantenna.

Optical antennas interface an object with optical radiation and boost the absorption and emission of light by the objects through the antenna modes. It has been much desired to enhance both excitation and emission processes of the quantum emitters as well as to interface multiwavelength channels for many nano-optical applications. Here we report the experimental implementation of an optical antenna operating in the full visible range via surface plasmon currents induced in a defect-free single-crystalline Ag nanowire (NW). With its atomically flat surface, the long Ag NW reliably establishes multiple plasmonic resonances and produces a unique rainbow antenna radiation in the Fresnel region. Detailed antenna radiation properties, such as radiating near-field patterns and polarization states, were experimentally examined and precisely analyzed by numerical simulations and antenna theory. The multiresonant Ag NW nanoantenna will find superb applications in nano-optical spectroscopy, high-resolution nanoimaging, photovoltaics, and nonlinear signal conversion.

Topotaxial fabrication of vertical Aux Ag1-x nanowire arrays: plasmon-active in the blue region and corrosion resistant.

Topotaxial growth of Au(x) Ag(1-x) alloy nanowires (NWs) by postepitaxial deposition of Ag vapor on Au NWs and investigation of their plasmonic properties are reported. Ag vapor is supplied onto the epitaxially grown Au NWs, topotaxially turning them into Au(x) Ag(1-x) alloy NWs. The original geometries and alignments of the Au nanostructures are well preserved, while the composition of the alloy NWs is controlled by varying the Ag vapor supply time. The Au(0.5) Ag(0.5) NWs show high surface-enhanced Raman scattering (SERS) activity comparable to that of Ag NWs as well as highly increased oxidation resistance. The plasmon-active wavelength range of the Au(0.5) Ag(0.5) NW is significantly extended to the blue region compared to Au NWs. The Au(x) Ag(1-x) alloy NWs that have plasmonic activity in the blue region in addition to high corrosion resistance will make a superb material for practical plasmonic devices including SERS sensors and optical nanoantennas.

Superplastic deformation of defect-free Au nanowires via coherent twin propagation.

We report that defect-free Au nanowires show superplasticity on tensile deformation. Evidences from high-resolution electron microscopes indicated that the plastic deformation proceeds layer-by-layer in an atomically coherent fashion to a long distance. Furthermore, the stress-strain curve provides full interpretation of the deformation. After initial superelastic deformation, the nanowire shows superplastic deformation induced by coherent twin propagation, completely reorientating the crystal from <110> to <100>. Uniquely well-disciplined and long-propagating atomic movements deduced here are ascribed to the superb crystallinity as well as the radial confinement of the Au nanowires.

Combining a nanowire SERRS sensor and a target recycling reaction for ultrasensitive and multiplex identification of pathogenic fungi.

Development of a rapid, sensitive, and multiplex pathogen DNA sensor enables early diagnosis and, subsequently, the proper treatment of infectious diseases, increasing the possibility to save the lives of infected patients. Here, the development of an ultrasensitive and multiplex pathogen DNA detection method that combines a patterned Au nanowire (NW)-on-film surface-enhanced resonance Raman scattering (SERRS) sensor with an exonuclease III-assisted target DNA recycling reaction is reported. Multiple probe DNAs are added to the target DNA solution, and among them, only the complementary probe DNA is selectively digested by exonuclease III, resulting in the decrease in its concentration. The digestion process is repeated by recycling of target DNAs. The decrease of the complementary probe DNA concentration is detected by SERRS. Combining the high sensitivity of the NW-on-film sensor and the target recycling reaction significantly improves DNA detection performance, resulting in the detection limit of 100 fM corresponding to 3 amole. By positioning Au NWs at specific addresses, multiple pathogen DNAs can be identified in a single step. Clinical sample tests with multiple genomic DNAs of pathogens show the potential of this sensor for practical diagnosis of infectious diseases.

Troponin Aptamer on an Atomically Flat Au Nanoplate Platform for Detection of Cardiac Troponin I.

Well-ordered bioreceptors on atomically flat Au surfaces can be a high-performance biosensor. Cardiac troponin I proteins (cTnIs) have been regarded as a specific biomarker for acute myocardial infarction (AMI). Here, we report the accurate detection of cTnIs using an aptamer-immobilized Au nanoplate platform. The single-crystalline and atomically flat Au nanoplate was characterized by atomic force microscopy. For the precise detection of cTnI, we immobilized an aptamer that can strongly bind to cTnI onto an atomically flat Au nanoplate. Using the aptamer-immobilized Au nanoplate, cTnIs were successfully detected at a concentration of 100 aM (2.4 fg/mL) in buffer solution. Furthermore, cTnIs in serum could be identified at a concentration of 100 fM (2.4 pg/mL). The total assay time was ~7 h. Importantly, the aptamer-immobilized Au nanoplate enabled us to diagnose AMI patients accurately, suggesting the potential of the present method in the diagnosis of AMI.

Epitaxially aligned submillimeter-scale silver nanoplates grown by simple vapor transport.

Epitaxially aligned large silver (Ag) nanoplate arrays with ultraclean surfaces are very attractive for novel plasmonic applications. Although solution-phase methods have been extensively employed to synthesize Ag nanoplates, these cannot be used to grow epitaxial large Ag nanoplates on substrates. Here we report a vapor-phase synthetic strategy to epitaxially grow submillimeter-scale Ag nanoplates on a variety of substrates. By simply transporting Ag vapor to the substrates at an optimal temperature (820 °C), we synthesize ∼100 µm-sized Ag nanoplates with atomically clean surfaces, which are three-dimensionally aligned on the substrates. We demonstrate that both the type of supported seed and their interfacial lattice matching with the substrates determine the epitaxial growth habit of the nanoplates, directing their crystallinity, shape, and orientation. (i) On r-cut sapphire substrates, twinned pentagonal nanoplates grow vertically from twinned triangular seeds through a seed → nanoplate process. (ii) On m-cut sapphire substrates, twinned trapezoidal Ag nanoplates grow slantingly from twinned decahedral seeds through a seed → NW → nanoplate process. (iii) Interestingly, twin-free single-crystalline trapezoidal Ag nanoplates grow from twin-free square pyramidal seeds on STO (001) substrates through a seed → NW → nanoplate process. The epitaxially aligned Ag nanoplate arrays could serve as a new platform for two-dimensional (2D) guiding of surface plasmons as well as for hierarchical 3D plasmonic nanoarchitecturing.

Atomically Flat Au Nanoplate Platforms Enable Ultraspecific Attomolar Detection of Protein Biomarkers.

Atomically flat surfaces of single-crystalline Au nanoplates can maximize the functionality of biomolecules, thus realizing extremely high-performance biosensors. Here, we report both highly specific and supersensitive detection of C-reactive protein (CRP) by employing atomically flat Au nanoplates. CRP is a protein biomarker for inflammation and infection and can be used as a predictive or prognostic marker for various cardiovascular diseases. To maximize the binding capacity for CRP, we carefully optimized the Au nanoplate-Cys3-protein G-anti-CRP structure by observing atomic force microscopy (AFM) images. The optimally anti-CRP-immobilized Au nanoplates allowed extremely specific detection of CRP at the attomolar level. To confirm the binding of CRP onto the Au nanoplate, we assembled Au nanoparticles (NPs) onto the CRP-captured Au nanoplate by sandwich immunoreaction and obtained surface-enhanced Raman scattering (SERS) spectra and scanning electron microscopy (SEM) images. Both the SERS and SEM results showed that we completely eliminated the nonspecific binding of Au NPs onto the optimally anti-CRP-immobilized Au nanoplate. Compared with the anti-CRP-immobilized rough Au film and the randomly anti-CRP-attached Au nanoplate, the optimally anti-CRP-immobilized Au nanoplate provided a highly improved detection limit of 10-17 M. In this study, it was validated that ultraclean and ultraflat Au nanoplates can maximize the sensing capability of CRP. We expect that these Au nanoplates will enable the feasible detection of many important biomarkers with high specificity and high sensitivity.

Development of Au nanowire injector system to deliver plasmid into mouse embryo.

In this data article, we developed a Au nanowire injector (Au NWI) for directly delivering plasmid into the 1-cell stage of the mouse embryos designed to successfully attach and detach the plasmid on the Au NWI, highly minimizing physical and chemical damage on the embryos. This data presents that a Au NWI system does not induce detrimental damages on development of embryos and efficiently express the green fluorescence protein in vitro. The data provided herein is in association with the research article related to reduce the occurrence of mosaicism by a Au NWI," Suppressing Mosaicism by Au Nanowire Injector-driven Direct Delivery of Plasmids into Mouse Embryos" (Park et al., 2017 [1]).

Suppressing mosaicism by Au nanowire injector-driven direct delivery of plasmids into mouse embryos.

Transgenic animals have become key tools in a variety of biomedical research areas. However, microinjection commonly used for producing transgenic animals has several challenges such as physical and chemical damage to the embryos due to microinjector with buffer, and low transgene integration rates with frequent mosaicism. Here, we report direct delivery of plasmids into mouse embryos using a Au nanowire injector (NWI) that significantly improved transgene integration efficiency and suppressed mosaicism. The Au NWI could deliver plasmid into the pronucleus (PN) of a mouse zygote without buffer and rapidly release it with electric pulse. Because zygote, which is a fertilized 1-cell stage embryo, has two physical barriers (cytoplasmic membrane and zona pellucida), direct delivery of plasmids into PN of zygote is more difficult than into a normal cell type. To penetrate the two physical barriers with minimal disruption of the embryo, we optimized the diameter and length of Au NWI. The mosaicism is more reduced in the Au NWI injected embryos than in micropipette injected embryos, which was determined by the expression of transgene in a blastocyst stage. We suggest that Au NWI can increase the efficiency of gene delivery into zygote with suppressed mosaicism and become a useful alternative.

Stereo-epitaxial growth of single-crystal Ni nanowires and nanoplates from aligned seed crystals.

Epitaxially grown anisotropic Ni nanostructures are promising building blocks for the development of miniaturized and stereo-integrated data storage kits because they can store multiple magnetic domain walls (DWs). Here, we report stereo-epitaxially grown single-crystalline Ni nanowires (NWs) and nanoplates, and their magnetic properties. Vertical and inclined Ni NWs were grown at the center and edge regions of c-cut sapphire substrates, respectively. Vertical Ni nanoplates were grown on r-cut sapphire substrates. The morphology and growth direction of Ni nanostructures can be steered by seed crystals. Cubic Ni seeds grow into vertical Ni NWs, tetrahedral Ni seeds grow into inclined Ni NWs, and triangular Ni seeds grow into vertical Ni nanoplates. The shapes of the Ni seeds are determined by the interfacial energy between the bottom plane of the seeds and the substrates. The as-synthesized Ni NWs and nanoplates have blocking temperature values greater than 300 K at 500 Oe, verifying that these Ni nanostructures can form large magnetic DWs with high magnetic anisotropy properties. We anticipate that epitaxially grown Ni NWs and nanoplates will be used in various types of 3-dimensional magnetic devices.

Single nanowire on graphene (SNOG) as an efficient, reproducible, and stable SERS-active platform.

Developing a well-defined nanostructure that can provide strong, reproducible, and stable SERS signals is quite important for the practical application of surface-enhanced Raman scattering (SERS) sensors. We report here a novel single nanowire (NW) on graphene (SNOG) structure as an efficient, reproducible, and stable SERS-active platform. Au NWs having a well-defined single-crystal geometry on a monolayer graphene-coated metal film can form a well-defined, continuous nanogap structure that provides extremely reproducible and stable SERS signals. The in-NW reproducibility was verified by 2-dimensional Raman mapping, and the NW-to-NW reproducibility was verified by the cumulative curves of 32 SERS spectra. The simulation also indicated that a highly regular, line-shaped hot spot formed between the Au NW and graphene. Furthermore, SNOG platforms showed improved photostability and long-term oxidation immunity. We anticipate that SNOG platforms will be appropriate for practical biological and chemical sensor applications that demand reproducible, stable, and strong signal production.

A twin-free single-crystal Ag nanoplate plasmonic platform: hybridization of the optical nano-antenna and surface plasmon active surface.

Surface plasmons based on metallic nanostructures enable light manipulation beyond the optical diffraction limit. We have epitaxially synthesized twin-free single-crystal Ag nanoplates on SrTiO3 substrates. Unlike the nanoplates synthesized in a solution phase, these nanoplates have perfectly clean surfaces as well as a quite large size of tens of micrometers. As-synthesized defect-free single-crystal Ag nanoplates have an atomically flat surface and sides with well-defined angles, allowing long distance propagation of surface plasmons and highly reliable plasmonic integration. By spatially separating receiving and transmitting antennas and plasmonically interfacing them, the signal quality of transmission/reception can be largely improved. Furthermore, by combining sub-dimensional nanostructures onto the two-dimensional space effective hierarchical plasmonic nano-complexes can be built up. Theoretical simulations well reproduced unique experimental results of coupling between SPPs and free-space radiation by the nanoplate antenna sides, low-loss long-range SPP propagation, and tunneling or scattering of SPPs at a nano-gap as well as a nano-structure introduced on the nanoplate. The single-crystal Ag nanoplate will find superb applications in plasmonic nano-circuitry and lab-on-a-chip for biochemical sensing.

Facile fabrication of multi-targeted and stable biochemical SERS sensors.

The direct transfer of single-crystalline Au nanowires (NWs) onto Au substrates was achieved by a simple attachment and detachment process. In the presence of a lubricant, Au NWs grown vertically on a sapphire substrate were efficiently moved to an Au substrate through van der Waals interactions. We demonstrate that the transferred Au NWs on the Au substrate can act as sensitive, reproducible, and long-term-stable surface-enhanced Raman scattering (SERS) sensors by detecting human α-thrombin as well as Pb(2+) and Hg(2+) ions. These three biochemically and/or environmentally important analytes were successfully detected with high sensitivity and selectivity by Au NW-SERS sensors bound by a thrombin-binding aptamer. Furthermore, the as-prepared sensors remained in working order after being stored under ambient conditions at room temperature for 80 days. Because Au NWs can be routinely transferred onto Au substrates and because the resultant Au NW-SERS sensors are highly stable and provide with high sensitivity and reproducibility of detection, these sensors hold potential for practical use in biochemical sensing.

Single-step multiplex detection of toxic metal ions by Au nanowires-on-chip sensor using reporter elimination.

We have developed a Au nanowires (NWs)-on-chip surface-enhanced Raman scattering (SERS) multiplex sensor that can sensitively detect multiple toxic metal ions. Most importantly, the reporter elimination method simplified the detection procedure to a single step, which has been much desired for remote environmental monitoring. This sensor has several notable features. First, it shows high reproducibility based on well-defined single-crystalline Au NWs. Second, single-NW-sensors that can detect a specific metal ion are combined for multiplex sensing of metal ions. Third, when a sample solution is put onto the NWs-on-chip sensor, a decrease in the SERS signal of a specific NW-sensor identifies the target metal ion. Simple, rapid, sensitive and quantitative detection of metal ions becomes possible through the measurement of the SERS signals. We successfully detected ions of mercury (Hg(2+)), silver (Ag(+)), and lead (Pb(2+)) coexisting in the same solution by using this sensor.

Pattern-selective epitaxial growth of twin-free Pd nanowires from supported nanocrystal seeds.

We report that twin-free single-crystalline Pd nanowire (NW) arrays grow epitaxially in a selected pattern on a substrate. Parallel aligned Pd NWs are synthesized on a SrTiO(3) (110) substrate in a very high density. On a SrTiO(3) (001) substrate, Pd NWs grow horizontally in two perpendicular directions. Vertical Pd NWs are synthesized instead of horizontal NWs when a c-cut sapphire substrate is employed. We reveal that the atomic structure of the substrate surface determines the geometry and orientation of seeds, which in turn direct the growth patterns of the NWs. The interface energy between the NW material and the substrate is also critical in determining the NW growth pattern. Polarization-dependent localized surface plasmon resonance of as-synthesized epitaxial Pd NW arrays is investigated for application as a plasmonic platform.