Ultrasensitive Upconversion Nanoparticle Immunoassay for Human Serum Cardiac Troponin I Detection Achieved with Resonant Waveguide Grating.

Selective detection of biomarkers at low concentrations in blood is crucial for the clinical diagnosis of many diseases but remains challenging. In this work, we aimed to develop an ultrasensitive immunoassay that can detect biomarkers in serum with an attomolar limit of detection (LOD). We proposed a sandwich-type heterogeneous immunosensor in a 3 × 3 well array format by integrating a resonant waveguide grating (RWG) substrate with upconversion nanoparticles (UCNPs). UCNPs were used to label a target biomarker captured by capture antibody molecules immobilized on the surface of the RWG substrate, and the RWG substrate was used to enhance the upconversion luminescence (UCL) of UCNPs through excitation resonance. The LOD of the immunosensor was greatly reduced due to the increased UCL of UCNPs and the reduction of nonspecific adsorption of detection antibody-conjugated UCNPs on the RWG substrate surface by coating the RWG substrate surface with a carboxymethyl dextran layer. The immunosensor exhibited an extremely low LOD [0.24 fg/mL (9.1 aM)] and wide detection range (1 fg/mL to 100 pg/mL) in the detection of cardiac troponin I (cTnI). The cTnI concentrations in human serum samples collected at different times during cyclophosphamide, epirubicin, and 5-fluorouracil (CEF) chemotherapy in a breast cancer patient were measured by an immunosensor, and the results showed that the CEF chemotherapy did cause cardiotoxicity in the patient. Having a higher number of wells in such an array-based biosensor, the sensor can be developed as a high-throughput diagnostic tool for clinically important biomarkers.

Focusing of surface plasmon polaritons propagating at the SiO2/Ag interface with 2-level and 4-level Fresnel phase zone pad structures.

We propose and demonstrate dielectric Fresnel phase zone pad (FPZP) structures for focusing surface plasmon polaritons (SPPs) propagating at the SiO2/Ag interfaces. We exploited up-conversion fluorescence microscopy to characterize the SPP focusing. We first report on the SPP focusing with 2-level FPZP structures that introduced a π-phase shift in the SPP wavefront between adjacent zones. We optimized the SPP focusing by fine-tuning the longitudinal width of the FPZP structure. This led to the enhancement of the peak intensity of the SPP focal spot and the reduction of the focal spot size in both the longitudinal and transverse directions. Such focusing was also demonstrated with different focal lengths. To further improve the SPP focusing, we developed a 4-level FPZP structure, which introduced a π/2-phase shift in the SPP wavefront between adjacent zones. With the optimized 4-level FPZP structure, the SPP focal spot peak intensity is further improved, and the spot size is reduced. To assist the design of the FPZP structures, we carried out theoretical analysis and numerical calculations to determine the SPP wavelengths at various oxide/Ag interfaces. We also carried out finite difference time domain (FDTD) calculations to simulate the SPP focusing with the FPZP structures. The results of the FDTD simulation agree with the experimental results qualitatively.

Subwavelength-resolution imaging of surface plasmon polaritons with up-conversion fluorescence microscopy.

Imaging and characterization of surface plasmon polaritons (SPPs) are crucial for the research and development of the plasmonic devices and circuits. Here, we report on direct imaging of SPPs propagation on SiO2/metal interface with subwavelength spatial resolution using up-conversion fluorescence microscopy, that exploits rare-earth ions, such as Er3+, Yb3+, and Nd3+, doped nanoparticles as the fluorophores. We demonstrated that by further taking the intensity ratio of the image obtained with fluorescent emission at different wavelengths, we are able to substantially enhance the features associated to the SPP wavefronts in the image for quantitative analysis, such as the wavevector and propagation direction of the SPPs. Our results agree with the theoretic prediction of the SPP wavelengths quantitatively. We further demonstrate the evolution of the SPP wavefronts due to refraction SPPs, and reproduced the experiment with finite difference time domain (FDTD) method simulations. The relative refractive index of SPP estimated from the experiment also agrees quantitatively with those extracted from the theory and the simulation.

The First Conducting Spin-Crossover Compound Combining a MnIII Cation Complex with Electroactive TCNQ Demonstrating an Abrupt Spin Transition with a Hysteresis of 50†K.

We present herein the synthesis, crystal structure, and electric and magnetic properties of the spin-crossover salt [Mn(5-Cl-sal-N-1,5,8,12)]TCNQ1.5 ⋅2 CH3 CN (I), where 5-Cl-sal-N-1,5,8,12=N,N'-bis(3-(2-oxy-5-chlorobenzylideneamino)propyl)-ethylenediamine, containing distinct conductive and magnetic blocks along with acetonitrile solvent molecules. The MnIII complex with a Schiff-base ligand, [Mn(5-Cl-sal-N-1,5,8,12)]+ , acts as the magnetic unit, and the π-electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ- ) is the conducting unit. The title compound (I) exhibits semiconducting behavior with room temperature conductivity σRT ≈1×10-4  ohm-1 cm-1 and activation energy Δ ≈0.20 eV. In the temperature range 73-123 K, it experiences a hysteretic phase transition accompanied by a crossover between the low-spin S=1 and high-spin S=2 states of MnIII and changes in bond lengths within the MnN4 O2 octahedra. The pronounced shrinkage of the basal Mn-N bonds in I at the spin crossover suggests that the d x 2 - y 2 orbital is occupied/deoccupied in this transition. Interestingly, the bromo isomorphic counterpart [Mn(5-Br-sal-N-1,5,8,12)]TCNQ1.5 ⋅2 CH3 CN (II) of the title compound evidences no spin-crossover phenomena and remains in the high-spin state in the temperature range 2-300 K. Comparison of the chloro and bromo compounds allows the thermal and spin-crossover contributions to the overall variation in bond lengths to be distinguished. The difference in magnetic behavior of these two salts has been ascribed to intermolecular supramolecular effects on the spin transition. Discrete hydrogen bonding exists between cations and cations and anions in both compounds. However, the hydrogen bonding in the crystals of II is much stronger than in I. The relatively close packing arrangement of the [Mn(5-Br-sal-N-1,5,8,12)]+ cations probably precludes their spin transformation.

Crossover between superconductivity and magnetism in SrRuO3 mesocrystal embedded YBa2Cu3O7-x heterostructures.

The competition between superconductivity and ferromagnetism poses great challenges and has attracted renewed interest for applications in novel spintronic devices. In order to emphasize their interactions, we fabricated a heterostructure composed of superconducting YBa2Cu3O7-δ (YBCO) film embedded with itinerant ferromagnetic SrRuO3 (SRO) mesocrystals. Starting from a doping concentration of 10 vol% of SRO mesocrystal in a YBCO matrix, corresponding to the density of SRO nanocrystals ∼5 × 109 cm-2, which exhibits the typical characteristic of a metal-superconductor transition, and then increasing the magnetic interactions as a function of SRO embedment, the electronic correlation and the interplay between superconductivity and magnetism throughout the temperature regime were investigated. A metal-insulator transition in the normal state of YBCO and a crossover between superconductivity and magnetism at low temperatures were found upon increasing the density of nano-size SRO crystallites in the YBCO matrix as a consequence of competing interactions between these two ordered phases.

Effects of strain on the electronic structure and magnetic properties in SrMn0.5Fe0.5O3.

The electronic structure and magnetic properties of SrMn0.5Fe0.5O3 powder and films grown on (1 0 0)-SrTiO3 (STO) and (1 0 0)-LaAlO3 (LAO) substrates by pulsed laser deposition (PLD) were investigated by temperature dependent magnetization and soft x-ray absorption. The results exhibit characteristics of 3d (5) Fe(3+), [Formula: see text], and 3d (3) + 3d (4) [Formula: see text] Mn(4+) at room temperature in all samples. However, the features of 3d (5) Fe(3+) and 3d (3) Mn(4+) increased significantly for SMFO/LAO at 35 K, which also displayed substantial competition between antiferromagnetic and ferromagnetic order well-above the Néel temperature of SrFeO3 (T N ~ 134 K). We attributed this to being caused by charge disproportionation resulting from ligand-hole localization, which is more favorable to take place when the sample is under compressive strain.

Control of the Metal-Insulator Transition at Complex Oxide Heterointerfaces through Visible Light.

The coupling of the localized surface plasmon resonance of Au nanoparticles is utilized to deliver a visible-light stimulus to control conduction at the LaAlO3 /SrTiO3 interface. A giant photoresponse and the controllable metal-insulator transition are characterized at this heterointerface. This study paves a new route to optical control of the functionality at the heterointerfaces.

Enhanced critical current density in the pressure-induced magnetic state of the high-temperature superconductor FeSe.

We investigate the relation of the critical current density (Jc) and the remarkably increased superconducting transition temperature (Tc) for the FeSe single crystals under pressures up to 2.43 GPa, where the Tc is increased by ~8 K/GPa. The critical current density corresponding to the free flux flow is monotonically enhanced by pressure which is due to the increase in Tc, whereas the depinning critical current density at which the vortex starts to move is more influenced by the pressure-induced magnetic state compared to the increase of Tc. Unlike other high-Tc superconductors, FeSe is not magnetic, but superconducting at ambient pressure. Above a critical pressure where magnetic state is induced and coexists with superconductivity, the depinning Jc abruptly increases even though the increase of the zero-resistivity Tc is negligible, directly indicating that the flux pinning property compared to the Tc enhancement is a more crucial factor for an achievement of a large Jc. In addition, the sharp increase in Jc in the coexisting superconducting phase of FeSe demonstrates that vortices can be effectively trapped by the competing antiferromagnetic order, even though its antagonistic nature against superconductivity is well documented. These results provide new guidance toward technological applications of high-temperature superconductors.

Manifestation of a Second Dirac Surface State and Bulk Bands in THz Radiation from Topological Insulators.

Topological insulators (TIs) are interesting quantum matters that have a narrow bandgap for bulk and a Dirac-cone-like conducting surface state (SS). The recent discovered second Dirac surface state (SS) and bulk bands (BBs) located ~1.5 eV above the first SS are important for optical coupling in TIs. Here, we report on the time-domain measurements of THz radiation generated from TIs n-type Cu(0.02)Bi2Se3 and p-type Bi2Te3 single crystals by ultrafast optical pulse excitation. The observed polarity-reversal of the THz pulse originated from transient current is unusual, and cannot be reconciled with the photo-Dember effect. The second SS and BBs are found to be indispensable for the explanation of the unusual phenomenon. Thanks to the existence of the second SS and BBs, TIs manifest an effective wide band gap in THz generation. The present study demonstrates that time-domain THz spectroscopy provide rich information of the optical coupling and the electronic structure of TIs.

Tuning electronic transport in a self-assembled nanocomposite.

Self-assembled nanocomposites with a high interface-to-volume ratio offer an opportunity to overcome limitations in current technology, where intriguing transport behaviors can be tailored by the choice of proper interactions of constituents. Here we integrated metallic perovskite oxide SrRuO3-wurzite semiconductor ZnO nanocomposites to investigate the room-temperature metal-insulator transition and its effect on photoresponse. We demonstrate that the band structure at the interface can be tuned by controlling the interface-to-volume ratio of the nanocomposites. Photoinduced carrier injection driven by visible light was detected across the nanocomposites. This work shows the charge interaction of the vertically integrated multiheterostructures by incorporating a controllable interface-to-volume ratio, which is essential for optimization of the design and functionality of electronic devices.

Large magnetoresistance in magnetically coupled SrRuO3 -CoFe2O4 self-assembled nanostructures.

A new way to induce a large magnetoresistance has been achieved by self-assembled nanostructures consisting of ferromagnetic spinel CoFe2O4 (CFO) and metallic perovskite SrRuO3 (SRO). The interdiffused Fe³âº ions in SRO have paved the way to strong magnetic couplings with CFO nanopillars, resulting in the suppression of spin-polarized electron scattering.

Ferroelectric control of the conduction at the LaAlO3/SrTiO3 heterointerface.

Modulation of band bending at a complex oxide heterointerface by a ferroelectric layer is demonstrated. The as-grown polarization (Pup ) leads to charge depletion and consequently low conduction. Switching the polarization direction (Pdown ) results in charge accumulation and enhances the conduction at the interface. The metal-insulator transition at a conducting polar/nonpolar oxide heterointerface can be controlled by ferroelectric doping.

Mapping band alignment across complex oxide heterointerfaces.

In this study, direct observation of the evolution of electronic structures across complex oxide interfaces has been revealed in the LaAlO(3)/SrTiO(3) model system using cross-sectional scanning tunneling microscopy and spectroscopy. The conduction and valence band structures across the LaAlO(3)/SrTiO(3) interface are spatially resolved at the atomic level by measuring the local density of states. This study directly maps out the electronic reconstructions and a built-in electric field in the polar LaAlO(3) layer. Results also clearly reveal the band bending and the notched band structure in the SrTiO(3) adjacent to the interface.

Measurement of membrane rigidity on trapped unilamellar phospholipid vesicles by using differential confocal microscopy.

We use optical tweezers to trap a unilamellar phospholipid vesicle and measure the out-of-plane thermal fluctuations by using differential confocal microscopy. Bending moduli of the lipid membranes are calculated directly from the mean-square values of the fluctuation amplitudes. Owing to the refractive index contrast between the inner and outer solutions of the vesicle, optical tweezers trap the vesicle laterally and improve the reliability of the measured fluctuation amplitudes along the optical axis. Bending moduli of membranes in gel or fluid phases obtained by the combination of differential confocal microscopy and optical tweezers are close to those reported previously. We also obtain the bending modulus of sphingomyelin membranes in the gel phase, which was not reported previously.

Asymmetric cancer-cell filopodium growth induced by electric-fields in a microfluidic culture chip.

We combine a micro-fluidic electric-field cell-culture (MEC) chip with structured-illumination nano-profilometry (SINAP) to quantitatively study the variations of cancer cell filopodia under external direct-current electric field (dcEF) stimulations. Because the lateral resolution of SINAP is better than 150 nm in bright-field image modality, filopodia with diameters smaller than 200 nm can be observed clearly without fluorescent labeling. In the MEC chip, a homogeneous EF is generated inside the culture area that simulates the endogenous EF environment. With this MEC chip-SINAP system, we directly observe and quantify the biased growth of filopodia of lung cancer cells toward the cathode. The epidermal growth factor receptors around the cell edges are also redistributed to the cathodal side. These results suggest that cancer-cell filopodia respond to the changes in EFs in the microenvironment.

Synthesis of epitaxial metal oxide nanocrystals via a phase separation approach.

Perovskite phase instability of BiMnO3 has been exploited to synthesize epitaxial metal oxide magnetic nanocrystals. Thin film processing conditions are tuned to promote the breakdown of the perovskite precursor into Bi2O3 matrix and magnetic manganese oxide islands. Subsequent cooling in vacuum ensures complete volatization of the Bi2O3, thus leaving behind an array of self-assembled magnetic Mn3O4 nanostructures. Both shape and size can be systematically controlled by the ambient oxygen environments and deposition time. As such, this approach can be extended to any other Bi-based complex ternary oxide system as it primarily hinges on the breakdown of parent Bi-based precursor and subsequent Bi2O3 volatization.

Seeding of a soft-x-ray laser in a plasma waveguide by high harmonic generation.

A strongly saturated waveguide-based optical-field-ionization soft-x-ray laser seeded by high harmonic generation was demonstrated for Ni-like Kr lasing at 32.8 nm. Compared with the same laser seeded only with spontaneous emission, seeding with high harmonics yields much smaller divergence, enhanced spatial coherence, and controlled polarization. The integration of high harmonic seeding, optically preformed plasma waveguide, and optical-field-ionization pumping forms one of the optimal archetypes of an ultrashort-pulse soft-x-ray laser.

Single-shot soft-x-ray digital holographic microscopy with an adjustable field of view and magnification.

Single-shot digital holographic microscopy with an adjustable field of view and magnification was demonstrated by using a tabletop 32.8 nm soft-x-ray laser. The holographic images were reconstructed with a two-dimensional fast-Fourier-transform algorithm, and a new configuration of imaging was developed to overcome the pixel-size limit of the recording device without reducing the effective NA. The image of an atomic-force-microscope cantilever was reconstructed with a lateral resolution of 480 nm, and the phase contrast image of a 20 nm carbon mesh foil demonstrated that profiles of sample thickness can be reconstructed with few-nanometers uncertainty. The ultrashort x-ray pulse duration combined with single-shot capability offers great advantage for flash imaging of delicate samples.

Observation of nanoparticle internalization on cellular membranes by using noninterferometric widefield optical profilometry.

We demonstrate the observation of gold-nanoparticle internalization in membranes of living cells by using noninterferometric widefield optical profilometry (NIWOP). The NIWOP technique can trace the height of an 80 nm gold particle on the membrane by calibrating the change of light intensity scattered from the particle along the optical axis. On the membrane, the depth resolution based on the scattering signal is similar to that based on the reflection signal, nearly 20 nm. Comparing the heights of the nanoparticle and the nearby cell membranes, we can identify the occurrence of particle internalization. Combining fluorescence microscopy with NIWOP, we also find actin aggregation around the site of the internalization process, which is an indication of endocytosis.

Transparent thin-film characterization by using differential optical sectioning interference microscopy.

We propose an optical thin-film characterization technique, differential optical sectioning interference microscopy (DOSIM), for simultaneously measuring the refractive indices and thicknesses of transparent thin films with submicrometer lateral resolution. DOSIM obtains the depth and optical phase information of a thin film by using a dual-scan concept in differential optical sectioning microscopy combined with the Fabry-Perot interferometric effect and allows the solution of refractive index and thickness without the 2pi phase-wrapping ambiguity. Because DOSIM uses a microscope objective as the probe, its lateral resolution achieves the diffraction limit. As a demonstration, we measure the refractive indices and thicknesses of SiO2 thin films grown on Si substrate and indium-tin-oxide thin films grown on a glass substrate. We also compare the measurement results of DOSIM with those of a conventional ellipsometer and an atomic force microscope.