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We investigated the magnetic effect of Mn2+ ions on an exciton of Mn-doped CsPbI3 quantum dots (QDs), where we looked for the signatures of an exciton magnetic polaron known to produce a large effective magnetic field in Mn-doped CdSe QDs. In contrast to Mn-doped CdSe QDs that can produce ∼100 T of magnetic field upon photoexcitation, manifested as a large change in the energy and relaxation dynamics of a bright exciton, Mn-doped CsPbI3 QDs exhibited little influence of a magnetic dopant on the behavior of a bright exciton. However, a μs-lived dark exciton in CsPbI3 QDs showed 40% faster decay in the presence of Mn2+, equivalent to the effect of ∼3 T of an external magnetic field. While further study is necessary to fully understand the origin of the large difference in the magneto-optic property of an exciton in two systems, we consider that the difference in antiferromagnetic coupling of the dopants is an important contributing factor.

Nanoparticles with multifunctionality and high colloidal stability are essential for biomedical applications. However, their use is often hindered by the formation of thick coating shells and/or nanoparticle agglomeration. Herein, we report a single nanoparticle coating strategy to form 1 nm polymeric shells with a variety of chemical functional groups and surface charges. Under exposure to alternating magnetic field, nanosecond thermal energy pulses trigger a polymerization in the region only a few nanometers from the magnetic nanoparticle (MNP) surface. Modular coatings containing functional groups, according to the respective choice of monomers, are possible. In addition, the surface charge can be tuned from negative through neutral to positive. We adopted a coating method for use in biomedical targeting studies where obtaining compact nanoparticles with the desired surface charge is critical. A single MNP with a zwitterionic charge can provide excellent colloidal stability and cell-specific targeting.

Contrast agents for magnetic resonance imaging (MRI) improve anatomical visualizations. However, owing to poor image resolution in whole-body MRI, resolving fine structures is challenging. Here, we report that a nanoparticle with a polysaccharide supramolecular core and a shell of amorphous-like hydrous ferric oxide generating strong T1 MRI contrast (with a relaxivity coefficient ratio of ~1.2) facilitates the imaging, at resolutions of the order of a few hundred micrometres, of cerebral, coronary and peripheral microvessels in rodents and of lower-extremity vessels in rabbits. The nanoparticle can be synthesized at room temperature in aqueous solution and in the absence of surfactants, has blood circulation and renal clearance profiles that prevent opsonization, and leads to better imaging performance than Dotarem (gadoterate meglumine), a clinically approved gadolinium-based MRI contrast agent. The nanoparticle's biocompatibility and imaging performance may prove advantageous in a broad range of preclinical and clinical applications of MRI.

Tactile pressure sensors as flexible bioelectronic devices have been regarded as the key component for recently emerging applications in electronic skins, health-monitoring devices, or human-machine interfaces. However, their narrow range of sensible pressure and their difficulty in forming high integrations represent major limitations for various potential applications. Herein, we report fully integrated, active-matrix arrays of pressure-sensitive MoS2 transistors with mechanoluminescent layers and air dielectrics for wide detectable range from footsteps to cellular motions. The inclusion of mechanoluminescent materials as well as air spaces can increase the sensitivity significantly over entire pressure regimes. In addition, the high integration capability of these active-matrix sensory circuitries can enhance their spatial resolution to the level sufficient to analyze the pressure distribution in a single cardiomyocyte. We envision that these wide-range pressure sensors will provide a new strategy toward next-generation electronics at biomachine interfaces to monitor various mechanical and biological phenomena at single-cell resolution.

Wireless communication through linkage with a smartphone and other portable devices in the sensor area are essential for increasing the efficiency of utilization by storing sensing-value data. Thus, the demand for wireless technology is increasing due to the advantages it provides for the various applications that use these data. However, there is still considerable ambiguity concerning the low portability of such technology due to the increased volume with component integration, the high consumption of power, and the necessity of having a separate battery. Herein, we present solutions for these problems with demonstrations that involve 1) the miniaturization of the device by altering the structure of the built-in battery, 2) the use of a pressure-activated switch for the low-power driving technology, and 3) the implementation of a wireless communication platform by integrating a Bluetooth module with the devices. In addition, we demonstrate a human-interactive display that enables users to instantly observe the changes in the brightness of the organic light-emitting diodes (OLED) as the pressure changes. We show that the system can display the measured, real-time pressure values on the screens of mobile devices, which represents a significant advancement in the fields of energy science and biomedical science.

The ideal combination of high optical transparency and high electrical conductivity, especially at very low frequencies of less than the gigahertz (GHz) order, such as the radiofrequencies at which electronic devices operate (tens of kHz to hundreds of GHz), is fundamental incompatibility, which creates a barrier to the realization of enhanced user interfaces and ‘device-to-device integration.’ Herein, we present a design strategy for preparing a megahertz (MHz)-transparent conductor, based on a plasma frequency controlled by the electrical conductivity, with the ultimate goal of device-to-device integration through electromagnetic wave transmittance. This approach is verified experimentally using a conducting polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), the microstructure of which is manipulated by employing a solution process. The use of a transparent conducting polymer as an electrode enables the fabrication of a fully functional touch-controlled display device and magnetic resonance imaging (MRI)-compatible biomedical monitoring device, which would open up a new paradigm for transparent conductors., The emergence of applications requiring device-to-device interactivity has to the need to develop conducting electrodes with high optical transparency at low radiofrequencies. Here, the authors demonstrate conductive polymer electrodes with high transparency in the MHz-order frequency range.

ConspectusInorganic nanocrystal design has been continuously evolving with a better understanding of the chemical reaction mechanisms between chemical stimuli and nanocrystals. Under certain conditions, molecular compounds can be effective as chemical stimuli to induce transformative reactions of nanocrystals toward new materials that would differ in geometric shape, composition, and crystallographic structure. To explore such evolutionary processes, two-dimensional (2D) layered transition-metal chalcogenide (TMC) nanostructures are an interesting structural platform because they not only exhibit unique transformation pathways due to their structural anisotropy but also present new opportunities for improved material properties for potential applications such as catalysis and energy conversion and storage. The high surface area/volume ratio, interlayer van der Waals (vdW) spacing, and different coordination states between the unsaturated edges and the fully saturated basal planes of the chalcogens are characteristic of 2D layered TMC nanostructures, which subsequently lead to anisotropic chemical processes during chemical transformations, such as regioselective reactions at the interfacial boundaries in the pathways for either porous or solid heteronanostructures. In this Account, we first discuss the chemical reactivity of 2D layered TMC nanostructures. By categorizing the external stimuli in terms of chemical principles, such as Lewis acid-base chemistry, a desirable regioselective chemical reaction can occur with controlled reactivity. In association with the knowledge obtained from the nanoscale chemical reactivity of 2D layered nanocrystals, similar efforts in other important morphologies such as 1D and isotropic 0D nanocrystals are introduced. For instance, for 1D and 0D metal oxide nanocrystals, the effects of molecular stimuli on the atomic-level changes in the crystal lattice are demonstrated, eventually leading to a variety of shape transformations.

Ideal electromagnetic (EM) wave absorbers can absorb all incident EM waves, regardless of the incident direction, polarization, and frequency. Absorptance and reflectance are intrinsic material properties strongly correlated with electrical conductivity; hence, achieving perfect absorptance with zero reflectance is challenging. Herein, we present a design strategy for preparing a nearly ideal EM absorber based on a layered metal that maximizes absorption by utilizing multiple internal reflections and minimizes reflection using a monotonic gradient of intrinsic impedance. This approach was experimentally verified using aluminum nanoflakes prepared via topochemical etching of lithium from Li9Al4, and the impedance-graded structure was obtained through the size-based sorting behavior of aluminum nanoflakes sinking in dispersion. Unlike in traditional shielding materials, strong absorption (26.76 dB) and negligible reflectivity (0.04 dB) with a ratio of >103 can be achieved in a 120 μm thick film. Overall, our findings exhibit potential for developing a novel class of antireflective shielding materials.

The fine structure of the band edge exciton and the dark exciton photoluminescence (PL) are topics of significant interest in the research of semiconducting metal halide perovskite nanocrystals, with several conflicting reports on the level ordering of the bright and dark states and the accessibility of the emitting dark states. Recently, we observed the intense dark exciton PL in strongly confined CsPbBr3 nanocrystals at cryogenic temperatures, in contrast to weakly confined nanocrystals lacking dark exciton PL, which was explained by the confinement enhanced bright-dark exciton splitting. In this work, we investigated the size-dependence of the dark exciton photoluminescence properties in CsPbBr3 and CsPbI3 quantum dots in the strongly confined regime, showing the clear role of confinement in determining the bright-dark energy splitting (ΔEBD) and the dark exciton lifetime (τD). We observe the increase in both ΔEBD and τD with increasing quantum confinement in CsPbBr3 and CsPbI3 QDs, consistent with the earlier predictions on the size-dependence of ΔEBD and τD. Our results show that quantum confinement plays a crucial role in determining the accessibility to the dark exciton PL and its characteristics in metal halide perovskite nanocrystals.

This study presents a smart, soft contact lens that provides real-time sensing for the wireless immunosensing of cortisol., Despite various approaches to immunoassay and chromatography for monitoring cortisol concentrations, conventional methods require bulky external equipment, which limits their use as mobile health care systems. Here, we describe a human pilot trial of a soft, smart contact lens for real-time detection of the cortisol concentration in tears using a smartphone. A cortisol sensor formed using a graphene field-effect transistor can measure cortisol concentration with a detection limit of 10 pg/ml, which is low enough to detect the cortisol concentration in human tears. In addition, this soft contact lens only requires the integration of this cortisol sensor with transparent antennas and wireless communication circuits to make a smartphone the only device needed to operate the lens remotely without obstructing the wearer’s view. Furthermore, in vivo tests using live rabbits and the human pilot experiment confirmed the good biocompatibility and reliability of this lens as a noninvasive, mobile health care solution.

Because of the absence of native dangling bonds on the surface of the layered transition metal dichalcogenides (TMDCs), the surface of colloidal quantum dots (QDs) of TMDCs is exposed directly to the solvent environment. Therefore, the optical and electronic properties of TMDCS QDs are expected to have stronger influence from the solvent than usual surface-passivated QDs due to more direct solvent-QD interaction. Study of such solvent effect has been difficult in colloidal QDs of TMDC due to the large spectroscopic heterogeneity resulting from the heterogeneity of the lateral size or (and) thickness in ensemble. Here, we developed a new synthesis procedure producing the highly uniform colloidal monolayer WS2 QDs exhibiting well-defined photoluminescence (PL) spectrum free from ensemble heterogeneity. Using these newly synthesized monolayer WS2 QDs, we observed the strong influence of the aromatic solvents on the PL energy and intensity of monolayer WS2 QD beyond the simple dielectric screening effect, whi...

Magnetic nanoparticle (MNP)-mediated heating systems have emerged as an effective strategy for the fine control of biological systems from hyperthermia to cell signaling in a spatiotemporally controlled fashion. To achieve satisfactory performance, advanced design concepts have been developed to tailor the magnetism that directly affects the heating properties of nanoparticles. In this review, we focus on recent advances in magnetism-engineered nanoparticles. Fundamental principles of magnetic heating mechanisms and related key magnetic parameters are discussed first to provide instructive guidelines for the design of MNPs with enhanced heating efficiency. Then, we highlight recent progress in MNPs for optimized heat generation with unique design approaches to control magnetism. Finally, we discuss highly effective biomedical application studies such as dual-mode magnetic hyperthermia, magnetothermally triggered drug delivery, and the magnetothermal control of cellular activities.

Dark ground state exciton in semiconductor nanocrystals has been a subject of much interest due to its long lifetime attractive for applications requiring long-lived electronic or spin states. Significant effort has been made recently to explore and access the dark exciton level in metal halide perovskite nanocrystals, which are emerging as a superior source of photons and charges compared to other existing semiconductor nanocrystals. However, the direct observation of long-lived photoluminescence from dark exciton has remained elusive in metal halide perovskite nanocrystals. Here, we report the observation of the intense emission from dark ground state exciton with 1-10 us lifetime in strongly quantum confined CsPbBr3 nanocrystals, which contrasts the behavior of weakly confined system explored so far. The study in CsPbBr3 nanocrystals with varying degree of confinement has revealed the crucial role of quantum confinement in enhancing the bright-dark exciton level splitting which is important for accessing the dark exciton. Our work demonstrates the future potential of strongly quantum-confined perovskite nanocrystals as a new platform to utilize dark excitons.

Phosphorene, a monolayer of black phosphorus (BP), is an elemental two-dimensional material with interesting physical properties, such as high charge carrier mobility and exotic anisotropic in-plane properties. To fundamentally understand these various physical properties, it is critically important to conduct an atomic-scale structural investigation of phosphorene, particularly regarding various defects and preferred edge configurations. However, it has been challenging to investigate mono- and few-layer phosphorene because of technical difficulties arising in the preparation of a high-quality sample and damages induced during the characterization process. Here, we successfully fabricate high-quality monolayer phosphorene using a controlled thinning process with transmission electron microscopy, and subsequently perform atomic-resolution imaging. Graphene protection suppresses the e-beam-induced damage to multi-layer BP and one-side graphene protection facilitates the layer-by-layer thinning of the samples, rendering high-quality monolayer and bilayer regions. We also observe the formation of atomic-scale crystalline edges predominantly aligned along the zigzag and (101) terminations, which is originated from edge kinetics under e-beam-induced sputtering process. Our study demonstrates a new method to image and precisely manipulate the thickness and edge configurations of air-sensitive two-dimensional materials., 21 pages, 5 figures

Recent suggestions of nanoscale heat confinement on the surface of synthetic and biogenic magnetic nanoparticles during heating by radio frequency-alternating magnetic fields have generated intense interest because of the potential utility of this phenomenon for noninvasive control of biomolecular and cellular function. However, such confinement would represent a significant departure from the classical heat transfer theory. Here, we report an experimental investigation of nanoscale heat confinement on the surface of several types of iron oxide nanoparticles commonly used in biological research, using an all-optical method devoid of the potential artifacts present in previous studies. By simultaneously measuring the fluorescence of distinct thermochromic dyes attached to the particle surface or dissolved in the surrounding fluid during radio frequency magnetic stimulation, we found no measurable difference between the nanoparticle surface temperature and that of the surrounding fluid for three distinct nanoparticle types. Furthermore, the metalloprotein ferritin produced no temperature increase on the protein surface nor in the surrounding fluid. Experiments mimicking the designs of previous studies revealed potential sources of the artifacts. These findings inform the use of magnetic nanoparticle hyperthermia in engineered cellular and molecular systems.

A flexible magnetic wire inserted in a blood vessel improves the capture of magnetically labelled circulating tumour cells.

Sensors that detect specific molecules of interest in a living organism can be useful tools for studying biological functions and diseases. Here, we provide a protocol for the construction of nanosensors that can noninvasively detect biologically important targets with magnetic resonance imaging (MRI). The key operating principle of these sensors is magnetic resonance tuning (MRET), a distance-dependent phenomenon occurring between a superparamagnetic quencher and a paramagnetic enhancer. The change in distance between the two magnetic components modulates the longitudinal (T1) relaxivity of the enhancer. In this MRET sensor, distance variation is achieved by interactive linkers that undergo binding, cleavage, or folding/unfolding upon their interaction with target molecules. By the modular incorporation of suitable linkers, the MRET sensor can be applied to a wide range of targets. We showcase three examples of MRET sensors for enzymes, nucleic acid sequences, and pH. This protocol comprises three stages: (i) chemical synthesis and surface modification of the quencher, (ii) conjugation with interactive linkers and enhancers, and (iii) MRI sensing of biological targets. The entire procedure takes up to 3 d. This protocol describes the synthesis of magnetic resonance tuning (MRET) sensors. The sensors consist of two magnetic components separated by a linker and can be modularly designed for targets such as enzymes, nucleic acid sequences, and pH values.

We report an unusual response of colloidal layered transition metal dichalcogenide (TMDC) nanodiscs to the electric field, where the orientational order is created transiently only during the time-varying period of the electric field while no orientational order is created by the DC field. This result is in stark contrast to the typical electrokinetic response of various other colloidal nanoparticles, where the permanent dipole or (and) anisotropic-induced dipole creates a sustaining orientational order under the DC field. This indicates the lack of a sizable permanent dipole or (and) anisotropic-induced dipole in colloidal TMDC nanodiscs, despite their highly anisotropic lattice structure. While the orientational order is created only transiently by the time-varying field, a near-steady-state orientational order can be obtained by using an AC electric field. We demonstrate the utility of this method for the controlled orientation of colloidal nanoparticles that cannot be controlled via the usual interaction of the electric field with the nanoparticle dipole.

Atomically thin layered transition metal dichalcogenides with highly anisotropic structure exhibit strong anisotropy in various material properties. Here, we report the anisotropic coupling between the interband optical transition and coherent acoustic phonon excited by ultrashort optical excitation in a colloidal solution of multilayered TiS2 nanodiscs. The transient absorption signal from the diameter- and thickness-controlled TiS2 nanodiscs dispersed in solution exhibited an oscillatory feature, which is attributed to the modulation of the interband absorption peak by the intralayer breathing mode. However, the signature of the interlayer acoustic phonon was not observed, while it has been previously observed in noncolloidal exfoliated sheets of MoS2. The dominance of the intralayer mode in modulating the interband optical transition was supported by the density functional theory (DFT) calculations of the optical absorption spectra of TiS2, which showed the stronger sensitivity of the interband absorpt...

Magnetic nanoparticles have been extensively explored as a versatile platform for magnetic resonance imaging (MRI) contrast agents due to their strong contrast enhancement effects together with the platform capability for multiple imaging modalities. In this tutorial review, we focus on recent progress in the use of magnetic nanoparticles for MRI contrast agents and multi-mode imaging agents such as T1-T2 MRI, MRI-optical, and MRI-radioisotopes. This review also highlights emerging magnetic imaging techniques such as magnetic particle imaging (MPI), magneto-motive ultrasound imaging (MMUS), and magneto-photoacoustic imaging (MPA).

Bulk magnetite (Fe3O4), the loadstone used in magnetic compasses, has been known to exhibit magnetoelectric (ME) properties below ~10 K; however, corresponding ME effects in Fe3O4 nanoparticles have been enigmatic. We investigate quantitatively the ME coupling of spherical Fe3O4 nanoparticles with uniform diameters (d) from 3 to 15 nm embedded in an insulating host, using a sensitive ME susceptometer. The intrinsic ME susceptibility (MES) of the Fe3O4 nanoparticles is measured, exhibiting a maximum value of ~0.6 ps/m at 5 K for d=15 nm. We found that the MES is reduced with reduced d but remains finite until d=~5 nm, which is close to the critical thickness for observing the Verwey transition. Moreover, with reduced diameter, the critical temperature below which the MES becomes conspicuous increased systematically from 9.8 K in the bulk to 19.7 K in the nanoparticles with d=7 nm, reflecting the core-shell effect on the ME properties. These results point to a new pathway for investigating ME effect in various nanomaterials., 19 pages, 4 figures

Colloidal 2-D layered transition metal dichalcogenide (TMDC) nanodiscs synthesized with uniform diameter and thickness can readily form the vertically stacked assemblies of particles in solution due to strong interparticle cohesive energy. The interparticle electronic coupling that modifies their optical and electronic properties poses a significant challenge in exploring their unique properties influenced by the anisotropic quantum confinement in different directions taking advantage of the controlled diameter and thickness. Here, we show that the assemblies of 2-D layered TiS2 nanodiscs are efficiently separated into individual nanodiscs via photoexcitation of the charge carriers by pulsed laser light, enabling the characterization of the properties of noninteracting TiS2 nanodiscs. Photoinduced separation of the nanodiscs is considered to occur via transient weakening of the interparticle cohesive force by the dense photoexcited charge carriers, which facilitates the solvation of each nanodisc by the s...

One of the holy grails in biomedical imaging technology is to achieve accurate imaging of biological targets. The development of sophisticated instrumentation and the use of contrast agents have improved the accuracy of biomedical imaging. However, the issue of false imaging remains a problem. Here, we developed a dual-mode artifact filtering nanoparticle imaging agent (AFIA) that comprises a combination of paramagnetic and superparamagnetic nanomaterials. This AFIA has the ability to perform “AND logic gate” algorithm to eliminate false errors (artifacts) from the raw images to enhance accuracy of the MRI. We confirm the artifact filtering capability of AFIA in MRI phantoms and further demonstrate that artifact-free imaging of stem cell migration is possible in vivo.

The atomic or molecular assembly on 2D materials through the relatively weak van der Waals interaction is quite different from the conventional heteroepitaxy and may result in unique growth behaviors. Here, it is shown that straight 1D cyanide chains display universal epitaxy on hexagonal 2D materials. A universal oriented assembly of cyanide crystals (AgCN, AuCN, and Cu0.5Au0.5CN) is observed, where the chains are aligned along the three zigzag lattice directions of various 2D hexagonal crystals (graphene, h‐BN, WS2, MoS2, WSe2, MoSe2, and MoTe2). The potential energy landscape of the hexagonal lattice induces this preferred alignment of 1D chains along the zigzag lattice directions, regardless of the lattice parameter and surface elements as demonstrated by first‐principles calculations and parameterized surface potential calculations. Furthermore, the oriented microwires can serve as crystal orientation markers, and stacking‐angle‐controlled vertical 2D heterostructures are successfully fabricated by using them as markers. The oriented van der Waals epitaxy can be generalized to any hexagonal 2D crystals and will serve as a unique growth process to form crystals with orientations along the zigzag directions by epitaxy., 1D cyanide chains show universal oriented van der Waals epitaxy on various hexagonal 2D crystals. The chain directions are always aligned along the zigzag lattice directions of the 2D substrates, regardless of differing lattice parameters and surface elements. Stacking‐angle‐controlled vertical 2D heterostructures can also be fabricated using cyanide microwire markers for identification of crystal orientations.

The multicatalytic ubiquitin-proteasome system (UPS) carries out proteolysis in a highly orchestrated way and regulates a large number of cellular processes. Deregulation of the UPS in many disorders has been documented. In some cases, such as carcinogenesis, elevated proteasome activity has been implicated in disease development, while the etiology of other diseases, such as neurodegeneration, includes decreased UPS activity. Therefore, agents that alter proteasome activity could suppress as well as enhance a multitude of diseases. Metal oxide nanoparticles, often developed as diagnostic tools, have not previously been tested as modulators of proteasome activity. Here, several types of metal oxide nanoparticles were found to adsorb to the proteasome and show variable preferential binding for particular proteasome subunits with several peptide binding "hotspots" possible. These interactions depend on the size, charge, and concentration of the nanoparticles and affect proteasome activity in a time-dependent manner. Should metal oxide nanoparticles increase proteasome activity in cells, as they do in vitro, unintended effects related to changes in proteasome function can be expected.

The magnetic exchange coupling interaction between hard and soft magnetic phases has been important for tailoring nanoscale magnetism, but spin interactions at the core–shell interface have not been well studied. Here, we systematically investigated a new interface phenomenon termed enhanced spin canting (ESC), which is operative when the shell thickness becomes ultrathin, a few atomic layers, and exhibits a large enhancement of magnetic coercivity (HC). We found that ESC arises not from the typical hard–soft exchange coupling but rather from the large magnetic surface anisotropy (KS) of the ultrathin interface. Due to this large increase in magnetism, ultrathin core–shell nanoparticles overreach the theoretical limit of magnetic energy product ((BH)max) and exhibit one of the largest values of specific loss power (SLP), which testifies to their potential capability as an effective mediator of magnetic energy conversion.

© 2017 The Royal Society of Chemistry. Magnetic nanoparticles (MNPs) are widely used in biomedical and clinical applications, including medical imaging, therapeutics, and biological sample processing. Rapid characterization of MNPs, notably their magnetic moments, should facilitate optimization of particle synthesis and accelerate assay development. Here, we report a compact and low-cost magnetometer for fast, on-site MNP characterization. Termed integrated microHall magnetometer (iHM), our device was fabricated using standard semiconductor processes: an array of Hall sensors, transistor switches, and amplifiers were integrated into a single chip, thus improving the detection sensitivity and facilitating chip operation. By applying the iHM, we demonstrate versatile magnetic assays. We measured the magnetic susceptibility and moments of MNPs using small sample amounts (∼10 pL), identified different MNP compositions in mixtures, and detected MNP-labeled single cells.

Sound perception via mechano-sensation is a remarkably sensitive and fast transmission process, converting sound as a mechanical input to neural signals in a living organism. Although knowledge of auditory hair cell functions has advanced over the past decades, challenges remain in understanding their biomechanics, partly because of their biophysical complexity and the lack of appropriate probing tools. Most current studies of hair cells have been conducted in a relatively low-frequency range (1000 Hz); therefore, fast kinetic study of hair cells has been difficult, even though mammalians have sound perception of 20 kHz or higher. Here, we demonstrate that the magnetic force nanoprobe (MFN) has superb spatiotemporal capabilities to mechanically stimulate spatially-targeted individual hair cells with a temporal resolution of up to 9 μs, which is equivalent to approximately 50 kHz; therefore, it is possible to investigate avian hair cell biomechanics at different tonotopic regions of the cochlea covering a full hearing frequency range of 50 to 5000 Hz. We found that the variation of the stimulation frequency and amplitude of hair bundles creates distinct mechanical responsive features along the tonotopic axis, where the kinetics of the hair bundle recovery motion exhibits unique frequency-dependent characteristics: basal, middle, and apical hair bundles can effectively respond at their respective ranges of frequency. We revealed that such recovery kinetics possesses two different time constants that are closely related to the passive and active motilities of hair cells. The use of MFN is critical for the kinetics study of free-standing hair cells in a spatiotemporally distinct tonotopic organization.

The regulation of cellular activities in a controlled manner is one of the most challenging issues in fields ranging from cell biology to biomedicine. Nanoparticles have the potential of becoming useful tools for controlling cell signalling pathways in a space and time selective fashion. Here, we have developed magnetic nanoparticles that turn on apoptosis cell signalling by using a magnetic field in a remote and non-invasive manner. The magnetic switch consists of zinc-doped iron oxide magnetic nanoparticles (Zn(0.4)Fe(2.6)O(4)), conjugated with a targeting antibody for death receptor 4 (DR4) of DLD-1 colon cancer cells. The magnetic switch, in its On mode when a magnetic field is applied to aggregate magnetic nanoparticle-bound DR4s, promotes apoptosis signalling pathways. We have also demonstrated that the magnetic switch is operable at the micrometre scale and that it can be applied in an in vivo system where apoptotic morphological changes of zebrafish are successfully induced.

With the aim of controlling nanoscale magnetism, we demonstrate an approach encompassing concepts of surface and exchange anisotropy while reflecting size, shape, and structural hybridization of nanoparticles. We visualize that cube has higher magnetization value than sphere with highest coercivity at 60 nm. Its hybridization into core-shell (CS) structure brings about a 14-fold increase in the coercivity with an exceptional energy conversion of magnetic field into thermal energy of 10600 W/g, the largest reported to date. Such capability of the CS-cube is highly effective for drug resistant cancer cell treatment.

The imaging and diagnosis with magnetic resonance imaging could be greatly benefitted by the use of contrast agents based on magnetic nanoparticles. Several strategies for enhancing sensitivity and accuracy have been introduced which include the enhancement of magnetization values and multi-modal imaging techniques. Especially multi-modalities into which several complementary imaging modalities are converged can greatly reduce possible false-positive signals and enhance diagnosing accuracy. We here explain some examples of integration strategies to achieve this high accuracy.

The conversion of electromagnetic energy into heat by nanoparticles has the potential to be a powerful, non-invasive technique for biotechnology applications such as drug release, disease treatment and remote control of single cell functions, but poor conversion efficiencies have hindered practical applications so far. In this Letter, we demonstrate a significant increase in the efficiency of magnetic thermal induction by nanoparticles. We take advantage of the exchange coupling between a magnetically hard core and magnetically soft shell to tune the magnetic properties of the nanoparticle and maximize the specific loss power, which is a gauge of the conversion efficiency. The optimized core-shell magnetic nanoparticles have specific loss power values that are an order of magnitude larger than conventional iron-oxide nanoparticles. We also perform an antitumour study in mice, and find that the therapeutic efficacy of these nanoparticles is superior to that of a common anticancer drug.

Two-dimensional crystals, single sheets of layered materials, often show distinct properties desired for optoelectronic applications, such as larger and direct band gaps, valley- and spinorbit effects. Being atomically thin, the low amount of material is a bottleneck in photophysical and photochemical applications. Here, we propose the formation of stacks of two-dimensional crystals intercalated with small surfactant molecules. We show, using first principles calculations, that already the very short surfactant methyl amine electronically decouples the layers. We demonstrate the indirect-direct band gap transition characteristic for Group 6 transition metal dichalcogenides experimentally by observing the emergence of a strong photoluminescence signal for ethoxide-intercalated WSe2 and MoSe2 multilayered nanoparticles with lateral size of about 10 nm and beyond. The proposed hybrid materials offer the highest possible density of the two-dimensional crystals with electronic properties typical for monolayers. Variation of the surfactant's chemical potential allows fine-tuning of electronic properties and potentially elimination of trap states caused by defects.

Recently a memristor ( Chua, L. O. IEEE Trans. Circuit Theory 1971 , 18 , 507 ), the fourth fundamental passive circuit element, has been demonstrated as thin film device operations ( Strukov, D. B.; Snider, G. S.; Stewart, D. R.; Williams, R. S. Nature (London) 2008 , 453 , 80 ; Yang, J. J.; Pickett. M. D.; Li, X.; Ohlberg, D. A. A.; Stewart, D. R.; Williams, R. S. Nat. Nanotechnol. 2008 , 3 , 429 ). A new addition to the memristor family can be nanoparticle assemblies consisting of an infinite number of monodispersed, crystalline magnetite (Fe(3)O(4)) particles. Assembly of nanoparticles that have sizes below 10 nm, exhibits at room temperature a voltage-current hysteresis with an abrupt and large bipolar resistance switching (R(OFF)/R(ON) approximately 20). Interestingly, observed behavior could be interpreted by adopting an extended memristor model that combines both a time-dependent resistance and a time-dependent capacitance. We also observed that such behavior is not restricted to magnetites; it is a general property of nanoparticle assemblies as it was consistently observed in different types of spinel structured nanoparticles with different sizes and compositions. Further investigation into this new nanoassembly system will be of importance to the realization of the next generation nanodevices with potential advantages of simpler and inexpensive device fabrications.

The structure of nano-crystalline MnFe2O4 was determined and refined with electron powder diffraction data employing the Rietveld refinement technique. A nano-crystalline sample (with average crystal size of about 10.9 nm) was characterized by selected area electron diffraction in an energy-filtering transmission electron microscope operated at 120 kV. All reflection intensities were extracted from a digitized image plate using the program ELD and then used in the course of structure refinements employing the program FULLPROF for the Rietveld analysis. The final structure was refined in space group Fd-3m (# 227) with lattice parameters a=8.3413(7) A. The reliability factors of the refinement are RF=7.98% and RB=3.55%. Comparison of crystallographic data between electron powder diffraction data and reference data resulted in better agreement with ICSD-56121 rather than with ICSD-28517 which assumes an initial structure model.

Doped up: The incorporation of Zn(2+) dopants in tetrahedral sites leads to the successful magnetism tuning of spinel metal ferrite nanoparticles (see picture). (Zn(0.4)Mn(0.6))Fe(2)O(4) nanoparticles exhibit the highest magnetization value among the metal ferrite nanoparticles. Such high magnetism results in the largest MRI contrast effects (r2=860 mm(-1) s(-1)) reported to date and also huge hyperthermic effects.

Two-dimensional (2D) layered nanostructures have received increasing interest due to their unique nanoscale phenomena and their potential applications ranging from electronics and energy to catalysis. Recent investigation has revealed that laterally confined layered nanocrystals (LCLN) have remarkably enhanced electrochemical properties compared to their bulk counterparts owing to nanoscale characteristics that include large surface areas, finite lateral sizes, and enhanced open-edge morphologies. Among the variety of layered materials that have been described, tin sulfides are of particular interest because of their unique structural properties. SnS2 has a layered CdI2-type structure, composed of tin atoms sandwiched between two layers of hexagonally disposed closepacked sulfur atoms. The 2D layered characteristics of this substance are revealed in alkali metal intercalation phenomena, and by investigating anisotropy of properties such as electric and photoelectric conductivity. Owing to their large theoretical capacities for battery applications, bulk or micron sized tin-based materials have been extensively studied as possible alternatives for commercially available carbon electrodes. However, the main drawback of this system has been stemming from the large volume changes and accompanying sharp decrease in capacity that occur during electrochemical cycles. Aifantis et al. have reported that active sites with spherical and smaller volume fraction could improve electrochemical properties of anode materials from the view point of fracture mechanics. Other researchers also have reported that nanoscale tin sulfide-based materials would lead to an improvement in the cycling stability of these systems. Especially, layered SnS2 nanoplates with swelling tolerant hosting spaces and enhanced guest accessibility would provide enhanced diffusion for Li ion, and lead to the formation of Li-Sn alloy during the cycle, and improve the

We measured the size- and shape-dependent compressibility of the TiO2 anatase nanoparticles using monochromatic synchrotron X-ray powder diffraction and high-pressure diamond-anvil cell techniques....

Magnetic nanoparticles, which exhibit a variety of unique magnetic phenomena that are drastically different from those of their bulk counterparts, are garnering significant interest since these properties can be advantageous for utilization in a variety of applications ranging from storage media for magnetic memory devices to probes and vectors in the biomedical sciences. In this Account, we discuss the nanoscaling laws of magnetic nanoparticles including metals, metal ferrites, and metal alloys, while focusing on their size, shape, and composition effects. Their fundamental magnetic properties such as blocking temperature (Tb), spin life time (tau), coercivity (Hc), and susceptibility (chi) are strongly influenced by the nanoscaling laws, and as a result, these scaling relationships can be leveraged to control magnetism from the ferromagnetic to the superparamagnetic regimes. At the same time, they can be used in order to tune magnetic values including Hc, chi, and remanence (Mr). For example, life time of magnetic spin is directly related to the magnetic anisotropy energy (KuV) and also the size and volume of nanoparticles. The blocking temperature (Tb) changes from room temperature to 10 K as the size of cobalt nanoparticles is reduced from 13 to 2 nm. Similarly, H c is highly susceptible to the anisotropy of nanoparticles, while saturation magnetization is directly related to the canting effects of the disordered surface magnetic spins and follows a linear relationship upon plotting of ms (1/3) vs r(-1). Therefore, the nanoscaling laws of magnetic nanoparticles are important not only for understanding the behavior of existing materials but also for developing novel nanomaterials with superior properties. Since magnetic nanoparticles can be easily conjugated with biologically important constituents such as DNA, peptides, and antibodies, it is possible to construct versatile nano-bio hybrid particles, which simultaneously possess magnetic and biological functions for biomedical diagnostics and therapeutics. As demonstrated in this Account, nanoscaling laws for magnetic components are found to be critical to the design of optimized magnetic characteristics of hybrid nanoparticles and their enhanced applicability in the biomedical sciences including their utilizations as contrast enhancement agents for magnetic resonance imaging (MRI), ferromagnetic components for nano-bio hybrid structures, and translational vectors for magnetophoretic sensing of biological species. In particular, systematic modulation of saturation magnetization of nanoparticle probes is important to maximize MR contrast effects and magnetic separation of biological targets.

nanosheetcrystalsfromthe tungsten oxide rods. The reaction between the carbondisulfide and hexadecylamine generates in situ hydrogendisulfideandhexadecylisothiocyanateviaN-hexadecyldithio-carbamate as a transient species [Eq.(1); see also Figures S1and S2 in the Supporting Information], and subsequent

Nanoparticles have the potential to revolutionize current bio-medical diagnostic and therapeutic methods. For example, magnetic nanoparticles with unique superparamagnetism are emerging as next-generation probes for high performance magnetic resonance (MR) imaging. Their enhanced properties and nanoscale controllability in terms of size, composition, surface states, and magnetic spin structure have allowed for the highly sensitive and target-specific MR imaging of various biological systems including cancer detection, cell trafficking, and angiogenesis. On the other hand, viruses can be utilized as excellent delivery vehicles due to their facile cellular transfection and gene expression efficacies within their target cells. Such excellent properties of viruses offer promising prospects for gene therapy of genetic diseases and cancers, as well as for the genetic engineering of cells. Despite these prospects, a lack of understanding of their biological behaviors including in vivo migration, molecular recognition, gene delivery, and ultimate fate following their desired biofunctional applications limits their further development. There have been previous studies in the development of nanoparticle probing systems for viruses including virus-gold and virus-quantum dot nanoparticle systems. However, their utilization in the probing of viral gene delivery has not been investigated so far. Recently, Gd-based MR contrast agent-coated viruses were developed, but their functional behaviors including targetrecognition, cellular transfection, and gene delivery capabilities have not been demonstrated partly due to the intrinsically low sensitivity of Gd-based MR contrast agents. Our strategy is to hybridize the virus with magnetic nanoparticles into a single nanoparticle system with the dual-functional capabilities of target-specific MR imaging and gene delivery. Specifically, we fabricate hybrid nanoparticles of “enhanced green fluorescent protein (eGFP) promoter genecontaining adenovirus” and “manganese-doped magnetism engineered iron oxide (abbreviated as MnMEIO) nanoparticle”. As the viral gene delivery vector, we selected adenoviruses. Adenoviruses are known to be highly effective for transferring double-stranded DNAs to various cell types. Along with a gene delivery capability, adenoviruses possess targetspecificity to the cells with overexpression of Coxsackievirus B adenovirus receptor (CAR) which is known to facilitate the binding and intrusion of adenoviruses to the host cells. As the magnetic nanoparticle component we selected manganese-doped magnetism-engineered iron oxide (MnFe2O4, MnMEIO) nanoparticles, since it is known that MnMEIO exhibits exceptional MR contrast effects (R2 (=1/T2) value of 358 sec mM) and therefore is advantageous as probes for ultra-sensitive MR imaging. Briefly, the thermal reaction of manganese chloride (MnCl2) and iron tris(2,4-pentadionate) in hot organic solvents containing oleic acid and oleylamine capping molecules yielded hydrophobically capped MnMEIO nanoparticles. Their water-solubility and biocompatibility were attained by introducing 2,3-dimercaptosuccinic acids to the nanoparticle surface. Nanoparticles obtained were 12 nm with a high sizemonodispersity (r < 7%) and possessed single crystallinity, and a saturation magnetization value of 110 emu g (Mn+Fe). Hybridization of adenoviruses with MnMEIO nanoparticles was performed through a slight modification of a literature method, as follows. First, the capsid lysine residues of the adenoviruses were converted to maleimide groups by reacting them with sulfo-succinimidyl(4-N-maleimidomethyl)cyclohexane-1-carboxylate (sulfo-SMCC) cross-linkers. These groups were allowed to react with a large stoichiometric amount of MnMEIO nanoparticles, which resulted in the formation of adenovirus-MnMEIO hybrid nanoparticles by way of the nucleophilic addition of a surface thiol group of MnMEIO to the C O M M U N IC A IO N

Successful development of ultra-sensitive molecular imaging nanoprobes for the detection of targeted biological objects is a challenging task. Although magnetic nanoprobes have the potential to perform such a role, the results from probes that are currently available have been far from optimal. Here we used artificial engineering approaches to develop innovative magnetic nanoprobes, through a process that involved the systematic evaluation of the magnetic spin, size and type of spinel metal ferrites. These magnetism-engineered iron oxide (MEIO) nanoprobes, when conjugated with antibodies, showed enhanced magnetic resonance imaging (MRI) sensitivity for the detection of cancer markers compared with probes currently available. Also, we successfully visualized small tumors implanted in a mouse. Such high-performance, nanotechnology-based molecular probes could enhance the ability to visualize other biological events critical to diagnostics and therapeutics.

Since inorganic nanocrystals exhibit unique shape-dependent nanoscale properties and can be utilized as basic building blocks for futuristic nanodevices, a systematic study on the shape control of these nanocrystals remains an important subject in materials and physical chemistry. In this feature article, we overview the recent progress on the synthetic development of symmetry-controlled colloidal nanocrystals of semiconductor and metal oxide, which are prepared through nonhydrolytic chemical routes. We describe their shape-guiding processes and illustrate the detailed key factors controlling their growth by examining various case studies of zero-dimensional spheres and cubes, one-dimensional rods, and quasi multidimensional structures such as disks, multipods, and stars. Specifically, the crystalline phase of nucleating seeds, surface energy, kinetic vs thermodynamic growth, and selective adhesion processes of capping ligands are found to be most crucial for the determination of the nanocrystal shape.

In this paper, we describe an easy and reliable method for the production of patterned monolayers of Co nanoparticles. A two-dimensional monolayer of Co nanoparticles is fabricated by spreading a nanoparticle solution over an air-water interface and then transferring it to a hydrophobic substrate by using the Langmuir-Blodgett (LB) method. Transmission electron microscopy (TEM) was used to show that, with increasing surface pressure, the Co nanoparticles become well-organized into a Langmuir monolayer with a hexagonal close-packed structure. By controlling the pH of the subphase, it was found that a monolayer of Co nanoparticles with long-range order could be obtained. Further, by transferring the Langmuir monolayer onto a poly(dimethoxysilane) (PDMS) mold, the selective micropatterning of the Co nanoparticles could be achieved on a patterned electronic circuit. The electronic transport properties of the Co nanoparticles showed the ohmic I-V curve.

We present a new strategy to fabricate a monolayer assembly of Br-terminated Co nanoparticles on functionalized Si surfaces by using chemical covalent bonding and microcontact printing method. Self-assembled monolayers (SAMs) of the Co nanoparticles formed on the hydroxyl-terminated Si surface exhibit two-dimensional island networks with locally ordered arrays via covalent linkage between nanoparticles and surface. On the other hand, SAMs of the nanoparticles on the aminopropyl-terminated Si surface show an individual and random distribution over an entire surface. Furthermore, we have fabricated striped architectures of Co nanoparticles using a combination of microcontact printing and covalent linkage. Microcontact printing of octadecyltrichlorosilane and selective covalent linkage between nanoparticles and functionalized Si surfaces lead to a hybrid nanostructure with selectively assembled nanoparticles stripes on the patterned functionalized Si surfaces.