Modulation of Nano-superstructures and Their Optical Properties.

Self-assembly, which enables spontaneous arrangement of objects, is of particular importance for nanomaterials in both fundamental and applied research fields. Multiple types of nanoparticle superstructures have been successfully built in highly controllable and efficient manners through balancing the nanoscale interactions. Uniform and proper arrangement of nanoparticles inside the assembled superstructures is essential to exhibit their constant, reliable, and homogeneous functionalities. To be specific, the long-range ordered superlattices not only succeed with their building blocks' intrinsic property, but also, more importantly, can display collective properties that are absent both in individual nanoparticles and in their bulk states. One of the most attractive aspects of nanomaterials is their exceptional optical properties that have tremendous application potential in multidisciplinary fields. In this regard, constructing the superstructures from optical nano units like noble metal nanostructures, semiconductor nanoparticles, or hybrid nanomaterials is critical for attaining the unique optical properties and exploring their practical applications in multiple fields including photonics, optoelectronics, optical sensing, photocatalysis, etc. In this Account, we provide guidelines for self-assembly strategies to fabricate the superstructures and discuss the optical properties that the superstructures display. In the first part, we categorize and discuss the key factors that strongly affect the self-assembly process and determine the configurational and integral quality of the superstructures. On one hand, the diversity and designability of nanoparticles offer the intrinsic complexity of the building blocks, including geometry, size, composition, and surface ligand, which efficiently tailors the assembly process and superstructure configuration. On the other hand, multiple factors originating from the introduction of extrinsic features are recognized to facilitate the metastable or dynamic self-assembly process. Such extrinsic features include both matter like DNA origami, peptides, small molecules, etc. and nonmatter involved with electric fields, magnetic fields, light, temperature, etc. In the second part, we introduce the state-of the art progress on the collective optical performances of the assembled superstructures, including (1) chiral optics, such as circular dichroism and circularly polarized luminescence, (2) plasmonic properties and related applications, and (3) luminescence related optics and their applications. Finally, we summarize the existing problems and main challenges briefly, and some future directions of this field are proposed. We envision that, with deep understanding of the assembly mechanism and development of the synthetic and surface chemistry, rational modulation of nanoassemblies will be the trend of this field, which is beneficial to achieve the emerging collective performances and create new generation devices with advanced functions.

Electrochemical Investigation of Porosity in Core-Shell Magnetoplasmonic Nanoparticles.

Porous core-shell nanoparticles (NPs) have emerged as a promising material for broad ranges of applications in catalysts, material chemistry, biology, and optical sensors. Using a typical Ag core-Fe3O4 shell NP, a.k.a., magnetoplasmonic (MagPlas) NP, two porous shell models were prepared: i.e., Ag@Fe3O4 NPs and its SiO2-covered NPs (Ag@Fe3O4@SiO2). We suggested using cyclic voltammetry (CV) to provide unprecedented insight into the porosity of the core-shell NPs caused by the applied potential, resulting in the selective redox activities of the core and porous shell components of Ag@Fe3O4 NPs and Ag@Fe3O4@SiO2 NPs at different cycles of CV. The porous and nonporous core-shell nanostructures were qualitatively and quantitatively determined by the electrochemical method. The ratio of the oxidation current peak (µA) of Ag to Ag+ in the porous shell to that in the SiO2 coated (nonporous) shell was 400:3.2. The suggested approach and theoretical background could be extended to other types of multicomponent NP complexes.

Chirality of Fingerprints: Pattern- and Curvature-Induced Emerging Chiroptical Properties of Elastomeric Grating Meta-Skin.

Fingerprint-inspired elastomeric grating meta-skin (EGMS) is herein fabricated to investigate the chirality of fingerprints. The EGMS is made by a facile nanoimprinting method with a diffraction grating as a template using polydimethylsiloxane, followed by gold deposition. The chirality of the surface is caused by symmetry breaking, induced by the pattern (P) and curvature (T). Furthermore, the chiroptical properties of EGMS are reconfigurable through the control of the skew angle (θ), which is the angle between P and T. The chiroptical properties of a fingerprint are also shown and interpreted in this perspective. On the basis of the results, we suggest the strategy to impart chirality on the surface, which is reconfigurable by controlling P and T. It will be a useful method to produce chirality in membranes, thin films, metasurfaces, and 2D nanomaterials, as well as advance biometric recognition.

Rapid Assembly of Magnetoplasmonic Photonic Arrays for Brilliant, Noniridescent, and Stimuli-Responsive Structural Colors.

There are usually trade-offs between maximizing the color saturation and brightness and minimizing the angle-dependent effect in structural colors. Here, a magnetic field-induced assembly for the rapid formation of scalable, uniform amorphous photonic arrays (APAs) featuring unique structural colors is demonstrated. The magnetic field plays a fundamental role in photonic film formation, making this assembly technology versatile for developing structural color patterns on arbitrary substrates. The synergistic combination of surface plasmonic resonance of the Ag core and broadband light absorption of high refractive index (RI) Fe3 O4 shell in hybrid magnetoplasmonic nanoparticles (MagPlas NPs) enables breaking the trade-offs to produce brilliant, noniridescent structural colors with high tunability and responsiveness. These features enable the fabrication of various types of highly sensitive and reliable colorimetric sensors for naked-eye detection without sophisticated instruments. Furthermore, large-scale structural color patterns are effortlessly achieved, demonstrating the high potential of the present approach for full-spectrum displays, active coatings, and rewritable papers.

Plasmonic Enhancement of Chiroptical Property in Enantiomers Using a Helical Array of Magnetoplasmonic Nanoparticles for Ultrasensitive Chiral Recognition.

Recognition of enantiomeric molecules is essential in pharmaceutical and biomedical applications. In this Article, a novel approach is introduced to monitor chiral molecules via a helical magnetic field (hB), where chiral-inactive magnetoplasmonic nanoparticles (MagPlas NPs, Ag@Fe3O4 core-shell NPs) are assembled into helical nanochain structures to be chiral-active. An in-house generator of hB-induced chiral NP assembly, that is, a plasmonic chirality enhancer (PCE), is newly fabricated to enhance the circular dichroism (CD) signals from chiral plasmonic interaction of the helical nanochain assembly with circularly polarized light, reaching a limit of detection (LOD) of 10-10 M, a 1000-fold enhancement as compared to that of conventional CD spectrometry. These enhancements were successfully observed from enantiomeric molecules, oligomers, polymers, and drugs. Computational simulation studies also proved that total chiroptical properties of helical plasmonic chains could be readily changed by modifying the chiral structure of the analytes. The proposed PCE has the potential to be used as an advanced tool for qualitative and quantitative recognition of chiral materials, enabling further application in pharmaceutical and biomedical sensing and imaging.

Emission-tunable probes using terbium(III)-doped self-activated luminescent hydroxyapatite for in vitro bioimaging.

Lanthanide ion (Ln3+)-doped nanoscale hydroxyapatites (nHAp) with tunable luminescence have attracted increasing attention due to their potential applications as useful biomedical tools (e.g., imaging and clinical therapy). In this study, we reported that doping Terbium (III) ions (Tb3+) in self-activated luminescent nHAp via a facile hydrothermal reaction, using trisodium citrate (Cit3-), generates unique emission-tunable probes known as Cit/Tb-nHAp. The morphology, crystal phase, and luminescence properties of these Cit/Tb-nHAp probes are studied in detail. Moreover, the results demonstrate that the luminescence of self-activated nHAp originates from the carbon dots trapped within the nHAp crystals, in which partial energy transfer occurs from carbon dots (CDs) to Tb3+. The color tunability is successfully achieved by regulating the addition of Cit3-. Biocompatibility study indicates that when co-cultured with C6 glioma cells in vitro for 3 days, ≤800 ppm Cit/Tb-nHAp is not cytotoxic for C6 glioma cells. We also present in vitro data showing efficient cytoplasmic localization of transferrin conjugated Cit/Tb-nHAp into C6 glioma cells by fluorescence cell imaging. We have successfully engineered Cit/Tb-nHAp, a promising biocompatible agent for future in vitro and in vivo fluorescence bioimaging.

Contralateral spreading of substances following intratympanic nanoparticle-conjugated gentamicin injection in a rat model.

This study was performed to investigate the Eustachian tube as a potential route for contralateral spreading following intratympanic nanoparticle (NP)-conjugated gentamicin injection in a rat model. Sprague-Dawley rats were divided into three groups and substances were injected in the right ear: group 1 (fluorescent magnetic nanoparticles [F-MNPs], n = 4), group 2 (F-MNP-conjugated gentamicin [F-MNP@GM], n = 2), and control group (no injections, n = 2). T2-weighted sequences corresponding to the regions of interest at 1, 2, and 3 h after intratympanic injection were evaluated, along with immunostaining fluorescence of both side cochlea. The heterogeneous signal intensity of F-MNPs and F-MNP@GM on T2-weighted images, observed in the ipsilateral tympanum, was also detected in the contralateral tympanum in 4 out of 6 rats, recapitulating fluorescent nanoparticles in the contralateral cochlear hair cells. Computational simulations demonstrate the contralateral spreading of particles by gravity force following intratympanic injection in a rat model. The diffusion rate of the contralateral spreading relies on the sizes and surface charges of particles. Collectively, the Eustachian tube could be a route for contralateral spreading following intratympanic injection. Caution should be taken when using the contralateral ear as a control study investigating inner-ear drug delivery through the transtympanic approach.

Helical Magnetic Field-Induced Real-Time Plasmonic Chirality Modulation.

The astrophysical phenomenon of mimetic helical magnetic field (hB)-assisted self-assembly is herein introduced to build helical superstructures that display chiroptical properties. As a building block, magnetoplasmonic (MagPlas) Ag@Fe3O4 core-shell nanoparticles are used to guide plasmonic Ag nanoparticles onto a helical magnetic flux. The chirality of the assembled helical structures and tailored circular dichroism are successfully tuned in real time, and the handedness of the assembled structures is dynamically switched by the hB at the millisecond level, which is at least 6000-fold faster than other template-assisted methods. The peak position of circular dichroism can be reconfigured by altering the plasmonic resonance or coupling by controlling the size of the Ag core and magnetic flux density. The hB-induced chirality modulation represents a method to control the polarization state of light at the nexus of plasmonics, magnetic self-assembly, colloidal science, liquid crystals, and chirality. It presents active and dynamic chiral assemblies of magnetoplasmonic nanomaterials, enabling further practical applications in optical devices.

Magnetic Layer-by-Layer Assembly: From Linear Plasmonic Polymers to Oligomers.

One-dimensional nanostructures with controllable aspect ratios are essential for a wide range of applications. An approach for magnetic superparticle (SP) assembly over large areas (55 mm × 25 mm) is introduced via co-assistance of electrostatic and magnetic fields, so-called magnetic layer-by-layer assembly, on an arbitrary hydrophilic substrate within minutes. The SP structures [diameter (d) = 120-350 nm] of Fe3O4 or Ag@Fe3O4 composites composed of hundreds of magnetite nanocrystals (d = 10-20 nm) are used as colloidal monomers to fabricate arrays of high aspect ratio (up to 102) linear nanochains, viz. colloidal polymers, where thermal disturbances were minimized. The arrays of colloidal polymers exhibit strong optical polarization effects owing to their geometrical anisotropy, which can be used as a simple optical filter. Furthermore, by using the binary colloidal mixture of different magnetic colloids, including different sized Fe3O4 and magnetoplasmonic Ag@Fe3O4, low aspect ratio (2-15) colloidal chains, viz. magnetic/plasmonic oligomers, with tunable lengths were fabricated, affording a facile but an effective approach to modulate the optical properties of the chains. The scalable fabrication of well-aligned, linear colloidal polymers and oligomers opens up appealing opportunities for the development of sensors, subwavelength waveguides, optical tweezers, and enhanced solar harvesting devices.

Synthesis and formation mechanism of bone mineral, whitlockite nanocrystals in tri-solvent system.

Whitlockite (WH, Ca18Mg2(HPO4)2(PO4)12) is the second most abundant bone mineral and has attracted attention as one of the novel bone regenerative materials. It has proven to enhance growth and promote osteogenesis of stem cells. However, investigating the mechanism of formation of pure phase WH nanocrystals remains a challenge. In this study, we introduced an interesting synthesis approach of WH nanocrystals using a tri-solvent system for the solid-liquid-solution (SLS) process. The ratio of precursor and reaction solvent composition was optimized to generate WH nanocrystals with tunable size, morphology (nanoplates, nanospheres), and surface properties (hydrophobic, hydrophilic), which is impossible to achieve using the traditional precipitation method. Molecular dynamics (MD) simulations revealed that the growth direction of nanoplates is highly related to the surfactant and its binding affinity. Finite element method (FEM) simulations elucidated that the ratio of ethanol/water plays an important role in defining the crystallinity and morphology of WH. In this study, we demonstrated that the cell proliferation of human bone marrow-derived mesenchymal stem cells (hBMSCs) is enhanced upon treatment with WH. The results of quantitative real-time polymerase chain reaction (qPCR) revealed that WH can positively accelerate the osteogenic differentiation in hBMSCs. The as-synthesized WH has a great potential in the future to be used in osteogenic tissue engineering. This study opens a new horizon for the synthesis and application of WH.

Magnetic-Field-Induced Electrochemical Performance of a Porous Magnetoplasmonic Ag@Fe3O4 Nanoassembly.

The Lorentz or Kelvin force generated by an externally applied magnetic field may introduce additional convection of the electrolyte near the working electrode and consequently produces magnetocurrent (MC), which can be attributed to the magnetohydrodynamic (MHD) flow and an extra electrochemical reaction. A magnetoplasmonic (MagPlas) composite of metallic and superparamagnetic nanoparticles (NPs) with a permanent dipole or magnetic moment have additional degree or order, which corresponds to directional correlation to electric and magnetic dipoles. In particular, an ordered self-assembly may boost up the MHD flow on a collectively reactive surface, leading to remarkable electrochemical performance. In this article, a proof-of-concept work explores the effect of the magnetic field on the electrocatalytic activity of the oxygen reduction reaction (ORR) as well as [Fe(CN)6]3-/4- redox probes using a precisely controlled three-dimensional (3D) nanostructure of a silver core and a porous magnetic shell (Ag@Fe3O4) assembly. Then, the reduction current was carefully monitored in the presence of a magnetic field (B, up to 380 mT), resulting in an extraordinary increment of reduction current (IR) of [Fe(CN)6]3- by 23% and a 1.13-fold high ORR efficiency owing to the additional magnetic field (Bin) from the 3D magnetoplasmonic nanoassembly. The computational simulation explained the plausible mechanism of current enhancement from the MagPlas nanoassembly. From our experimental and computational studies, it is probable that the 3D MagPlas nanoassembly is a unique and efficient catalyst under a low external magnetic field, which would be useful for further biomedical and energy-related applications.

Whitlockite Granules on Bone Regeneration in Defect of Rat Calvaria.

Whitlockite (WH; Ca18Mg2(HPO4)2(PO4)12) is a calcium phosphate based ceramic that contains magnesium ions. As the second most abundant mineral in living bone, WH occupies 25-35 wt % of the inorganic portion of human bone. Compared to hydroxyapatite (HAp, Ca10(PO4)6(OH)2), WH possesses better mechanical properties, faster resorbability, and promotion behavior on the osteogenesis. In this article, we introduced a fabrication method of interconnected porous WH granules through vacuum filtration, followed by sintering treatment based on the thermal stability of WH synthesized using the tri-solvent system. This study presents a histological, radiological, and immunohistochemical evaluation of the bone healing potential of these WH granules in a 5 mm diameter calvarial bone defect in rats. The histological evaluation shows no inflammation or foreign body reaction in the WH group. The WH group displays newly formed bone at the same thickness as the original bone. On the contrary, bone formation is not observed in the nontreated (NT) group. Besides, immunohistochemistry (IHC) confirmed that WH granules promoted bone regeneration with the significantly higher expression of bone morphogenetic proteins-2 (BMP-2), alkaline phosphatase (ALP), osteopontin (OPN), and osteocalcin (OCN) compared to the NT group without the addition of exogenous cells or growth factors. These results suggest that WH has excellent potential for application in bone tissue regeneration.

In vivo feasibility test using transparent carbon nanotube-coated polydimethylsiloxane sheet at brain tissue and sciatic nerve.

Carbon nanotubes, with their unique and outstanding properties, such as strong mechanical strength and high electrical conductivity, have become very popular for the repair of tissues, particularly for those requiring electrical stimuli. Polydimethylsiloxane (PDMS)-based elastomers have been used in a wide range of biomedical applications because of their optical transparency, physiological inertness, blood compatibility, non-toxicity, and gas permeability. In present study, most of artificial nerve guidance conduits (ANGCs) are not transparent. It is hard to confirm the position of two stumps of damaged nerve during nerve surgery and the conduits must be cut open again to observe regenerative nerves after surgery. Thus, a novel preparation method was utilized to produce a transparent sheet using PDMS and multiwalled carbon nanotubes (MWNTs) via printing transfer method. Characterization of the PDMS/MWNT (PM) sheets revealed their unique physicochemical properties, such as superior mechanical strength, a certain degree of electrical conductivity, and high transparency. Characterization of the in vitro and in vivo usability was evaluated. PM sheets showed high biocompatibility and adhesive ability. In vivo feasibility tests of rat brain tissue and sciatic nerve revealed the high transparency of PM sheets, suggesting that it can be used in the further development of ANGCs. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1736-1745, 2017.

In Vivo Study of Mastoid Obliteration Using Hydroxyapatite-Chitosan Patch.

Many artificial materials have been used for mastoid cavity obliteration in canal wall down tympanomastoidectomy. Among the artificial materials, hydroxyapatite is most popular material for mastoid cavity obliteration. Hydroxyapatite is biostable and osteoconductive, but it has poor mechanical properties, especially brittleness. To overcome the limitation, hydroxyapatite has been combined with natural chitosan polymer, which is biocompatible and flexible, to produce a hydroxyapatite-chitosan patch via a sublimation-assisted compression process. We evaluated this hydroxyapatite-chitosan patch for tympanic cavity obliteration in a rat model by comparing it with sham surgery group, bone cement and homologous cartilage. The cavity obliteration ratio and new bone formation in tympanic bullae were determined by computed tomography, histological analysis, field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Comparing the hydroxyapatite-chitosan patch with homologous cartilage and bone cement, the tympanic cavity obliteration ratio was superior in the patch group (40.96 ± 7.79%) than other groups (32.23 ± 6.93% and 16.07 ± 6.10%). Even the hydroxyapatite-chitosan patch made no difference in new bone formation ratio ranging from 27.92 ± 11.08 to 29.17 ± 10.96% with other groups. In conclusion, hydroxyapatite-chitosan patch for mastoid cavity obliteration showed easy handling, flexibility, favorable osteogenesis and biostability.

In vivo study on the biocompatibility of chitosan-hydroxyapatite film depending on degree of deacetylation.

Chitosan, produced from chitin, is one of the polymers with promising applications in various fields. However, despite diverse research studies conducted on its biocompatibility, its uses are still limited. The main reason is the degree of deacetylation (DOD), which represents the proportion of deacetylated units in the polymer and is directly correlated with its biocompatibility property. In this article, the in vivo biocompatibility of three chitosan-hydroxyapatite composite films composed of chitosan with different DOD values was investigated by traditional biological protocols and novel optical spectroscopic analyses. The DOD of the chitosan obtained from three different manufacturers was estimated and calculated by Raman spectroscopy, Fourier transform infrared spectroscopy, and proton nuclear magnetic resonance spectroscopy. The chitosan with the higher DOD induced a higher incidence of inflammation in skin cells. The amino group density, biodegradability, and crystallinity of chitosan are the three possible factors that need to be considered when determining the biocompatibility of the films for in vivo application, as they led to complicated biological results, resulting in either better or worse inflammation even when using chitosan products with the same DOD. This basic study on the relationship between the DOD and inflammation is valuable for the development of further chitosan-based researches. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1637-1645, 2017.