Ultrathin, High-Aspect-Ratio Bismuth Sulfohalide Nanowire Bundles for Solution-Processed Flexible Photodetectors.

In this study, a novel synthesis of ultrathin, highly uniform colloidal bismuth sulfohalide (BiSX where X = Cl, Br, I) nanowires (NWs) and NW bundles (NBs) for room-temperature and solution-processed flexible photodetectors are presented. High-aspect-ratio bismuth sulfobromide (BiSBr) NWs are synthesized via a heat-up method using bismuth bromide and elemental S as precursors and 1-dodecanethiol as a solvent. Bundling of the BiSBr NWs occurs upon the addition of 1-octadecene as a co-solvent. The morphologies of the BiSBr NBs are easily tailored from sheaf-like structures to spherulite nanostructures by changing the solvent ratio. The optical bandgaps are modulated from 1.91 (BiSCl) and 1.88 eV (BiSBr) to 1.53 eV (BiSI) by changing the halide compositions. The optical bandgap of the ultrathin BiSBr NWs and NBs exhibits blueshift, whose origin is investigated through density functional theory-based first-principles calculations. Visible-light photodetectors are fabricated using BiSBr NWs and NBs via solution-based deposition followed by solid-state ligand exchanges. High photo-responsivities and external quantum efficiencies (EQE) are obtained for BiSBr NW and NB films even under strain, which offer a unique opportunity for the application of the novel BiSX NWs and NBs in flexible and environmentally friendly optoelectronic devices.

Defect Engineering of Metal Halide Perovskite Nanocrystals via Spontaneous Diffusion of Ag Nanocrystals.

Perovskite nanocrystals (NCs) have emerged as a promising building block for the fabrication of optic-/optoelectronic-/electronic devices owing to their superior characteristics, such as high absorption coefficient, rapid ion mobilities, and tunable energy levels. However, their low structural stability and poor surface passivation have restricted their application to next-generation devices. Herein, a drug delivery system (DDS)-inspired post-treatment strategy is reported for improving their structural stability by doping of Ag into CsPbBr3 (CPB) perovskite NCs; delivery to damaged sites can promote their structural recovery slowly and uniformly, averting the permanent loss of their intrinsic characteristics. Ag NCs are designed through surface-chemistry tuning and structural engineering to enable their circulation in CPB NC dispersions, followed by their delivery to the CPB NC surface, defect-site recovery, and defect prevention. The perovskite-structure healing process through the DDS-type process (with Ag NCs as the drug) is analyzed by a combination of theoretical calculations (with density functional theory) and experimental analyses. The proposed DDS-inspired healing strategy significantly enhances the optical properties and stability of perovskite NCs, enabling the fabrication of white light-emitting diodes.

Biofunctional Inorganic Layered Double Hydroxide Nanohybrid Enhances Immunotherapeutic Effect on Atopic Dermatitis Treatment.

Atopic dermatitis (AD) is a widespread, recurrent, and chronic inflammatory skin condition that imposes a major burden on patients. Conventional treatments, such as corticosteroids, are associated with various side effects, underscoring the need for innovative therapeutic approaches. In this study, the possibility of using indole-3-acetic acid-loaded layered double hydroxides (IAA-LDHs) is evaluated as a novel treatment for AD. IAA is an auxin-class plant hormone with antioxidant and anti-inflammatory effects. Following the synthesis of IAA-LDH nanohybrids, their ability to induce M2-like macrophage polarization in macrophages obtained from mouse bone marrow is assessed. The antioxidant activity of IAA-LDH is quantified by assessing the decrease in intracellular reactive oxygen species levels. The anti-inflammatory and anti-atopic characteristics of IAA-LDH are evaluated in a mouse model of AD by examining the cutaneous tissues, immunological organs, and cells. The findings suggest that IAA-LDH has great therapeutic potential as a candidate for AD treatment based on its in vitro and in vivo modulation of AD immunology, enhancement of macrophage polarization, and antioxidant activity. This inorganic drug delivery technology represents a promising new avenue for the development of safe and effective AD treatments.

Colloidal inorganic nano- and microparticles for passive daytime radiative cooling.

Compared to traditional cooling systems, radiative cooling (RC) is a promising cooling strategy in terms of reducing energy consumption enormously and avoiding severe environmental issues. Radiative cooling materials (RCMs) reduce the temperature of objects without using an external energy supply by dissipating thermal energy via infrared (IR) radiation into the cold outer space through the atmospheric window. Therefore, RC has a great potential for various applications, such as energy-saving buildings, vehicles, water harvesting, solar cells, and personal thermal management. Herein, we review the recent progress in the applications of inorganic nanoparticles (NPs) and microparticles (MPs) as RCMs and provide insights for further development of RC technology. Particle-based RCMs have tremendous potential owing to the ease of engineering their optical and physical properties, as well as processibility for facile, inexpensive, and large area deposition. The optical and physical properties of inorganic NPs and MPs can be tuned easily by changing their size, shape, composition, and crystals structures. This feature allows particle-based RCMs to fulfill requirements pertaining to passive daytime radiative cooling (PDRC), which requires high reflectivity in the solar spectrum and high emissivity within the atmospheric window. By adjusting the structures and compositions of colloidal inorganic particles, they can be utilized to design a thermal radiator with a selective emission spectrum at wavelengths of 8-13 µm, which is preferable for PDRC. In addition, colloidal particles can exhibit high reflectivity in the solar spectrum through Mie-scattering, which can be further engineered by modifying the compositions and structures of colloidal particles. Recent advances in PDRC that utilize inorganic NPs and MPs are summarized and discussed together with various materials, structural designs, and optical properties. Subsequently, we discuss the integration of functional NPs to achieve functional RCMs. We describe various approaches to the design of colored RCMs including structural colors, plasmonics, and luminescent wavelength conversion. In addition, we further describe experimental approaches to realize self-adaptive RC by incorporating phase-change materials and to fabricate multifunctional RC devices by using a combination of functional NPs and MPs.

Nanoparticle-Based Chimeric Antigen Receptor Therapy for Cancer Immunotherapy.

Adoptive cell therapy with chimeric antigen receptor (CAR)-engineered T cells (CAR-Ts) has emerged as an innovative immunotherapy for hematological cancer treatment. However, the limited effect on solid tumors, complex processes, and excessive manufacturing costs remain as limitations of CAR-T therapy. Nanotechnology provides an alternative to the conventional CAR-T therapy. Owing to their unique physicochemical properties, nanoparticles can not only serve as a delivery platform for drugs but also target specific cells. Nanoparticle-based CAR therapy can be applied not only to T cells but also to CAR-natural killer and CAR-macrophage, compensating for some of their limitations. This review focuses on the introduction of nanoparticle-based advanced CAR immune cell therapy and future perspectives on immune cell reprogramming.

Dynamically tunable multicolor emissions from zero-dimensional Cs3LnCl6 (Ln: europium and terbium) nanocrystals with wide color gamut.

This study demonstrates dynamically tunable multicolor emissions from a single component, zero-dimensional (0-D) cesium europium chloride (Cs3EuCl6) and cesium terbium chloride (Cs3TbCl6) nanocrystals (NCs). Highly uniform colloidal Cs3EuCl6 and Cs3TbCl6 NCs are synthesized via the heating-up method. Excitation-wavelength-dependent multicolor emissions from Cs3EuCl6 and Cs3TbCl6 NCs are observed. Under excitation of 330-400 nm, both NCs exhibit blue photoluminescence (PL). Under wavelengths shorter than 330 nm, characteristic red and green emissions are observed from Cs3EuCl6 and Cs3TbCl6, respectively, owing to the atomic emissions from the f-orbitals in trivalent europium (Eu3+) and terbium (Tb3+) ions. Cs3EuCl6 and Cs3TbCl6 NCs exhibit broadband excitation spectra and enhanced absorption properties. Particularly, Cs3EuCl6 NCs exhibit a very narrow full-width at half-maximum in both blue and red PL and no overlap between the two spectra. The photophysical properties of these NCs are further investigated to understand the multicolor PL origins by time-resolved and temperature-dependent PL measurements. Finally, the potential applications of Cs3EuCl6 and Cs3TbCl6 NCs as anti-counterfeiting inks for high-level security are demonstrated. Given their broadband excitation with enhanced absorption properties and dynamically tunable colors with a wide color gamut, Cs3EuCl6 and Cs3TbCl6 NCs have great potential as novel multicolor NC emitters for many emerging applications.

Designing a self-classifying smart device with sensor, display, and radiative cooling functions via spectrum-selective response.

This paper presents a self-classifying smart device that intelligently differentiates and operates three functions: electroluminescence display, ultraviolet light sensor, and thermal management via radiative cooling. The optical and electrical properties of the materials and structures are designed to achieve a spectrum-selective response, which enables the integration of the aforementioned functions into one device without any noise or interference. Spectrum-selective materials that absorb, emit, and radiate light with ultraviolet to mid-infrared wavelengths and device structures designed to prevent interference are achieved by using thin metal films, dielectric layers, and nanocrystals. The designed self-classifying smart device exhibits bright blue light emission upon current supply (display), green light emission upon exposure to UV light (sensor), and radiative cooling (thermal management). Furthermore, a smart device and house system with a display, UV light sensor, and radiative cooling performance was demonstrated. The findings of this study open new avenues for device integration in next-generation wearable device fabrication.

Single-step acid-catalyzed synthesis of luminescent colloidal organosilica nanobeads.

We present a single-step, room-temperature synthesis of fluorescent organosilica nanobeads (FOS NBs). The FOS NBs were synthesized under aqueous conditions using (3-aminopropyl)triethoxysilane (APTES) as the silicon source in the presence of L-ascorbic acid (L-AA). In the APTES/L-AA/water ternary phase, the hydrolysis and condensation reaction of APTES occurred under acidic conditions to form spherical FOS NBs with an average diameter of 426.8 nm. FOS NBs exhibit excellent colloidal stability in aqueous media. The formation of FOS NBs was complete within a 10 min reaction time, which indicates potential for large-scale mass-production synthesis of luminescent colloidal NBs. The FOS NBs exhibited blue photoluminescence (PL) under UV excitation in the absence of an additional high temperature calcination process or with the incorporation of any fluorophores. This phenomenon is attributed to the presence of carbon-containing defects, which act as luminescent centers formed by the reaction between amino groups in the APTES and L-ascorbic acid reductant. Finally, the results of a cytotoxicity test and cellular uptake experiments revealed that the FOS NBs showed potential as optical contrast agents for bioimaging.

Multilevel Absorbers via the Integration of Undoped and Tungsten-Doped Multilayered Vanadium Dioxide Thin Films.

Reconfigurable light absorbers have attracted much attention by providing additional optical responses and expanding the number of degrees of freedom in security applications. Fabry-Pèrot absorbers based on phase change materials with tunable properties can be implemented over large scales without the need for additional steps such as lithography, while exhibiting reconfigurable optical responses. However, a fundamental limitation of widely used phase change materials such as vanadium dioxide and germanium-antimony-tellurium-based chalcogenide glasses is that they have only two distinct phases; therefore, only two different states of optical properties are available. Here, we experimentally demonstrate active multilevel absorbers that are tuned by controlling the external temperature. This is produced by creating large-scale lithography-free multilayer structures with both undoped and tungsten-doped solution-processed monoclinic-phase vanadium dioxide thin films. The doping of vanadium dioxide with tungsten allows for the modulation of the phase-transition temperature, which results in an extra degree of freedom and therefore an additional step for the tunable properties. The proposed multilevel absorber is designed and characterized both numerically and experimentally. Such large-scale multilevel tunable absorbers realized with nanoparticle-based solution fabrication techniques are expected to open the way for advanced thermo-optical cryptographic devices based on tunable reflective coloration and near-infrared absorption.

Recent Advances in Fabrication of Flexible, Thermochromic Vanadium Dioxide Films for Smart Windows.

Monoclinic-phase VO2 (VO2(M)) has been extensively studied for use in energy-saving smart windows owing to its reversible insulator-metal transition property. At the critical temperature (Tc = 68 °C), the insulating VO2(M) (space group P21/c) is transformed into metallic rutile VO2 (VO2(R) space group P42/mnm). VO2(M) exhibits high transmittance in the near-infrared (NIR) wavelength; however, the NIR transmittance decreases significantly after phase transition into VO2(R) at a higher Tc, which obstructs the infrared radiation in the solar spectrum and aids in managing the indoor temperature without requiring an external power supply. Recently, the fabrication of flexible thermochromic VO2(M) thin films has also attracted considerable attention. These flexible films exhibit considerable potential for practical applications because they can be promptly applied to windows in existing buildings and easily integrated into curved surfaces, such as windshields and other automotive windows. Furthermore, flexible VO2(M) thin films fabricated on microscales are potentially applicable in optical actuators and switches. However, most of the existing fabrication methods of phase-pure VO2(M) thin films involve chamber-based deposition, which typically require a high-temperature deposition or calcination process. In this case, flexible polymer substrates cannot be used owing to the low-thermal-resistance condition in the process, which limits the utilization of flexible smart windows in several emerging applications. In this review, we focus on recent advances in the fabrication methods of flexible thermochromic VO2(M) thin films using vacuum deposition methods and solution-based processes and discuss the optical properties of these flexible VO2(M) thin films for potential applications in energy-saving smart windows and several other emerging technologies.

Facile Sulfurization under Ambient Condition with Na2S to Fabricate Nanostructured Copper Sulfide.

The sulfurization reaction was investigated as a promising fabrication method for preparing metal sulfide nanomaterials. Traditional sulfurization processes generally require high vacuum systems, high reaction temperatures, and toxic chemicals, utilizing complicated procedures with poor composition and morphology controllability. Herein, a facile method is reported for synthesizing nanostructured copper sulfide using a sulfurization reaction with Na2S at room temperature under non-vacuum conditions. Moreover, we demonstrate that the morphology, composition, and optical properties of nanostructured copper sulfides could be controlled by the Na2S solution concentration and the reaction time. Nanostructured copper sulfides were synthesized in nanospheres, nanoplates, and nanoplate-based complex morphologies with various oxidation states. Furthermore, by comparing the optical properties of nanostructured copper sulfides with different oxidation states, we determined that reflectivity in the near infrared (NIR) region decreases with increasing oxidation states. These results reveal that the Na2S solution concentration and reaction time are key factors for designing nanostructured copper sulfides, providing new insights for synthesis methods of metal sulfide nanomaterials.

N,N-Dimethylformamide-Assisted Shape Evolution of Highly Uniform and Shape-Pure Colloidal Copper Nanocrystals.

In this paper, the N,N-dimethylformamide (DMF)-assisted shape evolution of highly uniform and shape-pure copper nanocrystals (Cu NCs) is presented for the first time. Colloidal Cu NCs are synthesized via the disproportionation reaction of copper (I) bromide in the presence of a non-polar solvent mixture. It is observed that the shape of Cu NCs is systematically controlled by the addition of different amounts of DMF to the reaction mixture in high-temperature reaction conditions while maintaining a high size uniformity and shape purity. With increasing amount of DMF in the reaction mixture, the morphology of the Cu NCs change from a cube enclosed by six {100} facets, to a sphere with mixed surface facets, and finally, to an octahedron enclosed by eight {111} facets. The origin of this shape evolution is understood via first-principles density functional theory calculations, which allows the study of the change in the relative surface stability according to surface-coordinating adsorbates. Further, the shape-dependent plasmonic properties are systematically investigated with highly uniform and ligand-exchanged colloidal Cu NCs dispersed in acetonitrile. Finally, the facet-dependent electrocatalytic activities of the shape-controlled Cu NCs are investigated to reveal the activities of the highly uniform and shape-pure Cu NCs in the methanol oxidation reaction.

Sub-100-nm Nearly Monodisperse n-Paraffin/PMMA Phase Change Nanobeads.

In this study, we demonstrate the colloidal synthesis of nearly monodisperse, sub-100-nm phase change material (PCM) nanobeads with an organic n-paraffin core and poly(methylmethacrylate) (PMMA) shell. PCM nanobeads are synthesized via emulsion polymerization using ammonium persulfate as an initiator and sodium dodecylbenzenesulfonate as a surfactant. The highly uniform n-paraffin/PMMA PCM nanobeads are sub-100 nm in size and exhibit superior colloidal stability. Furthermore, the n-paraffin/PMMA PCM nanobeads exhibit reversible phase transition behaviors during the n-paraffin melting and solidification processes. During the solidification process, multiple peaks with relatively reduced phase change temperatures are observed, which are related to the phase transition of n-paraffin in the confined structure of the PMMA nanobeads. The phase change temperatures are further tailored by changing the carbon length of n-paraffin while maintaining the size uniformity of the PCM nanobeads. Sub-100-nm-sized and nearly monodisperse PCM nanobeads can be potentially utilized in thermal energy storage and drug delivery because of their high colloidal stability and solution processability.

Post-synthetic oriented attachment of CsPbBr3 perovskite nanocrystal building blocks: from first principle calculation to experimental demonstration of size and dimensionality (0D/1D/2D).

Post-synthesis engineering methods that employ oriented attachment to precisely control the size and dimensionality (0D/1D/2D) of as-synthesized CsPbBr3 nanocrystals (NCs) are demonstrated. We investigated the chemical effects of the properties of polar solvents, including their immiscibility, polarity, and boiling point, on the surfaces of NCs, as well as their effect on the structural and optical properties of NCs. Appropriate exploitation of the solvent properties made it possible to use a polar solvent to mildly affect the NCs indirectly such that they discarded their ligands and became attached to proximal NCs without being destroyed. Based on our observations, we developed a method whereby a solution of the NCs in a non-polar solvent is mixed with a polar solvent to form an immiscible phase to induce epitaxial growth of CsPbBr3 NCs. The method enables the size of NCs to be easily regulated from 5 to 50 nm by controlling the engineering time. Taking advantage of the minimal effect of a mild solvent, we also developed a self-assembly method that operates at the liquid-air interface to systematically control the dimensionality. At this interface, the NCs self-assemble in the horizontal direction and grow into micron-sized, single-crystalline, defect-free nanowires (1D) and nanoplates (2D) via oriented attachment. Finally, we discuss the origin of the non-destructive oriented attachment phenomenon and the surface chemistry of a perovskite NC using density functional theory (DFT) simulations and a proposed model system.

Heating-up synthesis of cesium bismuth bromide perovskite nanocrystals with tailored composition, morphology, and optical properties.

This study represents the heating-up synthesis of lead-free cesium bismuth bromide perovskite nanocrystals (NCs). CsBr and BiBr3 precursors are used to synthesize uniform and phase-pure cesium bismuth bromide NCs, and the reaction is performed via an injection-free, heating-up method in the presence of a solvent mixture with a high boiling point. The size and composition of cesium bismuth bromide NCs are readily controlled by changing the reaction time, temperature, and amount of surfactant added to the reaction mixture. Upon heating, sequential phase evolution occurs, resulting in the formation of kinetically stable BiOBr in the early reaction stages, which transformed into the thermodynamically stable Cs3BiBr6 and Cs3Bi2Br9 with an increase in either the reaction time or the reaction temperature. Furthermore, the absorption and photoluminescence properties of Cs3BiBr6 and Cs3Bi2Br9 NCs are characterized to investigate their composition-dependent optical properties. This work provides the potential to synthesize various types of lead-free perovskite NCs by tailoring the size and compositions.

Colloidal Self-Assembly of Inorganic Nanocrystals into Superlattice Thin-Films and Multiscale Nanostructures.

The self-assembly of colloidal inorganic nanocrystals (NCs) offers tremendous potential for the design of solution-processed multi-functional inorganic thin-films or nanostructures. To date, the self-assembly of various inorganic NCs, such as plasmonic metal, metal oxide, quantum dots, magnetics, and dielectrics, are reported to form single, binary, and even ternary superlattices with long-range orientational and positional order over a large area. In addition, the controlled coupling between NC building blocks in the highly ordered superlattices gives rise to novel collective properties, providing unique optical, magnetic, electronic, and catalytic properties. In this review, we introduce the self-assembly of inorganic NCs and the experimental process to form single and multicomponent superlattices, and we also describe the fabrication of multiscale NC superlattices with anisotropic NC building blocks, thin-film patterning, and the supracrystal formation of superlattice structures.

Tailoring cubic and dodecagonal quasicrystalline mesophases of mesoporous organosilica nanoparticles and core/shell structure.

Herein, the synthesis of mesoporous organosilica nanoparticles with cubic and dodecagonal quasicrystalline mesophases is reported. Mesoporous nanoparticles are synthesized by base-catalyzed hydrolysis and condensation reactions of silane-based monomers in the presence of hexadecyltrimethylammonium bromide (CTAB), which is used as a structure-directing agent to form the mesostructures. Cubic orders in the mesophases are formed using tetraethoxysilane monomers, and the mesophase is tuned to the dodecagonal quasicrystalline order by using binary monomers including tetraethoxysilane and dimethyldiethoxysilane. The size of the quasicrystalline-phase organosilica is tailored by changing the amount of base catalyst used. Additionally, we obtained well-defined core/shell structures with quasicrystalline ordered mesoporous organosilica. Furthermore, we investigate the cytotoxicity of mesoporous organisilica nanoparticles using a CCK-8 assay to demonstrate that our NPs have a potential for the utilization as biomedical applications. These novel findings could guide the formation of mesophase structures with quasicrystalline order in silica-based mesoporous nanoparticles.

Nanobiosensing Platforms for Real-Time and Non-Invasive Monitoring of Stem Cell Pluripotency and Differentiation.

Breakthroughs in the biomedical and regenerative therapy fields have led to the influential ability of stem cells to differentiate into specific types of cells that enable the replacement of injured tissues/organs in the human body. Non-destructive identification of stem cell differentiation is highly necessary to avoid losses of differentiated cells, because most of the techniques generally used as confirmation tools for the successful differentiation of stem cells can result in valuable cells becoming irrecoverable. Regarding this issue, recent studies reported that both Raman spectroscopy and electrochemical sensing possess excellent characteristics for monitoring the behavior of stem cells, including differentiation. In this review, we focus on numerous studies that have investigated the detection of stem cell pluripotency and differentiation in non-invasive and non-destructive manner, mainly by using the Raman and electrochemical methods. Through this review, we present information that could provide scientific or technical motivation to employ or further develop these two techniques for stem cell research and its application.

The dendritic effect and magnetic permeability in dendron coated nickel and manganese zinc ferrite nanoparticles.

The collective magnetic properties of nanoparticle (NP) solid films are greatly affected by inter-particle dipole-dipole interactions and therefore the proximity of the neighboring particles. In this study, a series of dendritic ligands (generations 0 to 3, G0-G3) have been designed and used to cover the surface of magnetic NPs to control the spacings between the NP components in single lattices. The dendrons of different generations introduced here were based on the 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) scaffold and equipped with an appropriate surface binding group at one end and several fatty acid segments at the other extremity. The surface of the NPs was then modified by partial ligand exchange between the primary stabilizing surfactants and the new dendritic wedges. It was shown that this strategy permitted very precise tuning of inter-particle spacings in the range of 2.9-5.0 nm. As expected, the increase in the inter-particle spacings reduced the dipole-dipole interactions between magnetic NPs and therefore allowed changes in their magnetic permeability. The dendron size and inter-particle distance dependence was studied to reveal the dendritic effect and identify the optimal geometry and generation.