N, S-Codoped Carbon Dots-Based Reusable Solvatochromic Organogel Sensors for Detecting Organic Solvents.

The visualization and analysis of organic solvents using fluorescent sensors are crucial, given their association with environmental safety and human health. Conventional fluorescent sensors are typically single-use sensors and they often require sophisticated measurement instruments, which limits their practical and diverse applications. Herein, we develop solvatochromic nitrogen and sulfur codoped carbon dots (NS-CDs)-based organogel sensors that display color changes in response to different solvents. NS-CDs are synthesized using a solvothermal method to produce monodispersed particles with exceptional solubility in various organic solvents. NS-CDs exhibit distinct photoluminescent emission spectra that correlate with the solvent polarity, and the solvent-dependent photoluminescent mechanism is investigated in detail. To highlight the potential application of solvatochromic NS-CDs, portable and low-cost NS-CDs-embedded organogel sensors are fabricated. These sensors exhibit highly robust solvatochromic performance despite repeated solvent switches, thus ensuring consistent and reliable measurements in practical applications. This study provides valuable insights into the solvatochromism of carbon dots and opens up new avenues for designing real-time organic solvent sensing platforms.

Straightforward Manufacturing of 3D-Printed Metallic Structures toward Customized Electrical Components.

Metalizing three-dimensional (3D)-printed polymers has been spotlighted in the field of manufacturing high-end and customized electrical components. Conventional metalization approaches that rely on the electroless plating (ELP) process typically require the use of noble metal-based catalysts or involve multistep processes, limiting their practical applications. Herein, we propose a straightforward yet effective approach to manufacture 3D-printed polymers with conductive metal layers through a thiol-mediated ELP process without involving an additional catalytic activation process. A photocurable ternary resin based on thiol-ene-acrylate monomers was precisely designed to induce excess thiol moieties on the surface of 3D-printed structures. These exposed thiol moieties served as active sites for metal ion complexion via strong metal-sulfur bonds, allowing the deposition of metal layers on the 3D-printed polymers through the ELP. Diverse metal layers, including Cu, Ag, and NiP, could be deposited onto virtually any 3D-printed structures with high uniformity and adhesion stability. To highlight the potential application of our approach, we fabricated fully functional glucose sensors through the deposition of the Cu layer on 3D-printed electrode models, and these sensors displayed excellent nonenzymatic glucose sensing performance. The proposed approach offers great insights for designing functional metallic structures and opens up new avenues for manufacturing lightweight, customized electrical components.

Bismuth-Rich Co/Ni Bimetallic Metal-Organic Frameworks as Photocatalysts toward Efficient Removal of Organic Contaminants under Environmental Conditions.

Active photocatalysts with an efficiency of 99% were prepared for the degradation of the industrial dye, methylene blue (MB), under visible light irradiation. These photocatalysts comprised Co/Ni-metal-organic frameworks (MOFs), to which bismuth oxyiodide (BiOI) was added as a filler to prepare Co/Ni-MOF@BiOI composites. The composites exhibited remarkable photocatalytic degradation of MB in aqueous solutions. The effects of various parameters, including the pH, reaction time, catalyst dose, and MB concentration, on the photocatalytic activity of the prepared catalysts were also evaluated. We believe that these composites are promising photocatalysts for the removal of MB from aqueous solutions under visible light.

Selective engineering of oxygen-containing functional groups using the alkyl ligand oleylamine for revealing the luminescence mechanism of graphene oxide quantum dots.

Oxygen-containing functional groups such as epoxy, hydroxyl, carboxylic, and carboxyl groups have a great influence on the luminescence properties of graphene oxide quantum dots (GOQDs). Understanding their roles is essential for the design and optimization of GOQD performance. Herein, we investigate the effect of epoxide functional groups in GOQDs on the luminescence mechanism through passivation of the epoxide functional groups using the alkyl ligand oleylamine. Luminescence in the as-synthesized GOQDs has two separate origins: intrinsic states derived from localized sp2 carbon subdomains and extrinsic states formed by oxygen-functional groups. When the oleylamine ligand is conjugated on the GOQDs, intrinsic PL emission from the localized sp2 carbon subdomains decreases. This is discussed in detail, based on optical characterization and first-principles density functional theory calculations, which reveal that the role of the epoxide functional groups is to form localized sp2 carbon subdomains emitting intrinsic PL. To the best of our knowledge, this is the first investigation of the role of epoxide functional groups on the luminescence mechanism in GOQDs.

Surface engineering of graphene quantum dots and their applications as efficient surfactants.

The surface properties of graphene quantum dots (GQDs) control their dispersion and location within the matrices of organic molecules and polymers, thereby determining various properties of the hybrid materials. Herein, we developed a facile, one-step method for achieving systematic control of the surface properties of highly fluorescent GQDs. The surfaces of the as-synthesized hydrophilic GQDs were modified precisely depending on the number of grafted hydrophobic hexylamine. The geometry of the modified GQDs was envisioned by conducting simulations using density functional theory. In stark contrast to the pristine GQDs, the surface-modified GQDs can effectively stabilize oil-in-water Pickering emulsions and submicron-sized colloidal particles in mini-emulsion polymerization. These versatile GQD surfactants were also employed in liquid-solid systems; we demonstrated their use for tailoring the dispersion of graphite in methanol. Finally, the particles produced by the GQD surfactants were fluorescent due to luminescence of the GQDs, which offers great potential for various applications, including fluorescent sensors and imaging.

Anisotropically functionalized carbon nanotube array based hygroscopic scaffolds.

Creating ordered microstructures with hydrophobic and hydrophilic moieties that enable the collection and storage of small water droplets from the atmosphere, mimicking structures that exist in insects, such as the Stenocara beetle, which live in environments with limited amounts of water. Inspired by this approach, vertically aligned multiwalled carbon nanotube forests (NTFs) are asymmetrically end-functionalized to create hygroscopic scaffolds for water harvesting and storage from atmospheric air. One side of the NTF is made hydrophilic, which captures water from the atmosphere, and the other side is made superhydrophobic, which prevents water from escaping and the forest from collapsing. To understand how water penetrates into the NTF, the fundamentals of water/NTF surface interaction are discussed.

Efficient colorimetric pH sensor based on responsive polymer-quantum dot integrated graphene oxide.

In this paper, we report the development of a versatile platform for a highly efficient and stable graphene oxide (GO)-based optical sensor that exhibits distinctive ratiometric color responses. To demonstrate the applicability of the platform, we fabricated a colorimetric, GO-based pH sensor that responds to a wide range of pH changes. Our sensing system is based on responsive polymer and quantum dot (QD) hybrids integrated on a single GO sheet (MQD-GO), with the GO providing an excellent signal-to-noise ratio and high dispersion stability in water. The photoluminescence emissions of the blue and orange color-emitting QDs (BQDs and OQDs) in MQD-GO can be controlled independently by different pH-responsive linkers of poly(acrylic acid) (PAA) (pKa=4.5) and poly(2-vinylpyridine) (P2VP) (pKa=3.0) that can tune the efficiencies of Förster resonance energy transfer from the BQDs to the GO and from the OQDs to the GO, respectively. As a result, the color of MQD-GO changes from orange to near-white to blue over a wide range of pH values. The detailed mechanism of the pH-dependent response of the MQD-GO sensor was elucidated by measurements of time-resolved fluorescence and dynamic light scattering. Furthermore, the MQD-GO sensor showed excellent reversibility and high dispersion stability in pure water, indicating that our system is an ideal platform for biological and environmental applications. Our colorimetric GO-based optical sensor can be expanded easily to various other multifunctional, GO-based sensors by using alternate stimuli-responsive polymers.

Highly Luminescent Polymer Particles Driven by Thermally Reduced Graphene Quantum Dot Surfactants.

We report the use of highly luminescent graphene quantum dots (GQDs) as efficient surfactants to produce Pickering emulsions and novel polymer particles. To generate the GQD surfactants, the surface properties of 10 nm sized, non-reduced GQDs (nGQDs), which have strong hydrophilicity, were synthesized and modified in a systematic manner by the thermal reduction of oxygen-containing groups at different treatment times. In stark contrast to the behavior of the nGQDs, thermally reduced GQDs (rGQDs) can produce highly stable Pickering emulsions of oil-in-water systems. To demonstrate the versatility of the rGQD surfactants, they were applied in a mini-emulsion polymerization system that requires nanosized surfactants to synthesize submicron-sized polystyrene particles. In addition, the use of rGQD surfactants can be extended to generating block copolymer particles with controlled nanostructures. Particularly, the polymer particles were highly luminescent, a characteristic produced by the highly fluorescent GQD surfactants, which has great potential for various applications, including bioimaging, drug delivery, and optoelectronic devices. To the best of our knowledge, this is the first report in which nanosized GQDs were used as surfactants.

Covalently interconnected three-dimensional graphene oxide solids.

The creation of three-dimensionally engineered nanoporous architectures via covalently interconnected nanoscale building blocks remains one of the fundamental challenges in nanotechnology. Here we report the synthesis of ordered, stacked macroscopic three-dimensional (3D) solid scaffolds of graphene oxide (GO) fabricated via chemical cross-linking of two-dimensional GO building blocks. The resulting 3D GO network solids form highly porous interconnected structures, and the controlled reduction of these structures leads to formation of 3D conductive graphene scaffolds. These 3D architectures show promise for potential applications such as gas storage; CO2 gas adsorption measurements carried out under ambient conditions show high sorption capacity, demonstrating the possibility of creating new functional carbon solids starting with two-dimensional carbon layers.

Efficient temperature sensing platform based on fluorescent block copolymer-functionalized graphene oxide.

Efficient temperature-sensing platform was demonstrated using temperature-responsive, fluorescent P7AC-b-PNIPAM-b-PSN3 block copolymer-anchored graphene oxide sheets (FGO). FGO exhibited extraordinary stability in water and showed fast optical on-off switching behavior in response to temperature change.

'Click' preparation of CuPt nanorod-anchored graphene oxide as a catalyst in water.

In this paper, a simple and powerful method of producing nanoparticle-anchored graphene oxide (GO) composites using a 'click' reaction is demonstrated. This method affords a facile means of anchoring of nanoparticles with various shapes and sizes on the GO. CuPt nanorods with controlled size, aspect ratio (from 1 to 11), and uniformity are synthesized. Transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy measurements are made to monitor the formation and characterize the properties of the CuPt nanorod-grafted GO composites. Their catalytic properties in the water phase are investigated using an o-phenylenediamine oxidation reaction. The results of this study clearly demonstrate that nonpolar CuPt nanorods immobilized on GO can function as a catalyst in an aqueous solution and that GO can be used as a catalytic nanorod support.

A case of delayed oculocardiac reflex induced by an intraorbital foreign body.

A 56-year-old male presented with a history of left periorbital pain, nausea, vomiting, dyspnea, sweating, and pallor. His left eye was injured by a bomb explosion approximately 40 years ago. Evisceration was performed. There were no cardiopulmonary and gastroenterological findings except mild bradycardia (54/min). CT evaluation revealed a 4-cm-sized, sharp, metallic, intraorbital foreign body in the left orbit. After the removal of the foreign body, the symptoms completely resolved with a normal heart rate (69/min). The authors present a case of delayed oculocardiac reflex induced by an old intraorbital foreign body.