Synthesis,Separation, and Characterization of Small and Highly Fluorescent Nitrogen‐Doped Carbon NanoDots

A facile bottom‐up approach to carbon nanodots (CNDs) is reported, using a microwave‐assisted procedure under controlled conditions. The as‐prepared nitrogen‐doped CNDs (NCNDs) show narrow size‐distribution, abundant surface traps and functional groups, resulting in tunable fluorescent emission and excellent solubility in water. Moreover, we present a general method for the separation of NCNDs by low‐pressure size‐exclusion chromatography, leading to an even narrower size distribution, different surface composition, and optical properties. They display among the smallest size and the highest FLQYs reported so far. ¹³C‐enriched starting materials produced N¹³CNDs suitable for thorough NMR studies, which gave useful information on their molecular structure. Moreover, they can be easily functionalized and can be used as water‐soluble carriers. This work provides an avenue to size‐ and surface‐controllable and structurally defined NCNDs for applications in areas such as optoelectronics, biomedicine, and bioimaging.     

Multifunctional Nitrogen‐Doped Carbon Nanodots for Photoluminescence,Sensor, and Visible‐Light‐Induced H2 Production

Herein, multifunctional N‐doped carbon nanodots (NCNDs) were prepared through the one‐step hydrothermal treatment of yeast. Results show that the NCNDs can be used as a new photocatalyst to drive the water‐splitting reaction under UV light. Moreover, the NCNDs can efficiently catalyze the hydrogen evolution reaction. Under visible‐light irradiation, Eosin Y‐sensitized NCNDs exhibit excellent activity for hydrogen evolution. The hydrogen evolution rate of NCNDs (without any modification and co‐catalyst) reaches 107.1 μmol h^?1 (2142 μmol g^?1 h^?1). When Pt is loaded on the NCNDs, the hydrogen evolution rate reaches 491.2 μmol h^?1 (9824 μmol g^?1 h^?1) under visible‐light irradiation. In addition, the NCNDs show excellent fluorescent properties and can be applied as a fluorescent probe for the sensitive and selective detection of Fe³⁺.     

Amine‐Rich Nitrogen‐Doped Carbon Nanodots as a Platform for Self‐Enhancing Electrochemiluminescence

Amine‐rich nitrogen‐doped carbon nanodots (NCNDs) have been successfully used as co‐reactant in electrochemiluminescence (ECL) processes. Primary or tertiary amino groups on NCNDs have been studied as co‐reactant sites for Ru(bpy)₃²⁺ ECL, showing their eligibility as powerful alternatives to tripropylamine (TPrA). We also report the synthesis and ECL behavior of a new covalently linked hybrid of NCNDs and Ru(bpy)₃²⁺. Notably, the NCNDs in the hybrid act both as carrier for ECL labels and as co‐reactant for ECL generation. As a result, the hybrid shows a higher ECL emission as compared to the combination of the individual components, suggesting the self‐enhancing ECL of the ruthenium complex due to an intramolecular electron transfer process.     

Intramolecular Hydrogen Bonds Quench Photoluminescence and Enhance Photocatalytic Activity of Carbon Nanodots

Understanding the photoluminescence (PL) and photocatalytic properties of carbon nanodots (CNDs) induced by environmental factors such as pH through surface groups is significantly important to rationally tune the emission and photodriven catalysis of CNDs. Through adjusting the pH of an aqueous solution of CNDs, it was found that the PL of CNDs prepared by ultrasonic treatment of glucose is strongly quenched at pH 1 because of the formation of intramolecular hydrogen bonds among the oxygen‐containing surface groups. The position of the strongest PL peak and its corresponding excitation wavelength strongly depend on the surface groups. The origins of the blue and green emissions of CNDs are closely related to the carboxyl and hydroxyl groups, respectively. The deprotonated COO^? and CO^? groups weaken the PL peak of the CNDs and shift it to the red. CNDs alone exhibit photocatalytic activity towards degradation of Rhodamine B at different pH values under UV irradiation. The photocatalytic activity of the CNDs is the highest at pH 1 because of the strong intramolecular hydrogen bonds formed among the oxygen‐containing groups.     

Ultrasmall green-emitting carbon nanodots with 80% photoluminescence quantum yield for lysosome imaging

Carbon-based fluorescent nanomaterials have gained much attention in recent years. In this work, green-photoluminescent carbon nanodots (CNDs; also termed carbon dots, CDs) with amine termination were synthesized via the hydrothermal treatment of amine-containing spermine and rose bengal (RB) molecules. The CNDs have an ultrasmall size of ∼2.2 nm and present bright photoluminescence with a high quantum yield of ∼80% which is possibly attributed to the loss of halogen atoms (Cl and I) during the hydrothermal reaction. Different from most CNDs which have multicolor fluorescence emission, the as-prepared CNDs possess excitation-independent emission property, which can avoid fluorescence overlap with other fluorescent dyes. Moreover, the weakly basic amine-terminated surface endows the CNDs with the acidotropic effect. As a result, the CNDs can accumulate in the acidic lysosomes after cellular internalization and can serve as a favorable agent for lysosome imaging. Besides, the CNDs have a negligible impact on the lysosomal morphology even after 48 h incubation and exhibit excellent biocompatibility in the used cell models.     

Porphyrin Antennas on Carbon Nanodots: Excited State Energy and Electron Transduction

We report the synthesis and electron donor–acceptor features of a novel nanohybrid, in which the light‐harvesting and electron‐donating properties of a meso ‐tetraarylporphyrin (TArP) are combined with the electron‐accepting features of nitrogen‐doped carbon nanodots (NCNDs). In particular, in an ultrafast process (>10¹² s⁻¹), visible‐light excitation transforms the strongly quenched porphyrin singlet excited states into short‐lived (225 ps) charge‐separated states. On the other hand, ultraviolet light excitation triggers a non‐resolvable transduction of singlet excited state energy from the NCNDs to the porphyrins, followed by the same charge separation observed upon visible light excitation.     

Green Synthesis of Red‐Emitting Carbon Nanodots as a Novel “Turn‐on” Nanothermometer in Living Cells

Temperature measurements in biology and medical diagnostics, along with sensitive temperature probing of living cells, is of great importance; however, it still faces significant challenges. Herein, a novel “turn‐on” carbon‐dot‐based fluorescent nanothermometry device for spatially resolved temperature measurements in living cells is presented. The carbon nanodots (CNDs) are prepared by a green microwave‐assisted method and exhibit red fluorescence (λ_em=615 nm) with high quantum yields (15 %). Then, an on–off fluorescent probe is prepared for detecting glutathione (GSH) based on aggregation‐induced fluorescence quenching. Interestingly, the quenched fluorescence could be recovered by increasing temperature and the CNDs–GSH mixture could behave as an off–on fluorescent probe for temperature. Thus, red‐emitting CNDs can be utilized for “turn‐on” fluorescent nanothermometry through the fluorescence quenching and recovery processes, respectively. We employ MC3T3‐E1 cells as an example model to demonstrate the red‐emitting CNDs can function as “non‐contact” tools for the accurate measurement of temperature and its gradient inside a living cell.     

Carbon Nanodots as Electrocatalysts towards the Oxygen Reduction Reaction

Electrocatalysts perform a key role in increasing efficiency of the oxygen reduction reaction (ORR) and as a result, efforts have been made by the scientific community to develop novel and cheap materials that have the capability to exhibit low ORR overpotentials and allow the reaction to occur via a 4 electron pathway, thereby mimicking as close as possible to traditionally utilised platinum. In that context, two different types of carbon nanodots (CNDs) with amide (CND‐CONH₂) and carboxylic (CND‐COOH) surface groups, have herein been fabricated and shown to exhibit excellent electrocatalytic activity towards the ORR in acid and basic media (0.1 M H₂SO₄ and 0.1 M KOH). CND surface modified carbon screen‐printed electrodes allow for a facile electrode modification and enabling the study of the CNDs electrocatalytic activity towards the ORR. CND‐COOH modified SPEs are found to exhibit improved ORR peak current and reduced overpotential by 21.9 % and 26.3 %, respectively compared to bare/unmodified SPEs. Additionally, 424 μg cm⁻² CND‐COOH modified SPEs in oxygenated 0.1 M KOH are found to facilitate the ORR via a near optimal 4 (3.8) electron ORR pathway. The CNDs also exhibited excellent long‐term stability and tolerance with no degradation being observed in the achievable current with the ORR current returning to the baseline level within 100 seconds of exposure to a 1.5 M solution of methanol. In summary, the CND‐COOH could be utilised as a cathodic electrode for PEMFCs offering greater stability than a commercial Pt electrode.     

A Highly Stable Zeotype Mesoporous Zirconium Metal–Organic Framework with Ultralarge Pores

Through topological rationalization, a zeotype mesoporous Zr‐containing metal–organic framework (MOF), namely PCN‐777, has been designed and synthesized. PCN‐777 exhibits the largest cage size of 3.8 nm and the highest pore volume of 2.8 cm³ g^?1 among reported Zr‐MOFs. Moreover, PCN‐777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN‐777 and different guests can be varied to realize efficient immobilization.     

Unusual Ultra‐Hydrophilic,Porous Carbon Cuboids for Atmospheric‐Water Capture

There is significant interest in high‐performance materials that can directly and efficiently capture water vapor, particularly from air. Herein, we report a class of novel porous carbon cuboids with unusual ultra‐hydrophilic properties, over which the synergistic effects between surface heterogeneity and micropore architecture is maximized, leading to the best atmospheric water‐capture performance among porous carbons to date, with a water capacity of up to 9.82 mmol g^?1 at P/P₀=0.2 and 25 °C (20 % relative humidity or 6000 ppm). Benefiting from properties, such as defined morphology, narrow pore size distribution, and high heterogeneity, this series of functional carbons may serve as model materials for fundamental research on carbon chemistry and the advance of new types of materials for water‐vapor capture as well as other applications requiring combined highly hydrophilic surface chemistry, developed hierarchical porosity, and excellent stability.     

From a Molecular 2Fe‐2Se Precursor to a Highly Efficient Iron Diselenide Electrocatalyst for Overall Water Splitting

A highly active FeSe₂ electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe‐2Se precursor. The as‐synthesized FeSe₂ was electrophoretically deposited on nickel foam and applied to the oxygen and hydrogen evolution reactions (OER and HER, respectively) in alkaline media. When used as an oxygen‐evolution electrode, a low 245 mV overpotential was achieved at a current density of 10 mA cm⁻², representing outstanding catalytic activity and stability because of Fe(OH)₂/FeOOH active sites formed at the surface of FeSe₂. Remarkably, the system is also favorable for the HER. Moreover, an overall water‐splitting setup was fabricated using a two‐electrode cell, which displayed a low cell voltage and high stability. In summary, the first iron selenide material is reported that can be used as a bifunctional electrocatalyst for the OER and HER, as well as overall water splitting.     

Synthetization and Functionalization of Natural,Polymer, and Quantum-Based Carbon Nanodots and Their Application in Biomedicine

Carbon nanodots (CNDs) are a developing branch of nanomaterials and nanoscience. This has generated much more interest in the field and class of biomedicine science by way of unique particular properties, such as high stability, great photoluminescence, easy green synthesis, and simple surface modification. Numerous applications, such as bioimaging, biosensing, and treatment, have made use of CNDs. This review describes the most recent developments in CND research and talks about major changes in the understanding of CNDs and their prospects as biomedical tools. The importance of this work lies in the ability of CNDs to overcome many of the limitations associated with traditional materials used in biomedicine, such as toxicity, poor biocompatibility, and limited functionality. Furthermore, the use of CNDs as drug carriers, imaging agents, and sensors has shown great potential in improving the diagnosis and treatment of various diseases. The novelty of this work lies in the diversity of approaches used in the synthesis and functionalization of CNDs, and the unique properties of CNDs that make them versatile tools for biomedicine. In particular, the ability to tune the size, shape, and surface chemistry of CNDs allows for the creation of tailored materials with specific biomedical applications. The review also discusses the challenges and future prospects of CNDs in biomedicine, including the need for standardization and optimization of CND synthesis, functionalization, and characterization protocols.     

Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization

We prepared core–shell polymer–silsesquioxane hybrid microcapsules from cage‐like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core–shell latex particles were achieved. The polymer latex particles were subsequently transformed into well‐defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High‐resolution TEM and nitrogen adsorption–desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2–3 nm. The nanospheres exhibited large surface areas (up to 486 m² g^?1) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g^?1). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one‐step template‐free method for various applications.     

Upconverting Carbon Nanodots from Ethylenediaminetetraacetic Acid (EDTA) as Near-Infrared Activated Phototheranostic Agents

This work describes the synthesis of nitrogen-doped carbon nanodots (CNDs) synthesized from ethylenediaminetetraacetic acid (EDTA) as a precursor and their application as luminescent agents with a dual-mode theranostic role as near-infrared (NIR) triggered imaging and photodynamic therapy agents. Interestingly, these fluorescent CNDs are more rapidly and selectively internalized by tumor cells and exhibit very limited cytotoxicity until remotely activated with a NIR illumination source. These CNDs are excellent candidates for phototheranostic purposes, for example, simultaneous imaging and therapy can be carried out on cancer cells by using their luminescent properties and the in situ generation of reactive oxidative species (ROS) upon excitation in the NIR range. In the presence of CNDs, NIR remote activation induces the in vitro killing of U251MG cells. Through the use of flow imaging cytometry, we have been able to successfully map and quantify the different types of cell deaths induced by the presence of intracellular superoxide anions ( ^. O₂⁻) and hydrogen peroxide (H₂O₂) ROS generated in situ upon NIR irradiation.     

Combination of Optimization and Metalated‐Ligand Exchange: An Effective Approach to Functionalize UiO‐66(Zr) MOFs for CO2 Separation

The strategy to functionalize water‐stable metal–organic frameworks (MOFs) in order to improve their CO₂ uptake capacities for efficient CO₂ separation remains limited and challenging. We herein present an effective approach to functionalize a prominent water‐stable MOF, UiO‐66(Zr), by a combination of optimization and metalated‐ligand exchange. In particular, by systematic optimization, we have successfully obtained UiO‐66(Zr) of the highest BET surface area reported so far (1730 m² g^?1). Moreover, it shows a hybrid Type I/IV N₂ isotherm at 77 K and a mesopore size of 3.9 nm for the first time. The UiO‐66 MOF underwent a metalated‐ligand‐exchange (MLE) process to yield a series of new UiO‐66‐type MOFs, among which UiO‐66‐(COONa)₂‐EX and UiO‐66‐(COOLi)₄‐EX MOFs have both enhanced CO₂ working capacity and IAST CO₂/N₂ selectivity. Our approach has thus suggested an alternative design to achieve water‐stable MOFs with high crystallinity and gas uptake for efficient CO₂ separation.     

Preparation,properties, and application of polypropylene micro/nanofiber membranes

Nanofiber membranes have huge potential applications in many areas due to their unique properties. However, the thermoplastic micro/nanofiber membranes were rarely reported. In this paper, polypropylene (PP) nanofibers were prepared by melt extrusion of immiscible blends of PP, cellulose acetate butyrate (CAB), and subsequent removal of the CAB matrix. The wet‐laid application was used to make PP nanofiber membranes and PP‐g‐MAH/nonwoven micro/nanofiber membrane. The properties of membranes including morphology, apparent density, porosity, contact‐angle, pore size distribution, and water flux were characterized. The results showed that the consequent membranes were provided with optimistic porosity and pore size distribution. Moreover, they were all with high pure water fluxes, which were superior to that of PP microporous membrane. They performed an excellent separation performance of TiO₂ suspension and dyeing wastewater. The work revealed this method could be an efficient one to make thermoplastic polymer micro/nanofiber membranes, and they would have a brilliant potential application for water treatment. Copyright © 2010 John Wiley & Sons, Ltd.     

Constant Electricity Generation in Nanostructured Silicon by Evaporation‐Driven Water Flow

Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation‐induced water flow inside nanochannels. The device can yield direct current with a short‐circuit current density of over 55 μA cm^?2, which is three orders larger than a previously reported analogous device (approximately 40 nA cm^?2). Moreover, it exhibits a constant output power density of over 6 μW cm^?2 and an open‐circuit voltage of up to 400 mV. Our finding may pave a way for developing energy‐harvesting devices from ubiquitous evaporation‐driven internal water flow in nature with semiconductor material of silicon.     

Synthesis and Characterization of Nanostructured Fe3O4 Micron‐Spheres and Their Application in Removing Toxic Cr Ions from Polluted Water

We present a simple and effective method for the synthesis of nanostructured Fe₃O₄ micron‐spheres (NFMSs) by annealing hydrothermally formed FeCO₃ spheres in argon. The phase structure, particle size, and magnetic properties of the product have been characterized by X‐ray diffraction (XRD), Fourier‐transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and by means of a superconducting quantum interference device (SQUID). The results have shown that the as‐obtained NFMSs have a diameter of about 5 μm and are composed of nanometer‐sized porous lamellae. The NFMSs have a large specific surface area (135.9 m² g^?1), reductive Fe²⁺ incorporated into their structure, and intense magnetic properties. These properties suggest that NFMSs have potential application in removing toxic Cr⁶⁺ ions from polluted water. At 25 °C, each gram of NFMSs product can remove 43.48 mg of Cr⁶⁺ ions, as compared to just 10.2 mg for nanometer‐sized Fe₃O₄ and 1.89 mg for micron‐sized Fe₃O₄. The enhanced removal performance can be ascribed to the structural features. Moreover, the Cr⁶⁺ ion removal capacity of the NFMSs can reach up to 71.2 mg g^?1 at 50 °C. The influencing parameters in the removal of Cr⁶⁺ ions, such as contact time, pH, and temperature, have been evaluated. The Cr⁶⁺‐removal mechanism has been investigated. We have found that the NFMSs product not only serves as an effective adsorbent to remove toxic Cr⁶⁺ ions from polluted water, but also as an effective reductant in reducing the adsorbed toxic Cr⁶⁺ ions to much less toxic Cr³⁺ through the Fe²⁺ incorporated into its structure.     

Siloxane surfactants in polymer nanoparticles formulation

Carbohydrate‐modified cyclosiloxanes were synthesized by hydrosilylation reactions of protected allyl‐monosaccharides and subsequent deprotection with a gel‐type ion exchanger. They were characterized by ¹H and ¹³C‐NMR, FT‐IR, GPC and surface tension measurements. These compounds, as well as other water soluble, carboxylate‐based siloxanes were tested as stabilizers in nanoparticle formulations, with polydimethylsiloxane (PDMS), poly(ε‐caprolactone) (PCL) and UDEL polysulfone (PSF) as polymer cores. Owing to their low critical micelle concentrations (cmc), small amounts of surfactants were required. The particle size and granulometric distribution were measured by dynamic light scattering (DLS). Electron microscopy confirmed the DLS results and revealed aggregation phenomena in dry state, depending on the polymer core. In the tested conditions, the glass transition temperature of the polymer seems to be the driving force for the stability of dry nanoparticles. Copyright © 2006 John Wiley & Sons, Ltd.     

Knight Shift in 13C NMR Resonances Confirms the Coordination of N‐Heterocyclic Carbene Ligands to Water‐Soluble Palladium Nanoparticles

The coordination of N‐heterocyclic carbene (NHC) ligands to the surface of 3.7 nm palladium nanoparticles (PdNPs) can be unambiguously established by observation of Knight shift (KS) in the ¹³C resonance of the carbenic carbon. In order to validate this coordination, PdNPs with sizes ranging from 1.3 to 4.8 nm were prepared by thermal decomposition or reduction with CO of a dimethyl NHC Pd^II complex. NMR studies after ¹³CO adsorption established that the KS shifts the ¹³C resonances of the chemisorbed molecules several hundreds of ppm to high frequencies only when the particle exceeds a critical size of around 2 nm. Finally, the resonance of a carbenic carbon is reported to be Knight‐shifted to 600 ppm for ¹³C‐labelled NHCs bound to PdNPs of 3.7 nm. The observation of these very broad KS resonances was facilitated by using Car–Purcell–Meiboom–Gill (CPMG) echo train acquisition NMR experiments.