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Photoluminescent carbon nanoparticles, or carbon dots, are an emerging class of materials that has recently attracted considerable attention for biomedical and energy applications. They are defined by characteristic sizes of <10 nm, a carbon-based core and the possibility to add various functional groups at their surface for targeted applications. These nanomaterials possess many interesting physicochemical and optical properties, which include tunable light emission, dispersibility and low toxicity. In this Review, we categorize how chemical tools impact the properties of carbon dots. We look for pre- and postsynthetic approaches for the preparation of carbon dots and their derivatives or composites. We then showcase examples to correlate structure, composition and function and use them to discuss the future development of this class of nanomaterials. This Review discusses synthetic strategies to functionalize photoluminescent carbon nanomaterials, or carbon dots, for targeted applications.

The design of novel carbon dots with ad hoc properties requires a comprehensive understanding of their formation mechanism, which is a complex task considering the number of variables involved, such as reaction time, structure of precursors or synthetic protocol employed. Herein, we systematically investigated the formation of carbon nanodots by tracking structural, chemical and photophysical features during the hydrothermal synthesis. We demonstrate that the formation of carbon nanodots consists of 4 consecutive steps: (i) aggregation of small organic molecules, (ii) formation of a dense core with an extended shell, (iii) collapse of the shell and (iv) aromatization of the core. In addition, we provide examples of routes towards tuning the core-shell design, synthesizing five novel carbon dots that all consist of an electron-dense core covered by an amine rich ligand shell. Studying the formation processes of carbon nanodots remains crucial for understanding their properties and chemical structure. Here, the authors investigate the steps involved in their formation process and provide examples for tuning the core-shell design.

Carbon-based dots (CDs) and their functionalized (nano)composites have recently attracted attention due to their seemingly easy preparation and numerous potential applications, ranging from those in the biomedical field (i.e., imaging and drug delivery) to those in (opto)electronics (i.e., solar cells and LEDs). This protocol details step-by-step procedures for synthesis, purification, functionalization and characterization of nitrogen-doped carbon nanodots (NCNDs), which we have been preparing for the past few years. First, we describe the bottom-up synthesis of NCNDs, starting with the use of molecular precursors (arginine (Arg) and ethylenediamine (EDA)) and making use of microwave-assisted hydrothermal heating. We also provide guidelines for the purification of these materials, through either dialysis or low-pressure size-exclusion chromatography (SEC). Second, we outline post-functionalization procedures for the surface modification of NCNDs, such as alkylation and amidation reactions. Third, we provide instructions for the preparation of NCNDs with different properties, such as color emission, electrochemistry and chirality. Given the fast evolution of preparations and applications of CDs, issues that might arise from artifacts, errors and impurities should be avoided. In this context, the present protocol aims to provide details and guidelines for the synthesis of high-quality nanomaterials with high reproducibility, for various applications. Furthermore, specific needs might require the CDs to be prepared by different synthetic procedures and/or from different molecular precursors, but such CDs can still benefit from the purification and characterization procedures outlined in this protocol. The sample preparation takes various time frames, ranging from 4 to 18 d, depending on the adopted synthesis and purification steps. This protocol describes the synthesis, purification, functionalization and characterization of nitrogen-doped carbon nanodots (NCNDs). In addition, examples of how to tailor the color emission, electrochemistry and chirality of NCNDs are provided.

The chirality of (nano)structures is paramount in many phenomena, including biological processes, self-assembly, enantioselective reactions, and light or electron spin polarization. In the quest for new chiral materials, metallo-organic hybrids have been attractive candidates for exploiting the aforementioned scientific fields. Here, we show that chiral carbon nanoparticles, called carbon nanodots, can be readily prepared using hydrothermal microwave-assisted synthesis and easily purified. These particles, with a mean particle size around 3 nm, are highly soluble in water and display mirror-image profile both in the UV–Vis and in the infrared regions, as detected by electronic and vibrational circular dichroism, respectively. Finally, the nanoparticles are used as templates for the formation of chiral supramolecular porphyrin assemblies, showing that it is possible to use and transfer the chiral information. This simple (and effective) methodology opens up exciting opportunities for developing a variety of chiral composite materials and applications. A promising and efficient route to chiral materials involves the transfer of chirality across length scales. Here, the authors use chiral molecular precursors to synthesize chiral carbon nanodots, which in turn can template the formation of chiral supramolecular assemblies.

Carbon nanodots with opposite chirality possess the same major physicochemical properties such as optical features, hydrodynamic diameter, and colloidal stability. Here, a detailed analysis about the comparison of the concentration of both carbon nanodots is carried out, putting a threshold to when differences in biological behavior may be related to chirality and may exclude effects based merely on differences in exposure concentrations due to uncertainties in concentration determination. The present study approaches this comparative analysis evaluating two basic biological phenomena, the protein adsorption and cell internalization. We find how a meticulous concentration error estimation enables the evaluation of the differences in biological effects related to chirality. Chirality is known to impact the biological activity of materials but concentration differences can often lead to errors in analysis. Here, the authors report on detailed concertation analysis of different chiral carbon nanodots to accurately investigate chiral effects on the protein absorption and cell internalisation.

The oxygen in Earth’s atmosphere is there primarily because of water oxidation performed by photosynthetic organisms using solar light and one specialized protein complex, photosystem II (PSII). High-resolution imaging of the PSII ‘core’ complex shows the ideal co-localization of multi-chromophore light-harvesting antennas with the functional reaction centre. Man-made systems are still far from replicating the complexity of PSII, as the majority of PSII mimetics have been limited to photocatalytic dyads based on a 1:1 ratio of a light absorber, generally a Ru–polypyridine complex, with a water oxidation catalyst. Here we report the self-assembly of multi-perylene-bisimide chromophores (PBI) shaped to function by interaction with a polyoxometalate water-oxidation catalyst (Ru 4 POM). The resulting [PBI] 5 Ru 4 POM complex shows a robust amphiphilic structure and dynamic aggregation into large two-dimensional paracrystalline domains, a redshifted light-harvesting efficiency of >40% and favourable exciton accumulation, with a peak quantum efficiency using ‘green’ photons ( λ  > 500 nm). The modularity of the building blocks and the simplicity of the non-covalent chemistry offer opportunities for innovation in artificial photosynthesis. In native photosystem II (PSII), multi-chromophore antennas surround the reaction centre, capturing light and triggering the quantized (four-flashes) photo-oxidation of water to oxygen. The PSII ‘quantasome’ is the most efficient photo-electrolyser built so far. An artificial quantasome has now been developed; it is specifically designed for oxygen evolution by self-assembling light-harvesting-perylene bisimides with a ruthenium polyoxometalate water-oxidation catalyst.

Using metal coordination to assemble carbon nanodots (CND) into clusters can enhance their photophysical properties for applications in sensing and biomedicine. Water-soluble clusters of CNDs are prepared by one-step microwave synthesis starting from ethylenediaminetetraacetic acid, ethylenediamine and MnCl 2 ·4H 2 O as precursors. Transmission electron microscopy and powder X-Ray diffraction techniques indicate that the resulting clusters form spherical particles of 150 nm constituted by amorphous CNDs joined together with Mn ions in a laminar crystalline structure. The nanomaterial assemblies show remarkable fluorescence quantum yields (0.17–0.20) and magnetic resonance imaging capability (r 1  = 2.3-3.8 mM –1 .s –1 ). In addition, they can be stabilized in aqueous solutions by phosphate ligands, providing a promising dual imaging platform for use in biological systems. Using metal coordination to assemble carbon nanodots (CND) into clusters can enhance their photophysical properties for applications in sensing and biomedicine. Here, carboxylate groups on the surface of carbon nanodots serve as ligands for the coordination of manganese ions, enabling the assembly of optically and magnetically active CND clusters in a one-step microwave-assisted synthesis in water.

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H 2 per hour at 50 mV overpotential). The Tafel slope of ∼130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure. Hydrogen evolution by water electrolysis is a promising route to 'green energy', but efficiency is still an issue. Here, the authors make mixed organic/inorganic hierarchical nanostructures with high hydrogen evolution activity, identifying synergic effects in the material contributing to enhanced efficiency.

In tissue engineering strategies, the design of scaffolds based on nanostructures is a subject undergoing intense research: nanomaterials may affect the scaffolds properties, including their ability to interact with cells favouring cell growth and improving tissue performance. Hydrogels are synthetic materials widely used to obtain realistic tissue constructs, as they resemble living tissues. Here, different hydrogels with varying content of graphene, are synthesised by in situ radical polymerization of acrylamide in aqueous graphene dispersions. Hydrogels are characterised focusing on the contribution of the nanomaterial to the polymer network. Our results suggest that graphene is not a mere embedded nanomaterial within the hydrogels, rather it represents an intrinsic component of these networks, with a specific role in the emergence of these structures. Moreover, a hybrid hydrogel with a graphene concentration of only 0.2 mg mL −1 is used to support the growth of cultured brain cells and the development of synaptic activity, in view of exploiting these novel materials to engineer the neural interface of brain devices of the future. The main conclusion of this work is that graphene plays an important role in improving the biocompatibility of polyacrylamide hydrogels, allowing neuronal adhesion.

Carbon dots (CDs), defined by their size of less than 10 nm, are a class of photoluminescent (PL) and electrochemiluminescent (ECL) nanomaterials that include a variety of carbon‐based nanoparticles. However, the control of their properties, especially ECL, remains elusive and afflicted by a series of problems. Here, the authors report CDs that display ECL in water via coreactant ECL, which is the dominant mechanism in biosensing applications. They take advantage of a multicomponent bottom‐up approach for preparing and studying the luminescence properties of CDs doped with a dye acting as PL and ECL probe. The dependence of luminescence properties on the surface chemistry is further reported, by investigating the PL and ECL response of CDs with surfaces rich in primary, methylated, or propylated amino groups. While precursors that contribute to the core characterize the PL emission, the surface states influence the efficiency of the excitation‐dependent PL emission. The ECL emission is influenced by surface states from the organic shell, but states of the core strongly interact with the surface, influencing the ECL efficiency. These findings offer a framework of pre‐ and post‐synthetic design strategies to improve ECL emission properties, opening new opportunities for exploring biosensing applications of CDs. Pre‐ and post‐synthetic strategies enhance the electrochemiluminescence (ECL) of carbon dots (CDs). By using a fluorophore and ECL emitter in the bottom‐up synthesis, the major contribution of the surface emitting states to the ECL emission and the role from the states of the core are revealed. These findings have implications for advancing the ECL applications of CDs.