Carbon dots: materials, synthesis, properties and approaches to long-wavelength and multicolor emission.

Herein, we summarize recent research developments and progress of carbon dots (CDs), which have been attracting considerable attention as a new type of photoluminescent material. Raw materials, from single carbonaceous compounds to colorful natural substances, for the synthesis of CDs are discussed. A range of diverse synthetic methodologies to achieve better photoluminescence performance and more advanced functions are summarized, and these are basically divided into two classes: top-down and bottom-up. The inspiring properties, mainly including composites, optical properties and cytotoxicity, are listed. In particular, the luminescence mechanism and surface functionalization of the CDs are briefly discussed. Moreover, on the basis of the above, the long-wavelength and multicolor emission properties of CDs and ways to achieve these goals including surface state and size controlled by synthesis strategies, proper precursors, chemical doping and modification, solvatochromic effects and energy transfer are reviewed in detail.

The aggregation induced emission quenching of graphene quantum dots for visualizing the dynamic invasions of cobalt(ii) into living cells.

A highly sensitive and selective approach for cobalt(ii) detection based on the aggregation induced emission quenching strategy, which is opposite to aggregation induced emission enhancement, was developed using graphene quantum dots (GQDs). The detection could be achieved in the range of 10 nM-5 µM and the limit of detection was 2 nM. Importantly, the as-prepared GQDs showed a specific response to cobalt(ii) with excellent stability in A549 cells owing to their good biocompatibility and long-time anti-photobleaching. Thus, these environmentally and bio-friendly carbon nanomaterials were employed to visualize and monitor significant physiological changes of living cells induced by cobalt(ii). This shows great potential for in vitro analysis of cobalt(ii).

"Click" on Alkynylated Carbon Quantum Dots: An Efficient Surface Functionalization for Specific Biosensing and Bioimaging.

Surface functionalization is an essential pre requisite for wide and specific applications of nanoparticles such as photoluminescent (PL) carbon quantum dots (CQDs), but it remains a major challenge. In this report, alkynylated CQDs, prepared from carboxyl-rich CQDs through amidation with propargylamine in the presence of 1,1'-carbonyldiimidazole, were modified efficiently with azido molecular beacon DNA through a copper(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC). As a proof-of-concept, the DNA-modified CQDs are then bonded with gold nanoparticles (AuNPs, 5 nm) through a gold-sulfur bond. Owing to the emission enhancement, this complex can then be applied to the recognition of a single-base- mismatched target. The same functionalizing strategy applied to click the alkynylated CQDs with a nuclear localization sequence (NLS) peptide showed that the NLS-modified CQDs could target the nuclei specifically. These results indicate that surface functionalization of CQDs through a nonstoichiometric copper chalcogenide nanocrystal- (nsCuCNC-) catalyzed click reaction is efficient, and has significant potential in the fields of biosensing and bioimaging.

Highly selective and sensitive detection of 2,4,6-trinitrophenol by using newly developed blue-green photoluminescent carbon nanodots.

Though many methods of detecting 2,4,6-trinitrophenol (TNP) mainly have been developed recent years, quantification of TNP in environmental matrixes still faces up to great challenges because all the nitroaromatic explosives reveal highly similar chemical structure. In the present work, we have developed a selective and sensitive method for detection of TNP by amorphous photoluminescent carbon nanodots (CNDs), which are prepared through a simple hydrothermal route using spermine and m-phenylenediamine (MPD) as precursors. The as-prepared CNDs are found to show blue-green photoluminescence, excitation-wavelength independence, and excellent chemical and optical stability. Owing to the strong characteristic absorption of TNP at 356nm (ε=1.048×104cm-1M-1), which has a good spectral overlap with the excitation band of CNDs, the fluorescence intensity of CNDs at 490nm is linearly quenched with the adding concentration of TNP in the range of 0.1-100µM. The developing assay based on inner filter effect (IFE) mechanism for the detection of TNP is selective and convenient, showing that the as-prepared CNDs have applicable prospect in the concept of simplicity and specificity in analytical chemistry.

Highly selective detection of 2,4,6-trinitrophenol by using newly developed terbium-doped blue carbon dots.

The detection of nitroaromatic explosives is of great importance owing to their strong explosive power and harmfulness in terms of the environment, homeland security and public safety. Herein, rare earth-doped carbon dots with multifunctional features were firstly prepared by simply keeping the mixture of terbium(iii) nitrate pentahydrate and citric acid at 190 °C for 30 min. The as-prepared terbium doped carbon dots (Tb-CDs), through a rapid and simple direct carbonization route, have a size of about 3 nm, and exhibit excitation wavelength dependent emission of blue fluorescence, are stable, and can be applied for the selective and colorimetric detection of 2,4,6-trinitrophenol (TNP) in the range of 500 nM-100 µM with a limit of detection of 200 nM based on the inner filtering effect (IFE) of the excitation and emission bands of Tb-CDs by TNP and the electron transfer (ET) from Tb-CDs to TNP, giving a precise and highly reproducible result for detecting complex water samples.

Synthesis of nitrogen-doping carbon dots with different photoluminescence properties by controlling the surface states.

Surface states of carbon dots (CDs) are critical to the photoemission properties of CDs. By carefully adjusting the reaction conditions in a hydrothermal synthesis route, we have prepared a series of CDs with excitation-dependent emission (EDE) and excitation-independent emission (EIE) properties by controlling the content of nitrogen elements, confirming that the characteristic optical properties of CDs originate from their energy levels. It has been found that surface-passivation of the as-prepared CDs by nitrogen doping can improve the emission efficiency and be beneficial to EIE features due to the single electron transition resulting from the single functional groups. And the as-prepared CDs can specifically bind with Hg(2+) with the emission quenched because of the electron transfer from the LUMO levels of CDs to Hg(2+).

An inner filter effect based sensor of tetracycline hydrochloride as developed by loading photoluminescent carbon nanodots in the electrospun nanofibers.

The inner filter effect (IFE), which results from the absorption of the excitation or emission light by absorbers, has been employed as an alternative approach in sensing systems due to its flexibility and simplicity. In this work, highly photoluminescent carbon nanodots (CDs), which were simply prepared through a new one-step microwave synthesis route, were loaded in electrospun nanofibers, and the obtained nanofibers were then successfully applied to develop a fluorescent IFE-based visual sensor for tetracycline hydrochloride (Tc) sensing in milk. This developed visual sensor has high selectivity owing to the requirements of the spectral overlap between the CDs and Tc, showing high promise in sensing chemistry with an efficient response and economic effect.

Carbon dots with aggregation induced emission enhancement for visual permittivity detection.

Photoluminescent carbon dots (CDs), hydrothermally prepared using tannic acid (TA), show visual aggregation induced emission enhancement (AIEE) properties at 455 nm when excited at 350 nm owing to the rotational hindering of the surface groups on CDs such as aromatic rings and phenolic hydroxyl ones, causing exponential decay between the ratio of the photoluminescence intensity in organic solvents to that in water and the permittivity of the solvent, and thus dazzling emissions of the CDs in the presence of solvents with small permittivity, tetrahydrofuran (THF), for instance, could be visually observed.