A facile hydrothermal synthesis route to N and S, N co-doped graphene quantum dots (GQDs) was developed by using citric acid as the C source and urea or thiourea as N and S sources. Both N and S, N doped GQDs showed high quantum yield (78% and 71%), excitation independent under excitation of 340-400 nm and single exponential decay under UV excitation. A broad absorption band in the visible region appeared in S, N co-doped GQDs due to doping with sulfur, which alters the surface state of GQDs. However, S, N co-doped GQDs show different color emission under excitation of 420-520 nm due to their absorption in the visible region. The excellent photocatalytic performance of the S, N co-doped GQD/TiO2 composites was demonstrated by degradation of rhodamine B under visible light. The apparent rate of S, N:GQD/TiO2 is 3 and 10 times higher than that of N:GQD/TiO2 and P25 TiO2 under visible light irradiation, respectively.

As a new member of the carbon material family, carbon dots (CDots) endow carbon materials with luminescent property and expand their application in fluorescent field. Because of their unique optical property, they have attracted much more attention for their potential applications in the photoelectrical conversion, [1] photo catalysis, [2] bioimaging systems, [3] and light-emittaing devices (LEDs) [4] since CDots were discovered in 2004. [5] In early research, CDots had low photoluminescence (PL) quantum yield (QY) and the emission was limited at blue light emission. Over a decade, researchers have put much more effort to improve their PL QY through surface passivation and heteroatom doping methods to induce better charge/carrier transport. Since then, the PL QY of CDots can reach up to 94% for strong blue emission [6] and ≈60% for green emission. [7] This progress leads to potential applications for CDots in bioimaging, optoelectronic devices, and LEDs due to their low toxicity, biocompatibility, and excellent photostability. [3e,8] However, efficient red emissive CDots are still highly desired because red light has deep tissue penetration for bioimaging and is one of the primary colors for white LEDs. There are a few reports on the synthesis of red emissive CDots. For example, using expensive polythiophene phenylpropionic acid as a precursor, Wang and co-workers developed hydrothermal reaction processes to prepare red emissive CDots with low PL QY of 2.3%. [9] Our group reported synthesis of red emissive CDots with 8% PL QY using citric acid (CA) and thiourea, which results in S-and N-doped CDots with enhanced electron delocalization. [10] Lin and co-workers demonstrated synthesis of red emissive CDots with PL QY of 26%. The CDots were prepared through solvothermal route using phenylenediamine isomers. [11] Xiong and co-workers reported the red-emitting CDots with PL QY of ≈24%. The red emission was achieved by tuning the surface state from precursors p-phenylenediamine and urea that were prepared carefully through silica column chromatography. [12] Recently, Yang's group used dopamine and o-phenylenediamine as precursors and obtained near infrared emissive CDots by generating large sp 2 domains. The final QY of the CDots can reach to ≈30%. [13] Despite these efforts, the final materials are expensive for practical applications and lack of clear understanding of luminescence mechanism. Thus, Multiple-color-emissive carbon dots (CDots) have potential applications in various fields such as bioimaging, light-emitting devices, and photocatalysis. The majority of the current CDots to date exhibit excitation-wavelengthdependent emissions with their maximum emission limited at the blue-light region. Here, a synthesis of multiple-color-emission CDots by controlled graphitization and surface function is reported. The CDots are synthesized through controlled thermal pyrolysis of citric acid and urea. By regulating the thermal-pyrolysis temperature and ratio of reactants, the maximum emission of the resulting CDot...

Photoluminescent graphene quantum dots (GQDs) have received enormous attention because of their unique chemical, electronic and optical properties. Here a series of GQDs were synthesized under hydrothermal processes in order to investigate the formation process and optical properties of N-doped GQDs. Citric acid (CA) was used as a carbon precursor and self-assembled into sheet structure in a basic condition and formed N-free GQD graphite framework through intermolecular dehydrolysis reaction. N-doped GQDs were prepared using a series of N-containing bases such as urea. Detailed structural and property studies demonstrated the formation mechanism of N-doped GQDs for tunable optical emissions. Hydrothermal conditions promote formation of amide between –NH2 and –COOH with the presence of amine in the reaction. The intramoleculur dehydrolysis between neighbour amide and COOH groups led to formation of pyrrolic N in the graphene framework. Further, the pyrrolic N transformed to graphite N under hydrothermal conditions. N-doping results in a great improvement of PL quantum yield (QY) of GQDs. By optimized reaction conditions, the highest PL QY (94%) of N-doped GQDs was obtained using CA as a carbon source and ethylene diamine as a N source. The obtained N-doped GQDs exhibit an excitation-independent blue emission with single exponential lifetime decay.

Chromium(VI) [Cr(VI)] is considered as a severe environmental pollutant, due to its highly toxic and carcinogenic properties. Therefore, low cost, highly sensitive sensors for the determination of Cr(VI) are highly demanded. It is well-known that highly luminescent carbon dots (CDs) have been successfully applied as fluorescent nanosensors for pH, ions, and molecular substances. In the present work, we have demonstrated an on-off fluorescent CD probe for detecting Cr(VI) based on the inner filter effect (IFE) because the absorption bands of Cr(IV) fully covered the emission and excitation bands of CDs. This CD-based nanosensor provides obvious advantages of simplicity, convenience, rapid response, high selectivity, and sensitivity, which have potential application for the detection of Cr(VI) in the environmental industry. In addition, because Cr(VI) can be reduced to low valent chromium species easily by reductant, resulting in the elimination of the IFE and recovery of CD fluorescence, the CD-Cr(VI) mixture could behave as an off-on type fluorescent probe for reductant. We employed ascorbic acid (AA) as an example molecule to demonstrate this off-on type fluorescent probe.

A theranostic nanomedicine (CD-Oxa) is synthesized by means of the condensation reaction between the amino groups on the surface of fluorescent carbon dots (CDs) and the carboxyl group of the oxaliplatin derivative Oxa(IV)-COOH. CD-Oxa, which integrates the optical properties of CDs and the anticancer function of oxaliplatin, could be used for simultaneous drug delivery and fluorescent tracking.

Unlike inorganic quantum dots, fluorescent graphene quantum dots (GQDs) display excitation-dependent multiple color emission. In this study, we report N-doped GQDs (N-GQDs) with tailored single color emission by tuning p-conjugation degree, which is comparable to the inorganic quantum dot. Starting from citric acid and diethylenetriamine, as prepared N-GQDs display blue, green, and yellow light emission by changing the reaction solvent from water, dimethylformamide (DMF), and solvent free. The X-ray photoelectron spectroscopy, ultraviolet-visible spectra results clearly show the N-GQDs with blue emission (N-GQDs-B) have relatively short effective conjugation length and more carboxyl group because H 2 O is a polar protic solvent, which tends to donate proton to the reagent to depress the H 2 O elimination reaction. On the other hand, the polar aprotic solvent (DMF) cannot donate hydrogen, the elimination of H 2 O is promoted and more nitrogen units enter GQD framework. With the increase of effective p-conjugation length and N content, the emission band of N-GQDS red-shifts to green and yellow. We also demonstrate that N-GQDs could be a potential great biomarker for fluorescent bioimaging.

A new type of carbon dots (CD-Asp) with targeting function toward brain cancer glioma was synthesized via a straightforward pyrolysis route by using D-glucose and L-aspartic acid as starting materials. The as-prepared CD-Asp exhibits not only excellent biocompatibility and tunable full-color emission, but also significant capability of targeting C6 glioma cells without the aid of any extra targeting molecules. In vivo fluorescence images showed high-contrast biodistribution of CD-Asp 15 min after tail vein injection. A much stronger fluorescent signal was detected in the glioma site than that in normal brain, indicating their ability to freely penetrate the blood-brain barrier and precisely targeting glioma tissue. However, its counterparts, the CDs synthesized from D-glucose (CD-G), L-asparic acid (CD-A), or D-glucose and L-glutamic acid (CD-Glu) have no or low selectivity for glioma. Therefore, CD-Asp could act as a fluorescence imaging and targeting agent for noninvasive glioma diagnosis. This work highlights the potential application of CDs for constructing an intelligent nanomedicine with integration of diagnostic, targeting, and therapeutic functions.

It is highly desirable and a great challenge for red light emission of carbon dots under long wavelength excitation. Here, we developed a facile route to synthesize carbon dots with red emission due to the doping effect of S and N elements, borrowing from the concept of the semiconductor. The maximum emission locates at 594 nm under 560 nm excitation. The absolute photoluminescence (PL) quantum yield (QY) is as high as 29% and 22% in ethanol and water, respectively. XPS and FTIR spectra illustrated that there exist -SCN and -COOH groups on the surface of the carbon dots. They endow the carbon dots with high sensitivity for ion detection of Fe. The quenched PL emission of Fe-S,N-CDs can be recovered by adding ascorbic acid to release the -COOH and -SCN group due to Fe formation in the presence of ascorbic acid. High PL QY of red emission is beneficial to application in bioimaging. Doxorubicin was loaded onto carbon dots through π-π stacking to form a theranostic agent. When the CD-Dox was injected into the tumor site, a strong PL emission was observed. The PL intensity indicates the concentration of the theranostic agent. After 7 times injection, both the tumor size and weight clearly decrease. The results demonstrate that the S,N-CDs are a potentially excellent bioimaging component in the theranostic field.