Carbon Dots with an Emission in the Near Infrared Produced from Organic Dyes in Porous Silica Microsphere Templates.

Carbon dots (CDs) with an emission in the near infrared spectral region are attractive due to their promising applications in bio-related areas, while their fabrication still remains a challenging task. Herein, we developed a template-assisted method using porous silica microspheres for the formation of CDs with optical transitions in the near infrared. Two organic dyes, Rhodamine 6G and IR1061 with emission in the yellow and near infrared spectral regions, respectively, were used as precursors for CDs. Correlation of morphology and chemical composition with optical properties of obtained CDs revealed the origin of their emission, which is related to the CDs' core optical transitions and dye-derivatives within CDs. By varying annealing temperature, different kinds of optical centers as derivatives of organic dyes are formed in the microsphere's pores. The template-assisted method allows us to synthesize CDs with an emission peaked at 1085 nm and photoluminescence quantum yield of 0.2%, which is the highest value reported so far for CDs emitting at wavelengths longer than 1050 nm.

The influence of thermal treatment conditions (solvothermal versus microwave) and solvent polarity on the morphology and emission of phloroglucinol-based nitrogen-doped carbon dots.

The optical properties of chemically synthesized carbon dots (CDs) can be widely tuned via doping and surface modification with heteroatoms such as nitrogen, which results in a range of potential applications. Herein, two most commonly used synthesis approaches, namely, solvothermal and microwave-assisted thermal treatments, have been used for the preparation of CDs from phloroglucinol using three different nitrogen containing solvents, namely, ethylenediamine, dimethylformamide, and formamide. Based on the analysis of the morphology and optical properties, we demonstrate the tenability of the CD appearance from amorphous or well-carbonized spherical particles to onion-like ones, which is controlled by solvent polarity, whereas the thermal treatment conditions mostly influence the degree of N-doping and the nature of emissive centers of CDs formed. The findings of this study expand the toolkit of the available CDs with variable morphology and energy structure.

Magneto-Fluorescent Hybrid Sensor CaCO3-Fe3O4-AgInS2/ZnS for the Detection of Heavy Metal Ions in Aqueous Media.

Heavy metal ions are not subject to biodegradation and could cause the environmental pollution of natural resources and water. Many of the heavy metals are highly toxic and dangerous to human health, even at a minimum amount. This work considered an optical method for detecting heavy metal ions using colloidal luminescent semiconductor quantum dots (QDs). Over the past decade, QDs have been used in the development of sensitive fluorescence sensors for ions of heavy metal. In this work, we combined the fluorescent properties of AgInS2/ZnS ternary QDs and the magnetism of superparamagnetic Fe3O4 nanoparticles embedded in a matrix of porous calcium carbonate microspheres for the detection of toxic ions of heavy metal: Co2+, Ni2+, and Pb2+. We demonstrate a relationship between the level of quenching of the photoluminescence of sensors under exposure to the heavy metal ions and the concentration of these ions, allowing their detection in aqueous solutions at concentrations of Co2+, Ni2+, and Pb2+ as low as ≈0.01 ppm, ≈0.1 ppm, and ≈0.01 ppm, respectively. It also has importance for application of the ability to concentrate and extract the sensor with analytes from the solution using a magnetic field.

Strongly Luminescent Composites Based on Carbon Dots Embedded in a Nanoporous Silicate Glass.

Luminescent composites based on entirely non-toxic, environmentally friendly compounds are in high demand for a variety of applications in photonics and optoelectronics. Carbon dots are a recently developed kind of luminescent nanomaterial that is eco-friendly, biocompatible, easy-to-obtain, and inexpensive, with a stable and widely tunable emission. Herein, we introduce luminescent composites based on carbon dots of different chemical compositions and with different functional groups at the surface which were embedded in a nanoporous silicate glass. The structure and optical properties of these composites were comprehensively examined using electron microscopy, Fourier transform infrared transmission, UV-Vis absorption, and steady-state and time-resolved photoluminescence. It is shown that the silicate matrix efficiently preserved, and even enhanced the emission of different kinds of carbon dots tested. The photoluminescence quantum yield of the fabricated nanocomposite materials reached 35-40%, which is comparable to or even exceeds the values for carbon dots in solution.

Influence of the solvent environment on luminescent centers within carbon dots.

Carbon dots (CDs) are luminescent nanomaterials, with potential use in bioimaging and sensorics. Here, the influence of the surrounding solvent media on the optical properties of CDs synthesized from the most commonly employed precursors, namely citric acid and ethylenediamine, is investigated. The position of optical transitions of CDs can be tuned by the change of pH and solvent polarity. The most striking observation is related to the interaction of CDs with chlorine containing solvents, which results in resolving a set of narrow peaks within both the absorption and PL bands, similar to those observed for polycyclic aromatic hydrocarbons or organic dyes. We assume that the chlorine containing molecules penetrate the surface layers of CDs, which results in an increase of the distance between the luminescent centers; this correlates well with an enhanced D-band in their Raman spectra. A model of CDs composed of a matrix of hydrogenated amorphous carbon with the inclusions of sp2-domains formed by polycyclic aromatic hydrocarbons and their derivatives is suggested; the latter are stacked ensembles of the luminophores and are considered as the origin of the emission of CDs.

sp2-sp3-Hybridized Atomic Domains Determine Optical Features of Carbon Dots.

Carbon dots (CDots) are a promising biocompatible nanoscale source of light, yet the origin of their emission remains under debate. Here, we show that all the distinctive optical properties of CDots, including the giant Stokes shift of photoluminescence and the strong dependence of emission color on excitation wavelength, can be explained by the linear optical response of the partially sp2-hybridized carbon domains located on the surface of the CDots' sp3-hybridized amorphous cores. Using a simple quantum chemical approach, we show that the domain hybridization factor determines the localization of electrons and the electronic bandgap inside the domains and analyze how the distribution of this factor affects the emission properties of CDots. Our calculation data fully agree with the experimental optical properties of CDots, confirming the overall theoretical picture underlying the model. It is also demonstrated that fabrication of CDots with large hybridization factors of carbon domains shifts their emission to the red side of the visible spectrum, without a need to modify the size or shape of the CDots. Our theoretical model provides a useful tool for experimentalists and may lead to extending the applications of CDots in biophysics, optoelectronics, and photovoltaics.