Efficient
and selective methods for covalent derivatization of
graphene are needed because they enable tuning of graphene’s
surface and electronic properties, thus expanding its application
potential. However, existing approaches based mainly on chemistry
of graphene and graphene oxide achieve only limited level of functionalization
due to chemical inertness of the surface and nonselective simultaneous
attachment of different functional groups, respectively. Here we present
a conceptually different route based on synthesis of cyanographene via the controllable substitution and defluorination of
fluorographene. The highly conductive and hydrophilic cyanographene
allows exploiting the complex chemistry of −CN groups toward
a broad scale of graphene derivatives with very high functionalization
degree. The consequent hydrolysis of cyanographene results in graphene
acid, a 2D carboxylic acid with pKa of
5.2, showing excellent biocompatibility, conductivity and dispersibility
in water and 3D supramolecular assemblies after drying. Further, the
carboxyl groups enable simple, tailored and widely accessible 2D chemistry
onto graphene, as demonstrated via the covalent conjugation
with a diamine, an aminothiol and an aminoalcohol. The developed methodology
represents the most controllable, universal and easy to use approach
toward a broad set of 2D materials through consequent chemistries
on cyanographene and on the prepared carboxy-, amino-, sulphydryl-,
and hydroxy- graphenes.
Nanoscale biocompatible photoluminescence (PL) thermometers that can be used to accurately and reliably monitor intracellular temperatures have many potential applications in biology and medicine. Ideally, such nanothermometers should be functional at physiological pH across a wide range of ionic strengths, probe concentrations, and local environments. Here, we show that water-soluble N,S-co-doped carbon dots (CDs) exhibit temperature-dependent photoluminescence lifetimes and can serve as highly sensitive and reliable intracellular nanothermometers. PL intensity measurements indicate that these CDs have many advantages over alternative semiconductor- and CD-based nanoscale temperature sensors. Importantly, their PL lifetimes remain constant over wide ranges of pH values (5-12), CD concentrations (1.5 × 10 to 0.5 mg/mL), and environmental ionic strengths (up to 0.7 mol·L NaCl). Moreover, they are biocompatible and nontoxic, as demonstrated by cell viability and flow cytometry analyses using NIH/3T3 and HeLa cell lines. N,S-CD thermal sensors also exhibit good water dispersibility, superior photo- and thermostability, extraordinary environment and concentration independence, high storage stability, and reusability-their PL decay curves at temperatures between 15 and 45 °C remained unchanged over seven sequential experiments. In vitro PL lifetime-based temperature sensing performed with human cervical cancer HeLa cells demonstrated the great potential of these nanosensors in biomedicine. Overall, N,S-doped CDs exhibit excitation-independent emission with strongly temperature-dependent monoexponential decay, making them suitable for both in vitro and in vivo luminescence lifetime thermometry.
Materials based on metallic elements that have d orbitals and exhibit room temperature magnetism have been known for centuries and applied in a huge range of technologies. Development of room temperature carbon magnets containing exclusively sp orbitals is viewed as great challenge in chemistry, physics, spintronics and materials science. Here we describe a series of room temperature organic magnets prepared by a simple and controllable route based on the substitution of fluorine atoms in fluorographene with hydroxyl groups. Depending on the chemical composition (an F/OH ratio) and sp3 coverage, these new graphene derivatives show room temperature antiferromagnetic ordering, which has never been observed for any sp-based materials. Such 2D magnets undergo a transition to a ferromagnetic state at low temperatures, showing an extraordinarily high magnetic moment. The developed theoretical model addresses the origin of the room temperature magnetism in terms of sp2-conjugated diradical motifs embedded in an sp3 matrix and superexchange interactions via –OH functionalization.
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