No abstract

Graphene, a one-atom-thick two-dimensional (2D) layer of sp(2) -bonded carbon, has received worldwide attention owing to its extraordinary physical and chemical properties. Recently, great efforts have been devoted to explore potential applications of graphene and its oxide in life science, especially in disease-related diagnostics, near-Infrared (NIR) phototherapy and imaging. Here we will introduce recent advances and new horizons in this area, and focus on the rising progress on NIR photothermal therapy for cancer and Alzheimer's disease (AD), human telomerase detection, stem cell proliferation and differentiation on graphene substrate, diagnosis of cancer cell and related biomarkers, drug/nucleotide/peptide delivery and cell imaging, which have not been comprehensively reviewed. We hope to provide an outlook to the applications of graphene and its oxide, especially on the new horizons in this field, and inspire broader interests across various disciplines.

The non-enzymatic browning, namely Maillard reaction is commonly invoked to account for abiotic chemical transformations of organic matter. Here we report a new reaction pathway via the Maillard reaction to systematically synthesize a series of nitrogen-doped carbon dots (C-dots) with superhigh quantum yield (QY) and tunable multicolor luminescent displayment. The starting materials are glucose and the serial amino acid analogues which allow systemically controlling luminescent and physicochemical properties of C-dots at will. Unexpectedly, the as-prepared C-dots possess bright photoluminescence with QY up to 69.1% which is almost the highest ever reported, favorable biocompatibility, excellent aqueous and nonaqueous dispersibility, ultrahigh photostability, and readily functionalization. We have demonstrated that they are particularly suitable for multicolor luminescent display and long-term and real-time cellular imaging. Furthermore, the methodology is readily scalable to large yield, and can provide sufficient amount of C-dots for practical demands.

As a rising star in the family of fluorescent material, graphene quantum dots (GQDs) have attracted great attention because of their excellent properties such as high photostability against photobleaching and blinking, biocompatibility, and low toxicity. Herein, blue luminescent GQDs were prepared by photo-reducing GQDs with isopropanol. After photochemical reduction, the increasing of sp(2) domains and the formed hydroxyl in pGQDs can enhance the photoluminescence of GQDs. The quantum yield of the photo-reduced GQDs (pGQDs) was increased 3.7 fold. Because of its less negative surface charges and lower cytotoxicity than chemical reduced GQDs (cGQDs), the pGQDs were more easily uptaken by cells. This work may provide a simple and green pathway to enhance the QY of GQDs with satisfactory biocompatibility as fluorescent nanoprobes.

Alzheimer's disease (AD) is a complex multifactorial syndrome. Metal chelator and Aβ inhibitor are showing promise against AD. In this report, three small hybrid compounds (1, 2, and 3) have been designed and synthesized utilizing salicylaldehyde (SA) based Schiff bases as the chelators and benzothiazole (BT) as the recognition moiety for AD treatment. These conjugates can capture Cu(2+) from Aβ and become dimers upon Cu(2+) coordination and show high efficiency for both Cu(2+) elimination and Aβ assembly inhibition. Besides, the complexes have superoxide dismutase (SOD) activity and significant antioxidant capacity and are capable of decreasing intracellular reactive oxygen species (ROS) and increasing cell viability. All these results indicate that the multifunctional metal complexes which have Aβ specific recognition moiety and metal ion chelating elements show the potential for AD treatment. Therefore, our work will provide new insights into exploration of more potent amyloid inhibitors.

Herein, a pH stimuli-responsive vehicle for intracellular drug delivery using CeO2 capped mesoporous silica nanoparticles (MSN) is reported. β-Cyclodextrin-modified CeO2 nanoparticles could cap onto ferrocene-functionalized mesoporous silica through host-guest interactions. After internalization into A549 cells by a lysosomal pathway, the ferrocenyl moieties are oxidized to ferrocenium ions by CeO2 lids, which could trigger the uncapping of the CeO2 and cause the drugs release. Because of the pH-dependent toxicity, the CeO2 here behaves as a multi-purpose entity that not only acts as a lid but also exhibits a synergistic antitumor effect on cancer cells. Meanwhile, the cell protective effect of CeO2 nanoparticles alone is demonstrated, which ensures that the dissolved CeO2 nanoparticles can be non-toxic to normal cells.

Herein, we report a new kind of highly fluorescent probe for Cu(2+) sensing generated by hydrothermal treatment of graphene quantum dots (GQDs). After hydrothermal treatment in ammonia, the greenish-yellow fluorescent GQDs (gGQDs) with a low quantum yield (QY, 2.5%) are converted to amino-functionalized GQDs (afGQDs) with a high QY (16.4%). Due to the fact that Cu(2+) ions have a higher binding affinity and faster chelating kinetics with N and O on the surface of afGQDs than other transition-metal ions, the selectivity of afGQDs for Cu(2+) is much higher than that of gGQDs. Furthermore, afGQDs are biocompatible and eco-friendly, and the afGQDs with a positive charge can be easily taken up by cells, which makes it possible to sense Cu(2+) in living cells. The strategy presented here is simple in design, economical, and offers a "mix-and-detect" protocol without dye-modified oligonucleotides or complex chemical modification.

Long human telomeric fragments can form stable, higher-order G-quadruplex structures, recently identified in human cells, which are potential drug targets. However, there are very few examples of ligand binding to higher-order G-quadruplexes, and all the reported ligands are proposed to bind at the cleft between two G-quadruplexes. Here we report that zinc-finger-like chiral supramolecular complexes prefer binding to higher-order G-quadruplexes over a single G-quadruplex, with ∼200-fold higher selectivity. To our knowledge, this is the first example of a ligand that can distinguish higher-order G-quadruplexes from a single G-quadruplex with such high selectivity. Further studies indicate that the nanosized chiral complex would bind to two well-matched G-quadruplex units, instead of binding at the cleft between the two G-quadruplexes. These results provide new insights into the targeting of higher-order G-quadruplex ligands. Our work illustrates that dimeric G-quadruplex units can be ligand-preferred binding sites.