Cytotoxicity of NiO and Ni(OH)2 Nanoparticles Is Mediated by Oxidative Stress-Induced Cell Death and Suppression of Cell Proliferation.

The use of nanomaterial-based products continues to grow with advancing technology. Understanding the potential toxicity of nanoparticles (NPs) is important to ensure that products containing them do not impose harmful effects to human or environmental health. In this study, we evaluated the comparative cytotoxicity between nickel oxide (NiO) and nickel hydroxide (Ni(OH)2) in human bronchoalveolar carcinoma (A549) and human hepatocellular carcinoma (HepG2) cell lines. Cellular viability studies revealed cell line-specific cytotoxicity in which nickel NPs were toxic to A549 cells but relatively nontoxic to HepG2 cells. Time-, concentration-, and particle-specific cytotoxicity was observed in A549 cells. NP-induced oxidative stress triggered dissipation of mitochondrial membrane potential and induction of caspase-3 enzyme activity. The subsequent apoptotic events led to reduction in cell number. In addition to cell death, suppression of cell proliferation played an essential role in regulating cell number. Collectively, the observed cell viability is a function of cell death and suppression of proliferation. Physical and chemical properties of NPs such as total surface area and metal dissolution are in agreement with the observed differential cytotoxicity. Understanding the properties of NPs is essential in informing the design of safer materials.

Carbon Nitride Dots: A Selective Bioimaging Nanomaterial.

In contrast to the recent immense attention in carbon nitride quantum dots (CNQDs) as a heteroatom-doped carbon quantum dot (CQD), their biomedical applications have not been thoroughly investigated. Targeted cancer therapy is a prominently researched area in the biomedical field. Here, the ability of CNQDs as a selective bioimaging nanomaterial was investigated to assist targeted cancer therapy. CNQDs were first synthesized using four different precursor sets involving urea derivatives, and the characteristics were compared to select the best candidate material for bioapplications. Characterization techniques such as UV-vis, luminescence, X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, and transmission electron microscopy were used. These CNQDs were analyzed in in vitro studies of bioimaging and labeling using pediatric glioma cells (SJGBM2) for possible selective biolabeling and nanodistribution inside the cell membrane. The in vitro cellular studies were conducted under long-wavelength emission without the interference of blue autofluorescence. Thus, excitation-dependent emission of CNQDs was proved to be advantageous. Importantly, CNQDs selectively entered SJGBM2 tumor cells, while it did not disperse into normal human embryonic kidney cells (HEK293). The distribution studies in the cell cytoplasm indicated that CNQDs dispersed into lysosomes within approximately 6 h after the incubation. The CNQDs exhibited great potential as a possible nanomaterial in selective bioimaging and drug delivery for targeted cancer therapy.

Close-Packed Langmuir Monolayers of Saccharide-Based Carbon Dots at the Air-Subphase Interface.

Carbon dots (CDs) are zero-dimensional carbon-based spherical nanoparticles with diameters less than 10 nm. Here, we report for the first time CDs forming stable Langmuir monolayers at the air-subphase interface. Langmuir monolayers are of great interest both fundamentally to study the interactions at the interfaces and for many applications such as the development of sensors. However, CDs usually do not form Langmuir monolayers because of their highly hydrophilic nature. In this study, amphiphilic CDs were prepared through hydrothermal carbonization using saccharides as the precursors. The surface chemistry behavior and optical properties of CDs at the air-subphase interface were studied. CDs derived from saccharides consistently formed stable Langmuir monolayers which show all essential phases, namely, gas, liquid-expanded, liquid-condensed, and solid phases. The compression-decompression cycle method showed minimum hysteresis (4.3%), confirming the retaining capacity of the CDs as a monolayer. Limiting CD areas from surface pressure-area isotherm at the air-subphase interface were used to calculate the average diameter of the CDs at the air-subphase interface. UV/vis absorption spectra of CDs dispersed in water and in Langmuir monolayers had the same bands in the UV region. The intensity of the UV/vis absorption increases with increasing surface pressure at the air-subphase interface. Interestingly, photoluminescence (PL) of the Langmuir monolayer of CDs was excitation-independent, whereas the same CDs had excitation-dependent PL when dispersed in water.

Photoluminescent Carbon Dots: A Mixture of Heterogeneous Fractions.

Photoluminescent carbon dots (CDs) fractions have been isolated from a gel-like material (GM), which was synthesized using a convenient one-step solvothermal route. In terms of purification, size exclusion chromatography (SEC) and dialysis were compared with acetone wash, which revealed the advantage of acetone wash. The pre-purified GM with acetone wash (A-GM) was further isolated by the reversed-phase preparative thin layer chromatography (TLC) with acetonitrile-water mixture (7 : 3; va /vw ) as the developing solvent. As a result, there were four photoluminescent bands on the TLC plate, which indicated the presence of four photoluminescent fractions. Detailed characterization measurements such as UV/Vis absorption, fluorescence emission, attenuated total reflection Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, zeta potential, dynamic light scattering, atomic force microscopy, and TEM measurements were performed on all fractions to analyze their heterogeneous optical, structural, electrical, and morphological properties. Considering the comprehensive analysis, all isolated fractions were CDs. In addition, excitation wavelength-independent CDs were obtained with a mean size of 2.5 nm and high quantum yield (55 %). Furthermore, the study demonstrates that the excitation wavelength-dependent photoluminescence of GM could result from the mixture of different surface states of each CD fraction rather than multiple surface states of uniform CDs nanoparticles.

Metformin derived carbon dots: Highly biocompatible fluorescent nanomaterials as mitochondrial targeting and blood-brain barrier penetrating biomarkers.

Carbon dots (CDs) have been intensively studied since their discovery in 2004 because of their unique properties such as low toxicity, excellent biocompatibility, high photoluminescence (PL) and good water dispersibility. In this study metformin derived carbon dots (Met-CDs) were synthesized using a microwave assisted method. Met-CDs were meticulously characterized using ultra-violet spectroscopy (UV-vis), photoluminescence (PL), Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force (AFM) and transmission electron (TEM) microscopies. According to results of cytotoxicity studies, Met-CDs possess low-toxicity and excellent biocompatibility towards both non-tumor and tumor cell lines indicating that Met-CDs are outstanding candidates for living cell bioimaging studies. Furthermore, bioimaging studies have displayed that Met-CDs can penetrate the cell membrane and disperse throughout the cell structure including the nucleus and mitochondria. More specifically, Met-CDs tend to start localizing selectively inside the mitochondria of cancer cells, but not of non-tumor cells after 1 h of incubation. Finally, a zebrafish study confirmed that Met-CDs cross the blood-brain barrier (BBB) without the need of any other ligands. In summary, this study presents synthesis of Met-CDs which feature abilities such as mitochondrial and nucleus localizations along with BBB penetration.

Facile Synthesis of "Boron-Doped" Carbon Dots and Their Application in Visible-Light-Driven Photocatalytic Degradation of Organic Dyes.

Carbon dots (C-dots) were facilely fabricated via a hydrothermal method and fully characterized. Our study shows that the as-synthesized C-dots are nontoxic, negatively charged spherical particles (average diameter 4.7 nm) with excellent water dispersion ability. Furthermore, the C-dots have a rich presence of surface functionalities such as hydroxyls and carboxyls as well as amines. The significance of the C-dots as highly efficient photocatalysts for rhodamine B (RhB) and methylene blue (MB) degradation was explored. The C-dots demonstrate excellent photocatalytic activity, achieving 100% of RhB and MB degradation within 170 min. The degradation rate constants for RhB and MB were 1.8 × 10-2 and 2.4 × 10-2 min-1, respectively. The photocatalytic degradation performances of the C-dots are comparable to those metal-based photocatalysts and generally better than previously reported C-dots photocatalysts. Collectively considering the excellent photocatalytic activity toward organic dye degradation, as well as the fact that they are facilely synthesized with no need of further doping, compositing, and tedious purification and separation, the C-dots fabricated in this work are demonstrated to be a promising alternative for pollutant degradation and environment protection.

Direct conjugation of distinct carbon dots as Lego-like building blocks for the assembly of versatile drug nanocarriers.

As a promising drug nanocarrier, carbon dots (CDs) have exhibited many excellent properties. However, some properties such as bone targeting and crossing the blood-brain barrier (BBB) only apply to a certain CD preparation with limited drug loading capacity. Therefore, it is significant to conjugate distinct CDs to centralize many unique properties on the novel drug nanocarrier. Considering that CDs have abundant and tunable surface functionalities, in this study, a direct conjugation was initiated between two distinct CD models, black CDs (B-CDs) and gel-like CDs (G-CDs) via an amidation reaction. As a result of conjugation at a mass ratio of 5:3 (B-CDs to G-CDs) and a two-step purification process, the conjugate, black-gel CDs (B-G CDs) (5:3) inherited functionalities from both CDs and obtained an enhanced thermostability, aqueous stability, red-shifted photoluminescence (PL) emission, and a figure-eight shape with a width and length of 3 and 6 nm, respectively. In addition, the necessity of high surface primary amine (NH2) content in the CD conjugation was highlighted by replacing G-CDs with other CDs with lower surface NH2 content. Meanwhile, the carboxyl groups (COOH) on G-CDs were not enough to trigger self-conjugation between G-CDs. Moreover, the drug loading capacity was enhanced by 54.5% from B-CDs to B-G CDs (5:3). Furthermore, when the mass ratio of B-CDs to G-CDs was decreased from 5:30, 5:100 to 5:300, the obtained nanostructures revealed a great potential of CDs as Lego-like building blocks. Also, bioimaging of zebrafish demonstrated that various B-G CDs exhibited properties of both bone targeting and crossing the BBB, which are specific properties of B-CDs and G-CDs, respectively.

Tryptophan carbon dots and their ability to cross the blood-brain barrier.

Drug traversal across the blood-brain barrier has come under increasing scrutiny recently, particularly concerning the treatment of sicknesses, such as brain cancer and Alzheimer's disease. Most therapies and medicines are limited due to their inability to cross this barrier, reducing treatment options for maladies affecting the brain. Carbon dots show promise as drug carriers, but they experience the same limitations regarding crossing the blood-brain barrier as many small molecules do. If carbon dots can be prepared from a precursor that can cross the blood-brain barrier, there is a chance that the remaining original precursor molecule can attach to the carbon dot surface and lead the system into the brain. Herein, tryptophan carbon dots were synthesized with the strategy of using tryptophan as an amino acid for crossing the blood-brain barrier via LAT1 transporter-mediated endocytosis. Two types of carbon dots were synthesized using tryptophan and two different nitrogen dopants: urea and 1,2-ethylenediamine. Carbon dots made using these precursors show excitation wavelength-dependent emission, low toxicity, and have been observed inside the central nervous system of zebrafish (Danio rerio). The proposed mechanism for these carbon dots abilities to cross the blood-brain barrier concerns residual tryptophan molecules which attach to the carbon dots surface, enabling them to be recognized by the LAT1 transporter. The role of carbon dots for transport open promising avenues for drug delivery and imaging in the brain.

Size-Dependent Photocatalytic Activity of Carbon Dots with Surface-State Determined Photoluminescence.

Carbon dots (CDs) were synthesized by a microwave-mediated method and separated by size exclusion chromatography into three different size fractions. There was no correlation of the size with photoluminescence (PL) emission wavelength, which shows that the PL mechanism is not quantum-size dependent. UV/vis absorption and diffuse reflectance spectroscopies showed that the light absorption properties as well as the band gap of the CDs changed with the size of the particle. The combination of FTIR and XPS measurements revealed the composition on the surface of each fraction. The three CDs fractions were separately used in the photocatalytic degradation of organic dyes under simulated sunlight irradiation. The catalytic activity of the as-prepared CDs was found to increase as the size of the particles decreased. Complete degradation of both rhodamine B (RhB) and methylene blue (MB) was achieved in 150 min by the 2-nm CDs. The scavenger studies showed that the holes and superoxide radicals are the main species involved in the photocatalytic degradation of the dye by the 2-nm CDs. These CDs displayed high stability in the degradation of organic dyes for multiple cycles. The 2-nm CDs displayed promising photocatalytic degradation of p-nitrophenol (PNP) . These results demonstrate for the first time the application of bare carbon dots in the degradation of environmental contaminants.

Substantially enhanced rate capability of lithium storage in Na2Ti6O13 with self-doping and carbon-coating.

Na2Ti6O13 (NTO) has recently been reported for lithium ion storage and showed very promising results. In this work, we report substantially enhanced rate capability in NTO nanowires by Ti(iii) self-doping and carbon-coating. Ti(iii) doping and carbon coating were found to work in synergy to increase the electrochemical performances of the material. For 300 cycles at 1C (1C = 200 mA g-1) the charge capacity of the electrode is 206 mA h g-1, much higher than that (89 mA h g-1) of the pristine NTO electrode. For 500 cycles at 5C the electrode can still deliver a charge capacity of 180.5 mA h g-1 with a high coulombic efficiency of 99%. At 20C the capacity of the electrode is 2.6 times that of the pristine NTO. These results clearly demonstrate that the Ti(iii) self-doping and uniform carbon coating significantly enhanced the kinetic processes in the NTO nanowire crystal, making it possible for fast charge and discharge in Li-ion batteries.