Spectroscopic/colorimetric dual-mode rapid and ultrasensitive detection of reactive oxygen species based on shape-dependent silver nanostructures.

Excessive production of reactive oxygen species (ROS) from endogenous and exogenous pathways is linked to oxidative stress and various diseases. Although a variety of ROS probes have been developed, their multistep synthesis strategies and complicated instrumental operating procedures limit their frequent use. In this work, different shaped silver nanostructures including nanoparticles, nanoprisms, and nanocubes were utilized to demonstrate simple spectroscopic and colorimetric techniques for sensitive ROS detection. The nanostructures displayed different sensing behaviours recorded via plasmon tuning with morphological changes upon exposure to ROS. Among the nanostructures, silver nanocubes were found to be extremely efficient in recognising a particular ROS, namely hypochlorite ions. The detection limits of this ROS were calculated to be 23.76 nM, 85.71 nM, and 36.37 nM for silver nanoparticles, nanoprisms, and nanocubes, respectively. A time-dependent microscopic examination was carried out and revealed that the presence of hypochlorite ions deteriorates structural morphologies. The formation of highly reactive chlorite, chlorate, and chloride ions in hypochlorite ion solution was ascribed to the significant spectroscopic and microscopic changes in all the nanostructures. The attenuation of plasmonic peaks and etching of nanostructures by ROS were supported by the increment of the oxidation state of silver. In addition, silver nanocubes were successfully applied to recognize ROS in Spinacia oleracea and real water samples. The results confirm the potentiality of silver nanostructures for sensitive detection of ROS in biological and environmental systems.

A comprehensive review on multi-colored emissive carbon dots as fluorescent probes for the detection of pharmaceutical drugs in water.

Exposure to constituent hazardous chemicals in medical products has become a threat to environmental health across the globe. Excessive medication and the mishandling of pharmaceutical drugs can lead to the increased presence of chemicals in the aquatic environment, causing water pollution. Only a few nanomaterials exist for the detection of these chemicals and they are limited in use due to their adverse toxicity, instability, cost, and low aqueous solubility. In contrast, carbon dots (C-dots), a member of the family of carbon-based nanomaterials, have various beneficial properties including excellent biocompatibility, strong photoluminescence, low photobleaching, tunable fluorescence, and easy surface modification. Herein, we summarize recent advancements in various synthetic strategies for high-quality tunable fluorescent C-dots. The root of fluorescence has been briefly explained via the quantum confinement effect, surface defects, and molecular fluorescence. The surface functional moieties of C-dots have been investigated in depth to recognize the various types of pharmaceutical drugs that are used for the treatment of patients. The modulation of C-dot fluorescence in the course of their interactions with these drugs has been carefully explained. Different types of interaction mechanisms behind the C-dot fluorescence alteration have been discussed. Finally, the challenges and future perspectives of C-dots have been proposed for the vibrant field development of C-dot-based drug sensors.

Resveratrol Carbon Dots Disrupt Mitochondrial Function in Cancer Cells.

Resveratrol, a natural polyphenol, exhibits beneficial health properties and has been touted as a potential anti-tumor agent. Here, we demonstrate potent anti-cancer effects of carbon dots (C-dots) synthesized from resveratrol. The mild synthesis conditions retained resveratrol functional moieties upon the carbon dots' (C-dots) surface, an important requisite for achieving specificity toward cancer cells and biological activities. Indeed, the disruptive effects of the resveratrol-C-dot were more pronounced in several cancer cell types compared to normal cells, underscoring targeting capabilities of the C-dots, a pertinent issue for the development of cancer therapeutics. In particular, we observed impairment of mitochondrial functionalities, including intracellular calcium release, inhibition of cytochrome-C oxidase enzyme activity, and mitochondrial membrane perturbation. Furthermore, the resveratrol C-dots were more potent than either resveratrol molecules alone, known anti-cancer polyphenolic agents such as curcumin and triphenylphosphonium, or C-dots prepared from different carbonaceous precursors. This study suggests that resveratrol-synthesized C-dots may have promising therapeutic potential as anti-cancer agents.

Porous Silicon Bragg Reflector/Carbon Dot Hybrids: Synthesis, Nanostructure, and Optical Properties.

Carbon dots (C-dots) exhibit unique fluorescence properties, mostly depending upon their physical environments. Here we investigate the optical properties and nanostructure of Carbon dots (C-dots) which are synthesized in situ within different porous Silicon (PSi) Bragg reflectors. The resulting hybrids were characterized by photoluminescence, X-ray photoelectron, and Fourier Transform Infrared spectroscopies, as well as by confocal and transmission electron microscopy. We show that by tailoring the location of the PSi Bragg reflector photonic bandgap and its oxidation level, the C-dots emission spectral features can be tuned. Notably, their fluorescence emission can be significantly enhanced when the high reflection band of the PSi host overlaps with the confined C-dots' peak wavelength, and the PSi matrix is thermally oxidized at mild conditions. These phenomena are observed for multiple compositions of PSi Bragg reflectors/C-dots hybrids.

Chiral modulation of amyloid beta fibrillation and cytotoxicity by enantiomeric carbon dots.

Enantiomeric carbon dots (C-dots) synthesized from l-lysine or d-lysine, modulate aggregation and cytotoxicity of amyloid beta-42 (Aß42), the primary constituent of the amyloid plaques associated with Alzheimer's disease. In particular, l-Lys-C-dots dramatically remodeled Aß42 secondary structure and fibril morphologies, as well as inhibited Aß42 cytotoxicity and membrane interactions.

Carbon Dots-Plasmonics Coupling Enables Energy Transfer and Provides Unique Chemical Signatures.

Plasmonic nanostructures and carbon dots (C-dots) are fascinating optical materials, utilized in imaging, sensing, and color generation. Interaction between plasmonic materials and C-dots may lead to new hybrid materials with controllable optical properties. Herein, we demonstrate for the first time coupling between plasmonic modes and C-dots deposited upon a plasmonic silver hole array. The coupling leads to a remarkable visual attenuation and shifts of the plasmonic wavelengths (i.e., color tuning). In particular, the C-dots-plasmon couplings and pertinent color transformations depend both upon the C-dots' fluorescence emission wavelengths and functional residues displayed upon the C-dots' surface. This optical modulation corresponds to energy level alignment and consequent energy transfer between the C-dots and the plasmonic silver hole array. Notably, the energy coupling observed in the C-dot-plasmonic hybrid system allows distinguishing between C-dots species exhibiting similar optical properties, albeit displaying different functional residues.

Correction: Tuneable light-emitting carbon-dot/polymer flexible films prepared through one-pot synthesis.

Correction for 'Tuneable light-emitting carbon-dot/polymer flexible films prepared through one-pot synthesis' by Susanta Kumar Bhunia, et al., Nanoscale, 2016, 8, 3400-3406.

Colorimetric Polydiacetylene-Aerogel Detector for Volatile Organic Compounds (VOCs).

A new hybrid system comprising polydiacetylene (PDA), a chromatic conjugated polymer, embedded within aerogel pores has been constructed. The PDA-aerogel powder underwent dramatic color changes in the presence of volatile organic compounds (VOCs), facilitated through infiltration of the gas molecules into the highly porous aerogel matrix and their interactions with the aerogel-embedded PDA units. The PDA-aerogel composite exhibited rapid color/fluorescence response and enhanced signals upon exposure to low VOC concentrations. Encapsulation of PDA derivatives displaying different headgroups within the aerogel produced distinct VOC-dependent color transformations, forming a PDA-aerogel "artificial nose".

Bifunctional Carbon-Dot-WS2 Nanorods for Photothermal Therapy and Cell Imaging.

Multifunctional nanoparticles have attracted significant interest as biomedical vehicles, combining diagnostic, imaging, and therapeutic properties. We describe herein the construction of new nanoparticle conjugates comprising WS2 nanorods (NRs) coupled to fluorescent carbon dots (C-dots). We show that the WS2 -C-dot hybrids integrate the unique physical properties of the two species, specifically the photothermal activity of the WS2 NRs upon irradiation with near-infrared (NIR) light and the excitation-dependent luminescence emission of the C-dots. The WS2 -C-dot NRs have been shown to be non-cytotoxic and have been successfully employed for multicolour cell imaging and targeted cell killing under NIR irradiation, pointing to their potential utilization as effective therapeutic vehicles.

Thenoyltrifluoroacetone (TTA)-Carbon Dot/Aerogel Fluorescent Sensor for Lanthanide and Actinide Ions.

Contamination of groundwater with radioactive substances comprising actinides and lanthanides is a significant environmental hazard and thus the development of selective, sensitive, and easy-to-apply sensors for water-soluble actinide and lanthanide ions is highly sought. We constructed a new selective fluorescent sensor for UO2 2+, Sm3+, and Eu3+ based on a carbon dot (C-dot)-aerogel hybrid prepared through in situ carbonization of 2-thenoyltrifluoroacetone (TTA), a high-affinity heavy metal chelator. The TTA-C-dot-aerogel enabled the detection of UO2 2+ ions, which induced a significant red fluorescence shift, whereas Eu3+ and particularly Sm3+ ions gave rise to pronounced fluorescence quenching. Importantly, the lanthanide/actinide ion-selective TTA-C-dots could be synthesized only in situ inside the aerogel pores, indicating the crucial role of the aerogel host matrix both in enabling the formation of the C-dots and in promoting the adsorption and interactions of the lanthanide and actinide metal ions with the embedded C-dots.

Carbon-Dot/Silver-Nanoparticle Flexible SERS-Active Films.

Development of effective platforms for surface enhanced Raman scattering (SERS) sensing has mostly focused on fabrication of colloidal metal surfaces and tuning of their surface morphologies, designed to create "hot spots" in which plasmonic fields yield enhanced SERS signals. We fabricated distinctive SERS-active flexible films comprising polydimethylsiloxane (PDMS) embedding carbon dots (C-dots) and coated with silver nano-particles (Ag NPs). We show that the polymer-associated Ag NPs and C-dots intimately affected the physical properties of each other. In particular, the C-dot-Ag-NP-polymer films exhibited SERS properties upon deposition of versatile targets, both conventional SERS-active dyes as well as bacterial samples. We show that the SERS response was correlated to the formation C-dots within the polymer film and the physical proximity between the C-dots and Ag NPs, indicating that coupling between the plasmonic fields of the Ag NPs and C-dots' excitons constituted a prominent factor in the SERS properties.

Lipid-Bilayer Dynamics Probed by a Carbon Dot-Phospholipid Conjugate.

Elucidating the dynamic properties of membranes is important for understanding fundamental cellular processes and for shedding light on the interactions of proteins, drugs, and viruses with the cell surface. Dynamic studies of lipid bilayers have been constrained, however, by the relatively small number of pertinent molecular probes and the limited physicochemical properties of the probes. We show that a lipid conjugate comprised of a fluorescent carbon dot (C-dot) covalently attached to a phospholipid constitutes a versatile and effective vehicle for studying bilayer dynamics. The C-dot-modified phospholipids readily incorporated within biomimetic membranes, including solid-supported bilayers and small and giant vesicles, and inserted into actual cellular membranes. We employed the C-dot-phospholipid probe to elucidate the effects of polymyxin-B (a cytolytic peptide), valproic acid (a lipophilic drug), and amyloid-ß (a peptide associated with Alzheimer's disease) upon bilayer fluidity and lipid dynamics through the application of various biophysical techniques.

Red Fluorescent Carbon Nanoparticle-Based Cell Imaging Probe.

Fluorescent carbon nanoparticle-based probes with tunable visible emission are biocompatible, environment friendly and most suitable for various biomedical applications. However, synthesis of red fluorescent carbon nanoparticles and their transformation into functional nanoparticles are very challenging. Here we report red fluorescent carbon nanoparticle-based nanobioconjugates of <25 nm hydrodynamic size and their application as fluorescent cell labels. Hydrophobic carbon nanoparticles are synthesized via high temperature colloid-chemical approach and transformed into water-soluble functional nanoparticles via coating with amphiphilic polymer followed by covalent linking with desired biomolecules. Following this approach, carbon nanoparticles are functionalized with polyethylene glycol, primary amine, glucose, arginine, histidine, biotin and folic acid. These functional nanoparticles can be excited with blue/green light (i.e., 400-550 nm) to capture their emission spanning from 550 to 750 nm. Arginine and folic acid functionalized nanoparticles have been demonstrated as fluorescent cell labels where blue and green excitation has been used for imaging of labeled cells. The presented method can be extended for the development of carbon nanoparticle-based other bioimaging probes.

Tuneable light-emitting carbon-dot/polymer flexible films prepared through one-pot synthesis.

Development of efficient, inexpensive, and environmentally-friendly light emitters, particularly devices that produce white light, have drawn intense interest due to diverse applications in the lighting industry, photonics, solar energy, and others. We present a simple strategy for the fabrication of flexible transparent films exhibiting tuneable light emission through one-pot synthesis of polymer matrixes with embedded carbon dots assembled in situ. Importantly, different luminescence colours were produced simply by preparing C-dot/polymer films using carbon precursors that yielded C-dots exhibiting distinct fluorescence emission profiles. Furthermore, mixtures of C-dot precursors could be also employed for fabricating films exhibiting different colours. In particular, we successfully produced films emitting white light with attractive properties (i.e."warm" white light with a high colour rendering index) - a highly sought after goal in optical technologies.

Imaging Cancer Cells Expressing the Folate Receptor with Carbon Dots Produced from Folic Acid.

Development of new imaging tools for cancer cells in vitro and in vitro is important for advancing cancer research, elucidating drug effects upon cancer cells, and studying cellular processes. We showed that fluorescent carbon dots (C-dots) synthesized from folic acid can serve as an effective vehicle for imaging cancer cells expressing the folate receptor on their surface. The C-dots, synthesized through a simple one-step process from folic acid as the carbon source, exhibited selectivity towards cancer cells displaying the folate receptor, making such cells easily distinguishable in fluorescence microscopy imaging. Biophysical measurements and competition experiments both confirmed the specific targeting and enhanced uptake of C-dots by the folate receptor-expressing cells. The folic acid-derived C-dots were not cytotoxic, and their use in bioimaging applications could aid biological studies of cancer cells, identification of agonists/antagonists, and cancer diagnostics.

Reduced graphene oxide-silver nanoparticle composite as visible light photocatalyst for degradation of colorless endocrine disruptors.

Sunlight-induced degradation of organic pollutants is an ideal approach for environmental pollution control and wastewater treatment. Although a variety of photocatalysts have been designed toward this goal, efficient degradation of colorless organic pollutants by visible light is a challenging issue. Here, we show that a reduced graphene oxide (rGO)-based composite with silver nanoparticle (rGO-Ag) can act as an efficient visible-light photocatalyst for the degradation of colorless organic pollutants. We have developed a simple, large-scale synthesis method for rGO-Ag and used it for the degradation of three well-known endocrine disruptors (phenol, bisphenol A, and atrazine) under UV and visible light. It is found that photocatalytic efficiency by rGO-Ag under visible light is significantly higher compared to that of rGO or silver nanoparticles. It is proposed that Ag nanoparticles offer visible-light-induced excitation of silver plasmons, and conductive rGO offers efficient charge separation and thus induces oxidative degradation of the organic pollutant. This approach can be extended for sunlight-induced degradation of different organic pollutants.

Vitamin B1 derived blue and green fluorescent carbon nanoparticles for cell-imaging application.

A carbon-based fluorescent nanoparticle is considered to be a new generation nontoxic nanoprobe suitable for various bioimaging and sensing applications. However, the synthesis of such a high-quality nanoparticle is challenging, and its application potential is mostly unexplored. Here we report a vitamin B1 carbonization-based approach for blue and green fluorescent carbon nanoparticles of <10 nm size with a fluorescence quantum of up to 76%. We found that carbonization of vitamin B1 in the presence of phosphate salt at ∼90-130 °C for about 2 h produces highly fluorescent carbon nanoparticles of 1-6 nm size. The particle size and fluorescence property can be controlled by varying the reaction temperature and nature of phosphate salt. Elemental analysis shows the incorporation of a large percentage (up to 48 wt %) of other elements (such as nitrogen, oxygen, phophorus, and sulfur) in the carbon matrix. The chemical structure of vitamin B1 (thiamine) is unique in a sense that it consists of a large number of heteroatoms along with unsaturated bonds and offers low-temperature carbonization with the formation of a nanoparticle having an optimum ratio of sp(2) and sp(3) carbon atoms. These carbon nanoparticles have high colloidal stability and stable fluorescence and have been used as fluorescent imaging probes.

Carbon nanoparticle-based fluorescent bioimaging probes.

Fluorescent nanoparticle-based imaging probes have advanced current labelling technology and are expected to generate new medical diagnostic tools based on their superior brightness and photostability compared with conventional molecular probes. Although significant progress has been made in fluorescent semiconductor nanocrystal-based biological labelling and imaging, the presence of heavy metals and the toxicity issues associated with heavy metals have severely limited the application potential of these nanocrystals. Here, we report a fluorescent carbon nanoparticle-based, alternative, nontoxic imaging probe that is suitable for biological staining and diagnostics. We have developed a chemical method to synthesise highly fluorescent carbon nanoparticles 1-10 nm in size; these particles exhibit size-dependent, tunable visible emission. These carbon nanoparticles have been transformed into various functionalised nanoprobes with hydrodynamic diameters of 5-15 nm and have been used as cell imaging probes.

Peptide-functionalized colloidal graphene via interdigited bilayer coating and fluorescence turn-on detection of enzyme.

Synthesis of colloidal functional graphene is challenging because graphene is water-insoluble and its relatively inert surface made the functionalization a difficult task. Here we report interdigited bilayer type coating that provide both colloidal stability and functionalization option for graphene. Colloidal graphene oxide is first converted into interdigited bilayer coated graphene oxide and next they are transformed into colloidal graphene by hydrazine reduction. These coated graphenes can be further transformed into colloidal functional graphene using covalent conjugation chemistry. Functional graphene has been synthesized for optical detection of enzyme where a fluorescent dye is covalently linked through a peptide so that the dye fluorescence is quenched by graphene but switches on once enzymes cleave the peptide bond. The interdigited bilayer coating reported here is unique as it provides coating thickness <3 nm, offering optically responsive graphene-fluorophore substrate with high colloidal stability.