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Carbon nanomaterials have attracted significant attention for a variety of biomedical applications including sensing and detection, photothermal therapy, and delivery of therapeutic cargo. The ease of chemical functionalization, tunable length scales and morphologies, and ability to undergo complete enzymatic degradation make carbon nanomaterials an ideal drug delivery system. Much work has been done to synthesize carbon nanomaterials ranging from carbon dots, graphene, and carbon nanotubes to carbon nanocapsules, specifically carbon nanohorns or nitrogen-doped carbon nanocups. Here, we analyze specific properties of nitrogen-doped carbon nanotube cups which have been designed and utilized as drug delivery systems with the focus on the loading of these nanocapsules with specific therapeutic cargo and the targeted delivery for cancer therapy. We also summarize our targeted synthesis of gold nanoparticles on the open edge of nitrogen-doped carbon nanotube cups to create loaded and sealed nanocarriers for the delivery of chemotherapeutic agents to myeloid regulatory cells responsible for the immunosuppressive properties of the tumor microenvironment and thus tumor immune escape.

The combination of porosity and electrical conductivity in a single nanomaterial is important for a variety of applications. In this work, we demonstrate the growth of ZIF-8 on the surface of single-walled carbon nanotubes (SWCNTs). The growth mechanism was investigated and a molecularly ordered imidazole solvation layer was found to disperse SWCNTs and promote crystal growth on the sidewalls. The resultant ZIF-8/SWCNT composite demonstrates high microporosity and electrical conductivity. The ZIF-8/SWCNT composite displayed semiconducting electrical behavior and an increase in sensor sensitivity toward ethanol vapors versus pristine SWCNTs.

Carbon nanotube-based field-effect transistors (NTFETs) are ideal sensor devices as they provide rich information regarding carbon nanotube interactions with target analytes and have potential for miniaturization in diverse applications in medical, safety, environmental, and energy sectors. Herein, we investigate chemical detection with cross-sensitive NTFETs sensor arrays comprised of metal nanoparticle-decorated single-walled carbon nanotubes (SWCNTs). By combining analysis of NTFET device characteristics with supervised machine-learning algorithms, we have successfully discriminated among five selected purine compounds, adenine, guanine, xanthine, uric acid, and caffeine. Interactions of purine compounds with metal nanoparticle-decorated SWCNTs were corroborated by density functional theory calculations. Furthermore, by testing a variety of prepared as well as commercial solutions with and without caffeine, our approach accurately discerns the presence of caffeine in 95% of the samples with 48 features using a linear discriminant analysis and in 93.4% of the samples with only 11 features when using a support vector machine analysis. We also performed recursive feature elimination and identified three NTFET parameters, transconductance, threshold voltage, and minimum conductance, as the most crucial features to analyte prediction accuracy.

Early diagnosis of SARS-CoV-2 infection is critical for facilitating proper containment procedures, and a rapid, sensitive antigen assay is a critical step in curbing the pandemic. In this work, we report the use of a high-purity semiconducting (sc) single-walled carbon nanotube (SWCNT)-based field-effect transistor (FET) decorated with specific binding chemistry to assess the presence of SARS-CoV-2 antigens in clinical nasopharyngeal samples. Our SWCNT FET sensors, with functionalization of the anti-SARS-CoV-2 spike protein antibody (SAb) and anti-nucleocapsid protein antibody, detected the S antigen (SAg) and N antigen (NAg), reaching a limit of detection of 0.55 fg/mL for SAg and 0.016 fg/mL for NAg in calibration samples. SAb-functionalized FET sensors also exhibited good sensing performance in discriminating positive and negative clinical samples, indicating a proof of principle for use as a rapid COVID-19 antigen diagnostic tool with high analytical sensitivity and specificity at low cost.

Nanomaterial-based electronic sensors have demonstrated ultra-low detection limits, down to parts-per-billion (ppb) or parts-per-trillion (ppt) concentrations. However, these extreme sensitivities also make them susceptible to signal saturation at higher concentrations and restrict their usage primarily to low concentrations. Here, we report machine learning techniques to create a calibration method for carbon nanotube-based field-effect transistor (FET) devices. We started with linear regression, followed by regression splines to capture the non-linearity in the data. Further improvements in model performance were obtained with regression trees. Finally we lowered the model variance and further boosted the model performance by introducing random forest. The resulting performance as measured by R

Objective: Up to 10% of free flap cases are compromised, and without prompt intervention, amputation and even death can occur. Hourly monitoring improves salvage rates, but the gold standard for monitoring requires experienced personnel to operate and suffers from high false-positive rates as high as 31% that result in costly and unnecessary surgeries. In this paper, we investigate free flap patency monitoring using automatic hardware-only classification systems that eliminate the need for experienced personnel. The expected flow ranges of the antegrade and retrograde veins for breast reconstruction are studied using a syringe pump to create the laminar flow seen in veins. Methods: Feature data extracted from the Doppler blood flow signals are analyzed for sensitivity, specificity, and false-positive rates. Hardware is built to perform the classification automatically in real-time and output a decision at the end of the observation period. Results: Experimental results using the hardware-only classifier for a 50 ms window size show high sensitivity (96.75%), specificity (90.20%), and low false-positive rate (9.803%). The experimental and theoretical classification results show close agreement. Conclusion: This work indicates that automatic hardware-only classifiers can eliminate the need for experienced personnel to monitor free flap patency. Significance: The hardware-only classification is amenable to a monolithic implementation and future studies should study a totally implantable wirelessly-powered blood flow classifier. The high classifier performance in a short window period indicates that duty-cycled powering can be used to extend the safe operational depth of an implant. This is particularly relevant for the difficult buried free flap applications.

Hybrid nanomaterials comprising metal–graphitic interfaces are uniquely suitable to probe molecular interactions and the associated phenomena such as charge transfer and adsorbate spillover effects. Herein, we study the modulation of the electronic and chemical properties of gold nanoparticle-decorated single-walled carbon nanotubes (SWCNT) using Raman spectroscopy and measurements of field-effect transistor (FET) characteristics. SWCNT are extremely sensitive to changes in the local electronic environment and therefore gold-analyte interactions may be probed both through changes in FET characteristics (as an electrical transducer) and in surface-enhanced Raman scattering (as a chromophore). We study these changes both experimentally and theoretically in order to elucidate the electronic structure of complex nanocomposites, and the information gathered from these experiments is applied to the study of biomolecular interactions with gold nanoparticle-decorated SWCNT. This study, in addition to providing de...

We report a facile chemical method for fabricating holey graphene by catalytic oxidation of highly ordered pyrolytic graphite (HOPG) using an Fe(III) porphyrin complex-based covalent organic framework (COF) as a bifunctional surface catalyst–template. We demonstrate regular hole formation after oxidation with H(2)O(2) and NaOCl, COF removal, and HOPG exfoliation.

Single-walled carbon nanotubes (SWCNTs) have been incorporated in many emerging applications in the biomedical field including chemical sensing, biological imaging, drug delivery, and photothermal therapy. To overcome inherent hydrophobicity and improve their biocompatibility, pristine SWCNTs are often coated with surfactants, polymers, DNA, proteins, or lipids. In this paper, we report the effect of polyunsaturated fatty acids (PUFAs) on SWCNT photoluminescence. A decrease in the SWCNT bandgap emission (E(11)) and a new red-shifted emission (E(11)(−)) were observed in the presence of PUFAs. We attribute the change in SWCNT photoluminescence to the formation of oxygen-containing defects by lipid hydroperoxides through photo-oxidation. The observed changes in near-infrared emission of SWCNTs are important for understanding the interaction between SWCNTs and lipid biocorona. Our results also indicate that photo-excited SWCNTs can catalyze lipid peroxidation similarly to lipoxygenases.

Nanocellulose (NC) is emerging as a highly promising nanomaterial for a wide range of applications. Moreover, many types of NC are produced, each exhibiting a slightly different shape, size, and chemistry. The main objective of this study was to compare cytotoxic effects of cellulose nanocrystals (CNC) and nanofibrillated cellulose (NCF). The human lung epithelial cells (A549) were exposed for 24 h and 72 h to five different NC particles to determine how variations in properties contribute to cellular outcomes, including cytotoxicity, oxidative stress, and cytokine secretion. Our results showed that NCF were more toxic compared to CNC particles with respect to cytotoxicity and oxidative stress responses. However, exposure to CNC caused an inflammatory response with significantly elevated inflammatory cytokines/chemokines compared to NCF. Interestingly, cellulose staining indicated that CNC particles, but not NCF, were taken up by the cells. Furthermore, clustering analysis of the inflammatory cytokines revealed a similarity of NCF to the carbon nanofibers response and CNC to the chitin, a known immune modulator and innate cell activator. Taken together, the present study has revealed distinct differences between fibrillar and crystalline nanocellulose and demonstrated that physicochemical properties of NC are critical in determining their toxicity.

Single-walled carbon nanotubes (SWCNTs) are experimentally utilized in in vivo imaging and photothermal cancer therapy owing to their unique physicochemical and electronic properties. For these applications, pristine carbon nanotubes are often modified by polymer surfactant coatings to improve their biocompatibility, adding more complexity to their recognition and biodegradation by immuno-competent cells. Here, we investigate the oxidative degradation of SWCNTs catalyzed by neutrophil myeloperoxidase (MPO) using bandgap near-infrared (NIR) photoluminescence and Raman spectroscopy. Our results show diameter-dependence at the initial stages of the oxidative degradation of sodium cholate-, DNA-, and albumin-coated SWCNTs, but not phosphatidylserine-coated SWCNTs. Moreover, sodium deoxycholate- and phospholipid-polyethylene glycol coated SWCNTs were not oxidized under the same reaction conditions, indicating that a surfactant can greatly impact the biodegradability of a nanomaterial. Our data also revealed that possible binding between MPO and surfactant coated-SWCNTs was unfavorable, suggesting that oxidation is likely caused by a hypochlorite generated through halogenation cycles of free MPO, and not MPO bound to the surface of SWCNTs. The identification of SWCNT diameters and coatings that retain NIR fluorescence during the interactions with the components of an innate immune system is important for their applications in in vivo imaging.

Nanomaterial-based electronic sensors have demonstrated ultra-low detection limits, down to parts-per-billion (ppb) or parts-per-trillion (ppt) concentrations. However, these extreme sensitivities also make them susceptible to signal saturation at higher concentrations and restrict their usage primarily to low concentrations. Here, we report machine learning techniques to create a calibration method for carbon nanotube-based field-effect transistor (FET) devices. We started with linear regression, followed by regression splines to capture the non-linearity in the data. Further improvements in model performance were obtained with regression trees. Finally we lowered the model variance and further boosted the model performance by introducing random forest. The resulting performance as measured by R2 was estimated to be 0.8260 using out-of-bag error. The methodology avoids saturation and extends the dynamic range of the nanosensors up to 12 orders of magnitude in analyte concentrations. Further investigations of the sensing mechanism include analysis of feature importance in each of the model we tested. Functionalized nanosensors demonstrate selective detection of Hg2+ ions with detection limits 10−14.36±0.78 M, and maintain calibration to concentrations as high as 1 mM. Application of machine learning techniques to investigate which features in the FET signal maximally correlate with concentration changes provide valuable insight into the carbon nanotube sensing mechanism and assist in the rational design of future nanosensors.

Biopersistence of carbon nanotubes, graphene oxide (GO) and several other types of carbonaceous nanomaterials is an essential determinant of their health effects. Successful biodegradation is one of the major factors defining the life span and biological responses to nanoparticles. Here, we review the role and contribution of different oxidative enzymes of inflammatory cells - myeloperoxidase, eosinophil peroxidase, lactoperoxidase, hemoglobin, and xanthine oxidase - to the reactions of nanoparticle biodegradation. We further focus on interactions of nanomaterials with hemoproteins dependent on the specific features of their physico-chemical and structural characteristics. Mechanistically, we highlight the significance of immobilized peroxidase reactive intermediates vs diffusible small molecule oxidants (hypochlorous and hypobromous acids) for the overall oxidative biodegradation process in neutrophils and eosinophils. We also accentuate the importance of peroxynitrite-driven pathways realized in macrophages via the engagement of NADPH oxidase- and NO synthase-triggered oxidative mechanisms. We consider possible involvement of oxidative machinery of other professional phagocytes such as microglial cells, myeloid-derived suppressor cells, in the context of biodegradation relevant to targeted drug delivery. We evaluate the importance of genetic factors and their manipulations for the enzymatic biodegradation in vivo. Finally, we emphasize a novel type of biodegradation realized via the activation of the “dormant” peroxidase activity of hemoproteins by the nano-surface. This is exemplified by the binding of GO to cyt c causing the unfolding and “unmasking” of the peroxidase activity of the latter. We conclude with the strategies leading to safe by design carbonaceous nanoparticles with optimized characteristics for mechanism-based targeted delivery and regulatable life-span of drugs in circulation.

Titanium dioxide (TiO(2)) nanostructures and TiO(2)/graphene nanocomposites are intensively studied materials for energy conversion, energy storage, and organic contaminant photodegradation. However, for TiO(2)/graphene composites, impermeability across the graphitic basal plane for electrolytes, metal ions, and gas molecules hinders their practical applications. Herein we report a simple, environmentally-friendly synthetic route for mesoporous anatase TiO(2) nanospindles, and successfully apply this method to obtain in-situ grown TiO(2) nanospindles/graphene oxide composite. After a thermal reduction at 400 °C, holes are created in the reduced graphene oxide (RGO) sheets through a photocatalytic oxidation mechanism. The formation of holes in RGO is promoted by photogenerated hydroxyl radicals that oxidize and subsequently decarboxylate the graphitic surface of RGO. The proposed mechanism was supported by photo-catalytic electrochemical properties of the nanomaterials. The resulting TiO(2)/holey RGO composites may overcome the original impermeability of graphene sheets and find applications in catalysis, energy conversion/storage devices, and sensors.

Tumor microenvironment is characterized by immunosuppressive mechanisms associated with the accumulation of immune regulatory cells - myeloid-derived suppressor cells (MDSC). Therapeutic depletion of MDSC has been associated with inhibition of tumor growth and therefore represents an attractive approach to cancer immunotherapy. MDSC in cancer are characterized by enhanced enzymatic capacity to generate reactive oxygen and nitrogen species (RONS) which have been shown to effectively degrade carbonaceous materials. We prepared enzymatically openable nitrogen-doped carbon nanotube cups (NCNC) corked with gold nanoparticles and loaded with paclitaxel as a therapeutic cargo. Loading and release of paclitaxel was confirmed through electron microscopy, Raman spectroscopy and LC-MS analysis. Under the assumption that RONS generated by MDSCs can be utilized as a dual targeting and oxidative degradation mechanism for NCNC, here we report that systemic administration of paclitaxel loaded NCNC delivers paclitaxel to circulating and lymphoid tissue MDSC resulting in the inhibition of growth of tumors (B16 melanoma cells inoculated into C57BL/6 mice) in vivo. Tumor growth inhibition was associated with decreased MDSC accumulation quantified by flow cytometry that correlated with bio-distribution of gold-corked NCNC resolved by ICP-MS detection of residual gold in mouse tissue. Thus, we developed a novel immunotherapeutic approach based on unique nanodelivery vehicles, which can be loaded with therapeutic agents that are released specifically in MDSC via NCNC selective enzymatic "opening" affecting change in the tumor microenvironment.

Carbon nanomaterials have been proposed as effective drug delivery devices; however their perceived biopersistence and toxicological profile may hinder their applications in medical therapeutics. Nitrogen doping of carbon nanotubes results in a unique "stacked-cup" structure, with cups held together through van der Waals forces. Disrupting these weak interactions yields individual and short-stacked nanocups that can subsequently be corked with gold nanoparticles, resulting in sealed containers for delivery of cargo. Peroxidase-catalyzed reactions can effectively uncork these containers, followed by complete degradation of the graphitic capsule, resulting in effective release of therapeutic cargo while minimizing harmful side effects. The protocols reported herein describe the synthesis of stacked nitrogen-doped carbon nanotube cups followed by effective separation into individual cups and gold nanoparticle cork formation resulting in loaded and sealed containers.

During the last decades, changes have been observed in the frequency of different histologic subtypes of lung cancer, one of the most common causes of morbidity and mortality, with a declining proportion of squamous cell carcinomas and an increasing proportion of adenocarcinomas, particularly in developed countries. This suggests the emergence of new etiologic factors and mechanisms, including those defining the lung microenvironment, promoting tumor growth. Assuming that the lung is the main portal of entry for broadly used nanomaterials and their established proinflammatory propensities, we hypothesized that nanomaterials may contribute to changes facilitating tumor growth. Here, we report that an acute exposure to single-walled carbon nanotubes (SWCNT) induces recruitment and accumulation of lung-associated myeloid-derived suppressor cells (MDSC) and MDSC-derived production of TGFβ, resulting in upregulated tumor burden in the lung. The production of TGFβ by MDSC requires their interaction with both SWCNT and tumor cells. We conclude that pulmonary exposure to SWCNT favors the formation of a niche that supports ingrowth of lung carcinoma in vivo via activation of TGFβ production by SWCNT-attracted and -presensitized MDSC. Cancer Res; 75(8); 1615–23. ©2015 AACR.

Since 2011, an annual award system was instituted to recognize outstanding Sensors papers that are related to sensing technologies and applications and meet the aims, scope and high standards of this journal [1–4]. This year, the winners were chosen by the Section Editor-in-Chiefs of Sensors from among all the papers published in 2011 to track citations. Reviews and full research articles were considered separately. We gladly announce that the following eight papers were awarded the Sensors Best Paper Award in 2015.[...]

With the advancement of nanocarriers for drug delivery into biomedical practice, assessments of drug susceptibility to oxidative degradation by enzymatic mechanisms of inflammatory cells become important. Here, we investigate oxidative degradation of a carbon nanotube-based drug carrier loaded with Doxorubicin. We employed myeloperoxidase-catalysed and peroxynitrite-mediated oxidative conditions to mimic the respiratory burst of neutrophils and macrophages, respectively. In addition, we revealed that the cytostatic and cytotoxic effects of free Doxorubicin, but not nanotube-carried drug, on melanoma and lung carcinoma cell lines were abolished in the presence of tumor-activated myeloid regulatory cells that create unique myeloperoxidase- and peroxynitrite-induced oxidative conditions. Both ex vivo and in vitro studies demonstrate that the nanocarrier protects the drug against oxidative biodegradation.

Detection of malignant cells in tissue is a difficult hurdle in medical diagnostics and screening. Carbon nanotubes are extremely sensitive to their local environments, and nanotube-based field-effect transistors (NTFETs) provide a plethora of information regarding the mechanism of interaction with target analytes. Herein, we use a series of functionalized metal nanoparticle-decorated NTFET devices forming an array with multiple nonselective sensor units as the electronic “tongue”, sensing all five basic tastes. By extraction of selected NTFET characteristics and using linear discriminant analysis, we have successfully detected and discriminated between malignant and nonmalignant tissues and cells. We also studied the sensing mechanism and what NTFET characteristics are responsible for the variation of response between cell types, allowing for the design of future studies such as detection of malignant cells in a biopsy or the effects of malignant cells on healthy tissue.

Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Due to the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ=365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis for sensing oxygen gas in the concentration range between 300–100,000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. This work provides an example of a metal-free system for solid-gas interface sensing via a photoredox mechanism.

Hierarchical nanostructures grown directly on transparent conducting oxides hold the promise of overcoming the limitations of current semiconductor-sensitized solar cells based on random networks of nanoparticles. Here, we develop a facile substrate placement angle-dependent hydrothermal process to grow dandelion-like TiO2 nanostructures directly on transparent conductive oxides. TiO2 nanocrystals grown in solution during the synthesis process are found to promote the dandelion-like structure. By using these TiO2 nanostructures as photoanodes, Sb2S3 as the sensitizer, and P3HT as the hole-transporting material, we demonstrate fabrication of all-solid-state semiconductor-sensitized solar cells, which yield solar power conversion efficiency up to 4.71%. Electrochemical impedance spectroscopy indicates that moderate rod fusion at the base beneficially reduces electron recombination in the device. This work provides an innovative method for growing branched, one-dimensional TiO2 nanostructures that can be used for energy harvesting and storage.

One-dimensional TiO2 nanostructures that have large specific surface area have broadened their applications in solar cells and water splitting, but their synthesis still remains a challenge. In this report, vertically ordered rutile TiO2 nanowires with an ultra-high coverage density of 2.4 × 1011 cm−2 and ultra-small width of barely ∼16 nm were synthesized on transparent conducting oxide by a facile solvothermal reaction using methanol and aqueous hydrochloride as solvent. The nanowires were fabricated with Sb2S3 into solid-state solar cells, which yielded a power conversion efficiency of 2.03%. Such a photoanode showed reduced electron recombination, due to moderate wire fusion at the bottom.

We report on the reversible detection of CaptAvidin, a tyrosine modified avidin, with single-walled carbon nanotube (SWNT) field-effect transistors (FETs) noncovalently functionalized with biotin moieties using 1-pyrenebutyric acid as a linker. Binding affinities at different pH values were quantified, and the sensor’s response at various ionic strengths was analyzed. Furthermore, protein “fingerprints” of NeutrAvidin and streptavidin were obtained by monitoring their adsorption at several pH values. Moreover, gold nanoparticle decorated SWNT FETs were functionalized with biotin using 1-pyrenebutyric acid as a linker for the CNT surface and (±)-α-lipoic acid linkers for the gold surface, and reversible CaptAvidin binding is shown, paving the way for potential dual mode measurements with the addition of surface enhanced Raman spectroscopy (SERS).

In contrast to short-lived neutrophils, macrophages display persistent presence in the lung of animals after pulmonary exposure to carbon nanotubes. While effective in the clearance of bacterial pathogens and injured host cells, the ability of macrophages to “digest” carbonaceous nanoparticles has not been documented. Here, we used chemical, biochemical, and cell and animal models and demonstrated oxidative biodegradation of oxidatively functionalized single-walled carbon nanotubes via superoxide/NO* → peroxynitrite-driven oxidative pathways of activated macrophages facilitating clearance of nanoparticles from the lung.

Several lines of evidence indicate that exposure to nanoparticles (NPs) is able to modify airway immune responses, thus facilitating the development of respiratory diseases. Graphene oxide (GO) is a promising carbonaceous nanomaterial with unique physicochemical properties, envisioned for a multitude of medical and industrial applications. In this paper, we determined how exposure to GO modulates the allergic pulmonary response. Using a murine model of ovalbumin (OVA)-induced asthma, we revealed that GO, given at the sensitization stage, augmented airway hyperresponsiveness and airway remodeling in the form of goblet cell hyperplasia and smooth muscle hypertrophy. At the same time, the levels of the cytokines IL-4, IL-5, and IL-13 were reduced in broncho-alveolar lavage (BAL) fluid in GO-exposed mice. Exposure to GO during sensitization with OVA decreased eosinophil accumulation and increased recruitment of macrophages in BAL fluid. In line with the cytokine profiles, sensitization with OVA in the presence of GO stimulated the production of OVA-specific IgG2a and down-regulated the levels of IgE and IgG1. Moreover, exposure to GO increased the macrophage production of the mammalian chitinases, CHI3L1 and AMCase, whose expression is associated with asthma. Finally, molecular modeling has suggested that GO may directly interact with chitinase, affecting AMCase activity, which has been directly proven in our studies. Thus, these data show that GO exposure attenuates Th2 immune response in a model of OVA-induced asthma, but leads to potentiation of airway remodeling and hyperresponsiveness, with the induction of mammalian chitinases.

Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150-1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed.