Carbon dots versus nano-carbon/organic hybrids - dramatically different behaviors in fluorescence sensing of metal cations with structural and mechanistic implications.

Carbon dots (CDots) are defined as surface-passivated small carbon nanoparticles, with the effective passivation generally achieved by organic functionalization. Photoexcited CDots are both potent electron donors and acceptors, and their characteristic bright and colorful fluorescence emissions make them excellent fluorescence sensors for organic analytes and metal ions. For the latter extraordinarily low detection limits based on extremely efficient quenching of fluorescence intensities by the targeted metal cations have been observed and reported in the literature. However, all of the dot samples in those reported studies were made from "one-pot" carbonization of organic precursors mostly under rather mild processing conditions, unlikely to be sufficient for the required level of carbonization. Those dot samples should therefore be more appropriately considered as "nano-carbon/organic hybrids", characterized structurally as being highly porous and spongy, which must be playing a dominating role in the reported sensing results. In this study, we compared the dot samples from carbonization syntheses under similarly mild and also more aggressive processing conditions with the classically defined and structured CDots for the fluorescence sensing of copper(ii) cations in aqueous solutions. The observed dramatic decoupling between quenching results for fluorescence intensities and lifetimes of the carbonization samples, with the former being extraordinary and the latter within the diffusion controlled limit, suggested that the quenching of fluorescence intensities was greatly affected by the higher local quencher concentrations than the bulk associated with the porous and spongy sample structures, especially for the sample from carbonization under too mild processing conditions. The major differences between the classical CDots and the nano-carbon/organic hybrids are highlighted, and the tradeoffs between sensitivity and accuracy or reproducibility in the use of the latter for fluorescence sensing are discussed.

Carbon Dots: Zero-Dimensional Carbon Allotrope with Unique Photoinduced Redox Characteristics.

Carbon dots (CDots) exploit and enhance the intrinsic properties of small carbon nanoparticles. Their optical absorptions and photoinduced redox characteristics are competitive with those of conventional semiconductor quantum dots at one end and fullerenes and other carbon nanomaterials at the other. Highlighted in this mini review are the effective photon harvesting over a broad spectral range by CDots and their subsequent excited-state charge transfer processes and interactions, which have enabled their use as sensors, for photodynamic effects, and in various energy conversion technologies.

Zero-Dimensional Carbon Allotropes-Carbon Nanoparticles Versus Fullerenes in Functionalization by Electronic Polymers for Different Optical and Redox Properties.

Fullerene cages are known as being able to participate in radical initiated copolymerization reactions with vinyl monomers for polymer-functionalized fullerenes. In this work, poly(N-vinylcarbazole) (PVK) was selected as a representative of electronic polymers in the functionalization of fullerene C60 by the same copolymerization reaction to yield the PVK-C60. Similarly found was that small carbon nanoparticles could also participate in the same copolymerization reaction for the nanoparticles to be surface-functionalized and -passivated by the attached PVK polymers, which are structurally adhering to the general definition on carbon dots (CDots), thus PVK-CDots. In the comparison between PVK-CDots and PVK-C60, the former was found to be more absorptive and therefore more effective in photon harvesting across the visible spectral region and also brightly fluorescent, orders of magnitude more so than the latter. Similar to the PVK-C60 and C60 cages in general, the PVK-CDots exhibited significant photoinduced electron accepting characteristics and, at the same time, also extraordinary electron donating abilities that are not available to fullerenes. Because fullerene-based composites with electronic polymers including PVK have found significant applications in optoelectronic devices and systems, the prospect of CDots represented by the PVK-CDots for similar purposes is discussed.

Chemical and Morphological Inhomogeneity of Aluminum Metal and Oxides from Soft X-ray Spectromicroscopy.

Oxygen and aluminum K-edge X-ray absorption spectroscopy (XAS), imaging from a scanning transmission X-ray microscope (STXM), and first-principles calculations were used to probe the composition and morphology of bulk aluminum metal, α- and γ-Al2O3, and several types of aluminum nanoparticles. The imaging results agreed with earlier transmission electron microscopy studies that showed a 2 to 5 nm thick layer of Al2O3 on all the Al surfaces. Spectral interpretations were guided by examination of the calculated transition energies, which agreed well with the spectroscopic measurements. Features observed in the experimental O and Al K-edge XAS were used to determine the chemical structure and phase of the Al2O3 on the aluminum surfaces. For unprotected 18 and 100 nm Al nanoparticles, this analysis revealed an oxide layer that was similar to γ-Al2O3 and comprised of both tetrahedral and octahedral Al coordination sites. For oleic acid-protected Al nanoparticles, only tetrahedral Al oxide coordination sites were observed. The results were correlated to trends in the reactivity of the different materials, which suggests that the structures of different Al2O3 layers have an important role in the accessibility of the underlying Al metal toward further oxidation. Combined, the Al K-edge XAS and STXM results provided detailed chemical information that was not obtained from powder X-ray diffraction or imaging from a transmission electron microscope.

Photoexcited State Properties of Carbon Dots from Thermally Induced Functionalization of Carbon Nanoparticles.

Carbon dots are small carbon nanoparticles with various surface passivation schemes, in which more effective has been the deliberate chemical functionalization of the nanoparticles for brighter fluorescence emissions, though the synthesis method is more tedious and subject to some limitations in the selection of functionalization molecules. Another more popular synthesis method has been the carbonization of organic species, with the method being more efficient and versatile, but less controllable in the synthesis and for the desired dot structure and performance. In this work, a hybrid approach combining the advantageous characteristics of the two synthesis methods was applied to the preparation of carbon dots with polyethyleneimine (PEI) for surface passivation, where pre-processed and selected small carbon nanoparticles were functionalized with PEI in microwave-induced thermal reactions. The optical absorption and fluorescence emission properties were evaluated, and the results suggested that the carbon dots thus prepared shared the same photoexcited state characteristics with those from the deliberate chemical functionalization, including comparable fluorescence colors and other properties. A further demonstration on the similarity in photoexcited state properties was based on the same visible light-activated bactericidal functions of the PEI-carbon dots as those found in carbon dots from the deliberate chemical functionalization. The advantages and potential limitations of the hybrid approach for more controllable yet versatile and efficient syntheses of carbon dots are highlighted and discussed.

Enhanced Fluorescence Properties of Carbon Dots in Polymer Films.

Carbon dots of small carbon nanoparticles surface-functionalized with 2,2'-(ethylenedioxy)bis(ethylamine) (EDA) were synthesized, and the as-synthesized sample was separated on an aqueous gel column to obtain fractions of the EDA-carbon dots with different fluorescence quantum yields. As already discussed in the literature, the variations in fluorescence performance among the fractions were attributed to the different levels and/or effectiveness of the surface functionalization-passivation in the carbon dots. These fractions, as well as carbon nanoparticles without any deliberate surface functionalization, were dispersed into poly(vinyl alcohol) (PVA) for composite films. In the PVA film matrix, the carbon dots and nanoparticles exhibited much enhanced fluorescence emissions in comparison with their corresponding aqueous solutions. The increased fluorescence quantum yields in the films were determined quantitatively by using a specifically designed and constructed film sample holder in the emission spectrometer. The observed fluorescence decays of the EDA-carbon dots in film and in solution were essentially the same, suggesting that the significant enhancement in fluorescence quantum yields from solution to film is static in nature. Mechanistic implications of the results, including a rationalization in terms of the compression effect on the surface passivation layer (similar to a soft corona) in carbon dots when embedded in the more restrictive film environment resulting in more favorable radiative recombinations of the carbon particle surface-trapped electrons and holes, and also potential technological applications of the brightly fluorescent composite films are highlighted and discussed.

Infrared spectroscopy of Mg-CO2 and Al-CO2 complexes in helium nanodroplets.

The catalytic reduction of CO2 to produce hydrocarbon fuels is a topic that has gained significant attention. Development of efficient catalysts is a key enabler to such approaches, and metal-based catalysts have shown promise towards this goal. The development of a fundamental understanding of the interactions between CO2 molecules and metal atoms is expected to offer insight into the chemistry that occurs at the active site of such catalysts. In the current study, we utilize helium droplet methods to assemble complexes composed of a CO2 molecule and a Mg or Al atom. High-resolution infrared (IR) spectroscopy and optically selected mass spectrometry are used to probe the structure and binding of the complexes, and the experimental observations are compared with theoretical results determined from ab initio calculations. In both the Mg-CO2 and Al-CO2 systems, two IR bands are obtained: one assigned to a linear isomer and the other assigned to a T-shaped isomer. In the case of the Mg-CO2 complexes, the vibrational frequencies and rotational constants associated with the two isomers are in good agreement with theoretical values. In the case of the Al-CO2 complexes, the vibrational frequencies agree with theoretical predictions; however, the bands from both structural isomers exhibit significant homogeneous broadening sufficient to completely obscure the rotational structure of the bands. The broadening is consistent with an upper state lifetime of 2.7 ps for the linear isomer and 1.8 ps for the T-shaped isomer. The short lifetime is tentatively attributed to a prompt photo-induced chemical reaction between the CO2 molecule and the Al atom comprising the complex.

Carbon quantum dots and applications in photocatalytic energy conversion.

Quantum dots (QDs) generally refer to nanoscale particles of conventional semiconductors that are subject to the quantum-confinement effect, though other nanomaterials of similar optical and redox properties are also named as QDs even in the absence of strictly defined quantum confinement. Among such nanomaterials that have attracted tremendous recent interest are carbon dots, which are small carbon nanoparticles with some form of surface passivation, and graphene quantum dots in various configurations. In this article, we highlight these carbon-based QDs by focusing on their syntheses, on their photoexcited state properties and redox processes, and on their applications as photocatalysts in visible-light carbon dioxide reduction and in water-splitting, as well as on their mechanistic similarities and differences.

Helium droplet calorimetry of strongly bound species: carbon clusters from C2 to C12.

Helium droplet beam methods are a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. In recent years, methods have been developed to utilize helium droplets as nano-calorimeters to measure the binding energies of weakly bound complexes assembled within the droplet. In the current investigation we extend the helium droplet calorimetry approach to the study of a very strongly bound system: carbon clusters which are bound by several eV per atom. We utilize laser heating of bulk carbon samples to dope the helium droplets with evaporated carbon species. Depending on the laser target, the vaporization plume is found to consist primarily of C3 alone or C2 and C3. These species are sequentially captured by the droplet and assembled into larger carbon clusters in a stepwise manner. The assembled C(n) clusters are detected via mass spectrometry of the doped droplets and the droplet sizes required to detect the various carbon clusters observed are used to estimate the reaction energies of the associated assembly pathways. The helium droplet data qualitatively reflect the trends in assembly energetics, but at first glance appear to yield energies that differ dramatically from theoretical values. Statistical modeling of the helium droplet calorimetry experiment reconciles the differences quantitatively. Our modeling also generates a calibration curve that relates the assembly/reaction energy and threshold mean droplet size over a range of energies from van der Waals interactions to chemical bonding, enabling helium droplet calorimetry methods to be applied quantitatively to a large number of systems.

Migration of silver nanoparticles from silver decorated graphene oxide to other carbon nanostructures.

Decoration of graphene oxide (GO) sheets with Ag nanoparticles has been demonstrated using a simple sonication technique. By changing the ratio between Ag-decorated-GO and GO, a series of Ag-decorated-GO samples with different Ag loadings were synthesized. These Ag-decorated-GO samples were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) spectroscopy, thermal gravimetric analysis (TGA), and differential scanning calorimetric (DSC) techniques. TEM analysis showed that Ag nanoparticles were evenly distributed on GO sheets, and the size analysis of the particles using multiple TEM images indicated that Ag nanoparticles have an average size of 6-7 nm. TEM analysis also showed that Ag nanoparticles migrated from Ag-decorated-GO to later-added GO sheets. In XRD, all the Ag-decorated GO samples showed the characteristic peaks related to GO and face-centered-cubic (fcc) Ag. Thermal analysis showed peaks related to the combustion of graphitic carbon shifted to lower temperatures after GO sheets were decorated with Ag nanoparticles. In addition, further experiments performed using Ag-decorated-GO and multiwalled carbon nanotubes (MWNTs) confirmed that Ag nanoparticles migrated from Ag-decorated-GO to later-added carbon nanotubes without a noticeable coalescence of Ag nanoparticles.

Visible-light photoconversion of carbon dioxide into organic acids in an aqueous solution of carbon dots.

Carbon "quantum" dots (or carbon dots) have emerged as a new class of optical nanomaterials. Beyond the widely reported bright fluorescence emissions in carbon dots, their excellent photoinduced redox properties that resemble those found in conventional semiconductor nanostructures are equally valuable, with photon-electron conversion applications from photovoltaics to CO2 photocatalytic reduction. In this work we used gold-doped carbon dots from controlled synthesis as water-soluble catalysts for a closer examination of the visible-light photoconversion of CO2 into small organic acids, including acetic acid (for which the reduction requires many more electrons than that for formic acid) and, more interestingly, for the significantly enhanced photoconversion with higher CO2 pressures over an aqueous solution of the photocatalysts. The results demonstrate the nanoscale semiconductor-equivalent nature of carbon dots, with excellent potential in energy conversion applications.

Efficient fluorescence quenching in carbon dots by surface-doped metals--disruption of excited state redox processes and mechanistic implications.

The carbon dots in this study were small carbon nanoparticles with the particle surface functionalized by oligomeric poly(ethylene glycol) diamine molecules. Upon photoexcitation, the brightly fluorescent carbon dots in aqueous solution served the function of excellent electron donors to reduce platinum(IV) and gold(III) compounds into their corresponding metals to be deposited on the dot surface. The deposited metals even in very small amounts were found to have dramatic quenching effects on the fluorescence emission intensities, but essentially no effects on the observed fluorescence decays. The obviously exclusive near-neighbor static quenching could be attributed to the disruption of electron-hole radiative recombinations (otherwise responsible for the fluorescence emissions in carbon dots). The results provide important evidence for the availability of photogenerated electrons that could be harvested for productive purposes, which in turn supports the current mechanistic framework on fluorescence emission and photoinduced redox properties of carbon dots.

A threshold-based approach to calorimetry in helium droplets: measurement of binding energies of water clusters.

Helium droplet beam methods have emerged as a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. We have developed a method to measure the binding energies of clusters assembled in helium droplets by determining the minimum droplet sizes required to assemble and detect selected clusters in the spectrum of the doped droplet beam. The differences in the droplet sizes required between the various multimers are then used to estimate the incremental binding energies. We have applied this method to measure the binding energies of cyclic water clusters from the dimer to the tetramer. We obtain measured values of D(0) that are in agreement with theoretical estimates to within ∼20%. Our results suggest that this threshold-based approach should be generally applicable using either mass spectrometry or optical spectroscopy techniques for detection, provided that the clusters selected for study are at least as strongly bound as those of water, and that a peak in the overall spectrum of the beam corresponding only to the cluster chosen (at least in the vicinity of the threshold) can be located.

Aqueously dispersed silver nanoparticle-decorated boron nitride nanosheets for reusable, thermal oxidation-resistant surface enhanced Raman spectroscopy (SERS) devices.

The impurity-free aqueous dispersions of boron nitride nanosheets (BNNS) allowed the facile preparation of silver (Ag) nanoparticle-decorated BNNS by chemical reduction of an Ag salt with hydrazine in the presence of BNNS. The resultant Ag-BNNS nanohybrids remained dispersed in water, allowing convenient subsequent solution processing. By using substrate transfer techniques, Ag-BNNS nanohybrid thin film coatings on quartz substrates were prepared and evaluated as reusable surface enhanced Raman spectroscopy (SERS) sensors that were robust against repeated solvent washing. In addition, because ofthe unique thermal oxidation-resistant properties of the BNNS, the sensor devices may be readily recycled by short-duration high temperature air oxidation to remove residual analyte molecules in repeated runs. The limiting factor associated with the thermal oxidation recycling process was the Ostwald ripening effect of Ag nanostructures.

Carbon nanoparticles as chromophores for photon harvesting and photoconversion.

Carbon nanomaterials have generated a tremendous amount of attention in the scientific community. While most of the research and development efforts have been on fullerenes, carbon nanotubes, and graphene sheets, carbon nanoparticles (which are often considered as impurities or unwanted complications in the other carbon nanomaterials) have recently emerged as a unique class of highly fluorescent nano-dots. However, little or no attention has been paid to potential uses of carbon nanoparticles as chromophores in photochemical reactions or for photon harvesting and photoconversion in general. In the study reported herein we demonstrate the chromophore-equivalent functions of aqueous-suspended small carbon nanoparticles in harvesting visible photons for the reductive coating of the nanoparticles with silver and gold and, as a result, the preparation of unique carbon-noble-metal core-shell nanostructures.

Graphene oxide: a nonspecific enhancer of cellular growth.

There have been multiple conflicting reports about the biocompatibility and antimicrobial activity of graphene oxide. To address this, we conducted a study to characterize the antimicrobial properties of graphene oxide (GO) and its biocompatibility with mammalian cells. When GO was added to a bacterial culture at 25 µg/mL, the results showed that bacteria grew faster and to a higher optical density than cultures without GO. Scanning electron microscopy indicated that bacteria formed dense biofilms in the presence of GO. This was shown by a large mass of aggregated cells and extracellular polymeric material. Bacterial growth on filters coated with 25 and 75 µg of GO grew 2 and 3 times better than on filters without GO. Closer analysis showed that bacteria were able to attach and proliferate preferentially in areas containing the highest GO levels. Graphene oxide films failed to produce growth inhibition zones around them, indicating a lack of antibacterial properties. Also, bacteria were able to grow on GO films to 9.5 × 10(9) cells from an initial inoculation of 1.0 × 10(6), indicating that it also lacks bacteriostatic activity. Thus, silver-coated GO films were able to produce clearing zones and cell death. Also, graphene oxide was shown to greatly enhance the attachment and proliferation of mammalian cells. This study conclusively demonstrates that graphene oxide does not have intrinsic antibacterial, bacteriostatic, and cytotoxic properties in both bacteria and mammalian cells. Furthermore, graphene oxide acts as a general enhancer of cellular growth by increasing cell attachment and proliferation.

Aluminum nanoparticles capped by polymerization of alkyl-substituted epoxides: ratio-dependent stability and particle size.

We report here on the polymerization of epoxide monomers on incipient aluminum nanoparticle cores and the effects of changing the epoxide-capping precursor and the metallic monomer ratio on the resultant stability and particle size of passivated and capped aluminum nanoparticles. When altering the ratio of aluminum to cap monomer precursor, nanoparticles capped with epoxydodecane, epoxyhexane, and epoxyisobutane show a clear decreasing trend in stability with decreasing alkane substituent length. The nanoparticle core size was unaffected by cap ratio or composition. PXRD (powder X-ray diffraction) and DSC/TGA (differential scanning calorimetry/thermal gravimetric analysis) confirm the presence of successfully passivated face-centered cubic (fcc) aluminum nanoparticles. We also report preliminary results from ATR-FTIR (attenuated total reflectance-Fourier transform infrared), (13)C CPMAS (cross-polarization/magic-angle spinning), and (27)Al MAS solid-state NMR (nuclear magnetic resonance) measurements. The most stable aluminum nanoparticle-polyether core-shell nanoparticles are found at an Al:monomer mole ratio of 10:1 with an active Al(0) content of 94%.

Carbon nanoparticles as visible-light photocatalysts for efficient CO2 conversion and beyond.

Increasing atmospheric CO(2) levels have generated much concern, driving the ongoing carbon sequestration effort. A compelling CO(2) sequestration option is its photocatalytic conversion to hydrocarbons, for which the use of solar irradiation represents an ultimate solution. Here we report a new strategy of using surface-functionalized small carbon nanoparticles to harvest visible photons for subsequent charge separation on the particle surface in order to drive the efficient photocatalytic process. The aqueous solubility of the catalysts enables photoreduction under more desirable homogeneous reaction conditions. Beyond CO(2) conversion, the nanoscale carbon-based photocatalysts are also useful for the photogeneration of H(2) from water under similar conditions.

Classification of jet fuels by fuzzy rule-building expert systems applied to three-way data by fast gas chromatography--fast scanning quadrupole ion trap mass spectrometry.

A fast method that can be used to classify unknown jet fuel types or detect possible property changes in jet fuel physical properties is of paramount interest to national defense and the airline industries. While fast gas chromatography (GC) has been used with conventional mass spectrometry (MS) to study jet fuels, fast GC was combined with fast scanning MS and used to classify jet fuels into lot numbers or origin for the first time by using fuzzy rule-building expert system (FuRES) classifiers. In the process of building classifiers, the data were pretreated with and without wavelet transformation and evaluated with respect to performance. Principal component transformation was used to compress the two-way data images prior to classification. Jet fuel samples were successfully classified with 99.8 ± 0.5% accuracy for both with and without wavelet compression. Ten bootstrapped Latin partitions were used to validate the generalized prediction accuracy. Optimized partial least squares (o-PLS) regression results were used as positively biased references for comparing the FuRES prediction results. The prediction results for the jet fuel samples obtained with these two methods were compared statistically. The projected difference resolution (PDR) method was also used to evaluate the fast GC and fast MS data. Two batches of aliquots of ten new samples were prepared and run independently 4 days apart to evaluate the robustness of the method. The only change in classification parameters was the use of polynomial retention time alignment to correct for drift that occurred during the 4-day span of the two collections. FuRES achieved perfect classifications for four models of uncompressed three-way data. This fast GC/fast MS method furnishes characteristics of high speed, accuracy, and robustness. This mode of measurement may be useful as a monitoring tool to track changes in the chemical composition of fuels that may also lead to property changes.

Classification of jet fuel properties by near-infrared spectroscopy using fuzzy rule-building expert systems and support vector machines.

Monitoring the changes of jet fuel physical properties is important because fuel used in high-performance aircraft must meet rigorous specifications. Near-infrared (NIR) spectroscopy is a fast method to characterize fuels. Because of the complexity of NIR spectral data, chemometric techniques are used to extract relevant information from spectral data to accurately classify physical properties of complex fuel samples. In this work, discrimination of fuel types and classification of flash point, freezing point, boiling point (10%, v/v), boiling point (50%, v/v), and boiling point (90%, v/v) of jet fuels (JP-5, JP-8, Jet A, and Jet A1) were investigated. Each physical property was divided into three classes, low, medium, and high ranges, using two evaluations with different class boundary definitions. The class boundaries function as the threshold to alarm when the fuel properties change. Optimal partial least squares discriminant analysis (oPLS-DA), fuzzy rule-building expert system (FuRES), and support vector machines (SVM) were used to build the calibration models between the NIR spectra and classes of physical property of jet fuels. OPLS-DA, FuRES, and SVM were compared with respect to prediction accuracy. The validation of the calibration model was conducted by applying bootstrap Latin partition (BLP), which gives a measure of precision. Prediction accuracy of 97 ± 2% of the flash point, 94 ± 2% of freezing point, 99 ± 1% of the boiling point (10%, v/v), 98 ± 2% of the boiling point (50%, v/v), and 96 ± 1% of the boiling point (90%, v/v) were obtained by FuRES in one boundaries definition. Both FuRES and SVM obtained statistically better prediction accuracy over those obtained by oPLS-DA. The results indicate that combined with chemometric classifiers NIR spectroscopy could be a fast method to monitor the changes of jet fuel physical properties.