Advances in Studies of Boron Nitride Nanosheets and Nanocomposites for Thermal Transport and Related Applications.

Hexagonal boron nitride (h-BN) and exfoliated nanosheets (BNNs) not only resemble their carbon counterparts graphite and graphene nanosheets in structural configurations and many excellent materials characteristics, especially the ultra-high thermal conductivity, but also offer other unique properties such as being electrically insulating and extreme chemical stability and oxidation resistance even at elevated temperatures. In fact, BNNs as a special class of 2-D nanomaterials have been widely pursued for technological applications that are beyond the reach of their carbon counterparts. Highlighted in this article are significant recent advances in the development of more effective and efficient exfoliation techniques for high-quality BNNs, the understanding of their characteristic properties, and the use of BNNs in polymeric nanocomposites for thermally conductive yet electrically insulating materials and systems. Major challenges and opportunities for further advances in the relevant research field are also discussed.

Boron nitride nanomaterials for thermal management applications.

Hexagonal boron nitride nanosheets (BNNs) are analogous to their two-dimensional carbon counterparts in many materials properties, in particular, ultrahigh thermal conductivity, but also offer some unique attributes, including being electrically insulating, high thermal stability, chemical and oxidation resistance, low color, and high mechanical strength. Significant recent advances in the production of BNNs, understanding of their properties, and the development of polymeric nanocomposites with BNNs for thermally conductive yet electrically insulating materials and systems are highlighted herein. Major opportunities and challenges for further studies in this rapidly advancing field are also discussed.

Photoluminescence properties of graphene versus other carbon nanomaterials.

Photoluminescent nanomaterials continue to garner research attention because of their many applications. For many years, researchers have focused on quantum dots (QDs) of semiconductor nanocrystals for their excellent performance and predictable fluorescence color variations that depend on the sizes of the nanocrystals. Even with these advantages, QDs can present some major limitations, such as the use of heavy metals in the high-performance semiconductor QDs. Therefore, researchers continue to be interested in developing new QDs or related nanomaterials. Recently, various nanoscale configurations of carbon have emerged as potential new platforms in the development of brightly photoluminescent materials. As a perfect π-conjugated single sheet, graphene lacks electronic bandgaps and is not photoluminescent. Therefore, researchers have created energy bandgaps within graphene as a strategy to impart fluorescence emissions. Researchers have explored many experimental techniques to introduce bandgaps, such as cutting graphene sheets into small pieces or manipulating the π electronic network to form quantum-confined sp(2) "islands" in a graphene sheet, which apparently involve the formation or exploitation of structural defects. In fact, defects in graphene materials not only play a critical role in the creation of bandgaps for emissive electronic transitions, but also contribute directly to the bright photoluminescence emissions observed in these materials. Researchers have found similar defect-derived photoluminescence in carbon nanotubes and small carbon nanoparticles, dubbed carbon "quantum" dots or "carbon dots". However, they have not systematically examined the emissions properties of these different yet related carbon nanomaterials toward understanding their mechanistic origins. In this Account, we examine the spectroscopic features of the observed photoluminescence emissions in graphene materials. We associate the structural characteristics in the underlying graphene materials with those emission properties as a way of classifying them into two primary categories: emissions that originate from created or induced energy bandgaps in a single graphene sheet and emissions that are associated with defects in single- and/or multiple-layer graphene. We highlight the similarities and differences between the observed photoluminescence properties of graphene materials and those found in other carbon nanomaterials including carbon dots and surface defect-passivated carbon nanotubes, and we discuss their mechanistic implications.

Crosslinked carbon dots as ultra-bright fluorescence probes.

Carbon dots (surface-passivated small carbon nanoparticles) are crosslinked to result in fluorescence probes containing one or multiple dots. For the single-dot probes, the crosslinking further stabilizes the dot structure, while for those packed with multiple dots, the individual probe imaging results demonstrate that the fluorescence properties are additive, with more dots for higher emission intensities in a proportional fashion, thus enabling the preparation of ultra-bright fluorescence probes.

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.

Polymer/boron nitride nanocomposite materials for superior thermal transport performance.

Boron nitride nanosheets were dispersed in polymers to give composite films with excellent thermal transport performances approaching the record values found in polymer/graphene nanocomposites. Similarly high performance at lower BN loadings was achieved by aligning the nanosheets in poly(vinyl alcohol) matrix by simple mechanical stretching (see picture).

Efficient Route for the Preparation of Composite Resin Incorporating Silver Nanoparticles with Enhanced Antibacterial Properties.

An efficient and facile route for the immobilization of silver (Ag) nanoparticles (NPs) in anion exchange resin beads with different silver loading is proposed. In this method, BH4- ions were first introduced into chloride-form resin through an ion exchange process with Cl- ions, followed by in-situ chemical reduction of Ag+ ions at the surface of the resin to form metallic Ag nanoparticles. Morphology and structure of the resulting Ag-resin nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Fourier transform infra-red (FTIR), inductively coupled plasma-optical emission spectrometry (ICP-OES), and thermogravimetry analysis (TGA). The results confirmed the presence of smaller diameter Ag NPs incorporated into the resin beads having an average diameter on the order of 10 nm with a few Ag NP clusters of 20-100 nm. The nanoparticles were homogeneously distributed throughout the resin. There were no dramatic increases in average particle sizes even at very high Ag loadings. The resin retained its structure and stability, allowing higher stability of immobilized AgNPs than the colloidal ones. The Ag-loaded resins made with 50 mM AgNO3 were tested for antibacterial activity in vitro against Escherichia coli (E. coli) as a model microbial contaminant in water. Results showed greater than 99% bacterial inhibition within 3 h of exposure. The resin form offers greater ease of handling, long-term storage at room temperature, reusability in repeated reactions, and reduces the risk of environmental contamination.

Poly(ethylene glycol)-conjugated multi-walled carbon nanotubes as an efficient drug carrier for overcoming multidrug resistance.

The acquisition of multidrug resistance poses a serious problem in chemotherapy, and new types of transporters have been actively sought to overcome it. In the present study, poly(ethylene glycol)-conjugated (PEGylated) multi-walled carbon nanotubes (MWCNTs) were prepared and explored as drug carrier to overcome multidrug resistance. The prepared PEGylated MWCNTs penetrated into mammalian cells without damage plasma membrane, and its accumulation did not affect cell proliferation and cell cycle distribution. More importantly, PEGylated MWCNTs accumulated in the multidrug-resistant cancer cells as efficient as in the sensitive cancer cells. Intracellular translocation of PEGylated MWCNTs was visualized in both multidrug-resistant HepG2-DR cells and sensitive HepG2 cells, as judged by both fluorescent and transmission electron microscopy. PEGylated MWCNTs targeted cancer cells efficiently and multidrug-resistant cells failed to remove the intracellular MWCNTs. However, if used in combination with drugs without conjugation, PEGylated MWCNTs prompted drug efflux in MDR cells by stimulating the ATPase activity of P-glycoprotein. This study suggests that PEGylated MWCNTs can be developed as an efficient drug carrier to conjugate drugs for overcoming multidrug resistance in cancer chemotherapy.

Separated metallic and semiconducting single-walled carbon nanotubes: opportunities in transparent electrodes and beyond.

Ever since the discovery of single-walled carbon nanotubes (SWNTs), there have been many reports and predictions on their superior properties for use in a wide variety of potential applications. However, an SWNT is either metallic or semiconducting; these properties are distinctively different in electrical conductivity and many other aspects. The available bulk-production methods generally yield mixtures of metallic and semiconducting SWNTs, despite continuing efforts in metallicity-selective nanotube growth. Presented here are significant advances and major achievements in the development of postproduction separation methods, which are now capable of harvesting separated metallic and semiconducting SWNTs from different production sources with sufficiently high enrichment and quantities for satisfying at least the needs in research and technological explorations. Opportunities and some available examples for the use of metallic SWNTs in transparent electrodes and semiconducting SWNTs in various device nanotechnologies are highlighted and discussed.

On the myth of "red/near-IR carbon quantum dots" from thermal processing of specific colorless organic precursors.

Carbon dots were originally found and reported as surface-passivated small carbon nanoparticles, where the effective surface passivation was the chemical functionalization of the carbon nanoparticles with organic molecules. Understandably, the very broad optical absorptions of carbon dots are largely the same as those intrinsic to the carbon nanoparticles, characterized by progressively decreasing absorptivities from shorter to longer wavelengths. Thus, carbon dots are generally weak absorbers in the red/near-IR and correspondingly weak emitters with low quantum yields. Much effort has been made on enhancing the optical performance of carbon dots in the red/near-IR, but without meaningful success due to the fact that optical absorptivities defined by Mother Nature are in general rather inert to any induced alterations. Nevertheless, there were shockingly casual claims in the literature on the major success in dramatically altering the optical absorption profiles of "carbon dots" by simply manipulating the dot synthesis to produce samples of some prominent optical absorption bands in the red/near-IR. Such claims have found warm receptions in the research field with a desperate need for carbon dots of the same optical performance in the red/near-IR as that in the green and blue. However, by looking closely at the initially reported synthesis and all its copies in subsequent investigations on the "red/near-IR carbon dots", one would find that the "success" of the synthesis by thermal or hydrothermal carbonization processing requires specific precursor mixtures of citric acid with formamide or urea. In the study reported here, the systematic investigation included precursor mixtures of citric acid with not only formamide or urea but also their partially methylated or permethylated derivatives for the carbonization processing under conditions similar to and beyond those commonly used and reported in the literature. Collectively all of the results are consistent only with the conclusion that the origins of the observed red/near-IR optical absorptions in samples from some of the precursor mixtures must be molecular chromophores from thermally induced chemical reactions, nothing to do with any nanoscale carbon entities produced by carbonization.

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.

Effective purification of single-walled carbon nanotubes with reversible noncovalent functionalization.

An effective purification method for single-walled carbon nanotubes (SWNTs) based on a combination of oxidative acid treatment and reversible noncovalent functionalization with 1-pyreneacetic acid is reported. The functionalization was selective toward the nanotubes, allowing a nearly complete removal of residual metal catalysts and carbonaceous impurities. The resulting highly pure SWNTs remained solvent-dispersible, a valuable feature to potential applications that require solvent-based processing. The functionalization agent could be recovered quantitatively and reused. Effects of the purification process on the composition and properties of the nanotube sample were evaluated.

Carbon Dots as Potent Antimicrobial Agents.

Carbon dots (CDots) have emerged to represent a highly promising new platform for visible/natural light-activated microbicidal agents. In this article, the syntheses, structures, and properties of CDots are highlighted, representative studies on their activities against bacteria, fungi, and viruses reviewed, and the related mechanistic insights discussed. Also highlighted and discussed are the excellent opportunities for potentially extremely broad applications of this new platform, including theranostics uses.

Dispersion of high-quality boron nitride nanosheets in polyethylene for nanocomposites of superior thermal transport properties.

High-quality boron nitride nanosheets (BNNs) characterized by large aspect ratios and less defective surfaces and structures are in demand for thermal management and other uses that exploit the uniquely advantageous properties of boron nitride, such as being highly thermally conductive yet electrically insulating and extreme chemical and thermal stabilities. In this study, an ammonia-assisted exfoliation processing method was developed and applied to the preparation of high-quality BNNs. As a demonstration of the excellent potential of these nanomaterials, the BNNs were dispersed in polyethylene polymers for nanocomposite films of superior thermal transport performance at levels significantly beyond the state of the art in the literature. Effects of crosslinking in the nanocomposite film structure on thermal transport were also explored and favorable outcomes were achieved.

Carbon dots for optical imaging in vivo.

It was found and recently reported that small carbon nanoparticles can be surface-passivated by organic or biomolecules to become strongly fluorescent. These fluorescent carbon nanoparticles, dubbed "carbon dots", can be successfully used for in vitro cell imaging with both one- and two-photon excitations, as already demonstrated in the literature. Here we report the first study using carbon dots for optical imaging in live mice. The results suggest that the carbon dots remain strongly fluorescent in vivo, which, coupled with their biocompatibility and nontoxic characteristics, might offer great potential for imaging and related biomedical applications.

Biodefunctionalization of functionalized single-walled carbon nanotubes in mice.

Chemically modified carbon nanotubes with hydrophilic functionalities such as polyethylene glycols (PEGs) are widely pursued for potential biological and biomedical applications. In this study, PEGylated single-walled carbon nanotubes (PEG-SWNT) were intravenously administrated into mice to study their biodefunctionalization in vivo by using complementary Raman and photoluminescence measurements. There was meaningful defunctionalization of PEG-SWNT in liver over time, but not in spleen under similar conditions. The evidence from spectroscopic characterization and analyses is presented, and mechanistic implications are discussed.

Photoinduced electron transfers with carbon dots.

The photoluminescence in carbon dots (surface-passivated small carbon nanoparticles) could be quenched efficiently by electron acceptor or donor molecules in solution, namely that photoexcited carbon dots are both excellent electron donors and excellent electron acceptors, thus offering new opportunities for their potential uses in light energy conversion and related applications.

Polymer functionalization and solubilization of carbon nanosheets.

Few-layer graphene materials or "carbon nanosheets" were covalently functionalized with poly(vinyl alcohol) via ester linkages, and the resulting functionalized sample became soluble, allowing solution-phase processing for various purposes such as the fabrication of polymer-carbon nanosheets composites containing no dispersion agents or any other foreign substances.

Metallic single-walled carbon nanotubes for conductive nanocomposites.

This article reports an unambiguous demonstration that bulk-separated metallic single-walled carbon nanotubes offer superior performance (consistently and substantially better than the as-produced nanotube sample) in conductive composites with poly(3-hexylthiophene) and also in transparent conductive coatings based on PEDOT:PSS. The results serve as a validation on the widely held view that the carbon nanotubes are competitive in various technologies currently dominated by conductive inorganic materials (such as indium tin oxide).

Single-walled carbon nanotube as a unique scaffold for the multivalent display of sugars.

Single-walled carbon nanotube (SWNT) is a pseudo-one-dimensional nanostructure capable of carrying/displaying a large number of bioactive molecules and species in aqueous solution. In this work, a series of dendritic beta-D-galactopyranosides and alpha-D-mannopyranosides with a terminal amino group were synthesized and used for the functionalization of SWNTs, which targeted the defect-derived carboxylic acid moieties on the nanotube surface. The higher-order sugar dendrons were more effective in the solubilization of SWNTs, with the corresponding functionalized nanotube samples of improved aqueous solubility characteristics. Through the functionalization, the nanotube apparently serves as a unique scaffold for displaying multiple copies of the sugar molecules in pairs or quartets. Results on the synthesis and characterization of these sugar-functionalized SWNTs and their biological evaluations in binding assays with pathogenic Escherichia coli and with Bacillus subtilis (a nonvirulent simulant for Bacillus anthracis or anthrax) spores are presented and discussed.