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.

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.

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.

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.

Visible-Light-Activated Bactericidal Functions of Carbon "Quantum" Dots.

Carbon dots, generally defined as small carbon nanoparticles with various surface passivation schemes, have emerged as a new class of quantum-dot-like nanomaterials, with their optical properties and photocatalytic functions resembling those typically found in conventional nanoscale semiconductors. In this work, carbon dots were evaluated for their photoinduced bactericidal functions, with the results suggesting that the dots were highly effective in bacteria-killing with visible-light illumination. In fact, the inhibition effect could be observed even simply under ambient room lighting conditions. Mechanistic implications of the results are discussed and so are opportunities in the further development of carbon dots into a new class of effective visible/natural light-responsible bactericidal agents for a variety of bacteria control applications.

Pharmaceuticals in grocery market fish fillets by gas chromatography-mass spectrometry.

Occurrences of pharmaceuticals are evident in aquatic organisms. A reproducible gas chromatography-mass spectrometry (GC-MS) method using selected ion monitoring (SIM) has been used to determine the anti-histamine diphenhydramine (DPH), anti-anxiety diazepam (DZP), anti-seizure carbamazepine (CZP) drugs and their metabolites in grocery stores fish that were homogenized, extracted, pre-concentrated, cleaned up, and examined. Identifications of the compounds in extracts were obtained by comparing similar mass spectral features and retention properties with standards. Among nine frequently detected drugs, only DPH and DZP were observed and ranged from 0.61 to 6.21 and 1.99 to 16.57 ng/g, respectively, in fourteen fish species. These concentration values were lower than the environmental fish. Mean spike recoveries of analytes exceeded 75% with relative standard deviations (RSD)<10%. The statistically-derived method detection limits (MDLs) for nine compounds ranged from 0.13 to 5.56 ng/g. Average surrogate recoveries were 80-85% with 4-9% RSD.

Carbon "Quantum" Dots for Fluorescence Labeling of Cells.

The specifically synthesized and selected carbon dots of relatively high fluorescence quantum yields were evaluated in their fluorescence labeling of cells. For the cancer cell lines, the cellular uptake of the carbon dots was generally efficient, resulting in the labeling of the cells with bright fluorescence emissions for both one- and two-photon excitations from predominantly the cell membrane and cytoplasm. In the exploration on labeling the live stem cells, the cellular uptake of the carbon dots was relatively less efficient, though fluorescence emissions could still be adequately detected in the labeled cells, with the emissions again predominantly from the cell membrane and cytoplasm. This combined with the observed more efficient internalization of the same carbon dots by the fixed stem cells might suggest some significant selectivity of the stem cells toward surface functionalities of the carbon dots. The needs and possible strategies for more systematic and comparative studies on the fluorescence labeling of different cells, including especially live stem cells, by carbon dots as a new class of brightly fluorescent probes are discussed.

Host-Guest Carbon Dots for Enhanced Optical Properties and Beyond.

Carbon dots, generally small carbon nanoparticles with various forms of surface passivation, have achieved the performance level of semiconductor quantum dots in the green spectral region, but their absorption and fluorescence in red/near-IR are relatively weaker. Conceptually similar to endofullerenes, host-guest carbon dots were designed and prepared with red/near-IR dyes encapsulated as guest in the carbon nanoparticle core. Beyond the desired enhancement in optical properties, the host-guest configuration may significantly broaden the field of carbon dots.

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.

Flexible graphene-graphene composites of superior thermal and electrical transport properties.

Graphene is known for high thermal and electrical conductivities. In the preparation of neat carbon materials based on graphene, a common approach has been the use of well-exfoliated graphene oxides (GOs) as the precursor, followed by conversion to reduced GOs (rGOs). However, rGOs are more suitable for the targeted high electrical conductivity achievable through percolation but considerably less effective in terms of efficient thermal transport dictated by phonon progression. In this work, neat carbon films were fabricated directly from few-layer graphene sheets, avoiding rGOs completely. These essentially graphene-graphene composites were of a metal-like appearance and mechanically flexible, exhibiting superior thermal and electrical transport properties. The observed thermal and electrical conductivities are higher than 220 W/m · K and 85000 S/m, respectively. Some issues in the further development of these mechanically flexible graphene-graphene nanocomposite materials are discussed and so are the associated opportunities.

Simultaneous detection and quantification of select nitromusks, antimicrobial agent, and antihistamine in fish of grocery stores by gas chromatography-mass spectrometry.

Continually detected biologically persistent nitromusks; galaxolide (HHCB), tonalide (AHTN) and musk ketone (MK), antimicrobial triclosan (TCS), and antihistamine diphenhydramine (DPH) were examined for the first time in edible fillets originating from eight fish species grown in salt- and fresh-water. The sampled fish collected from local grocery stores were homogenized, extracted, pre-concentrated and analyzed by gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring (SIM). The presence of the target compounds in fish extracts was confirmed based on similar mass spectral features and retention behavior with standards. Internal standard based calibration plots were used for quantification. The HHCB, AHTN, TCS and DPH were consistently observed with concentration of 0.163-0.892, 0.068-0.904, 0.189-1.182, and 0.942-7.472 ng g(-1), respectively. These values are at least 1-3 orders of magnitude lower than those obtained in environmental fish specimens. The MK was not detected in any fish.

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.

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.

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).

Graphene oxides dispersing and hosting graphene sheets for unique nanocomposite materials.

Graphene oxides (GOs), beyond their widely reported use as precursors for single-layer graphene sheets, are in fact excellent materials themselves (polymers in two-dimension, polyelectrolyte-like, aqueous solubility and biocompatibility, etc.). In this reported work we used aqueous GOs to effectively disperse few-layer graphene sheets (GNs) in suspension for facile wet-processing into nanocomposites of GNs embedded in GOs (as the polymeric matrix). The resulting lightweight and plastic-like nanocomposite materials remained mechanically flexible even at high loadings of GNs, and they were found to be highly efficient in thermal transport, with the experimentally determined thermal diffusivity competitive to those typically observed only in well-known thermally conductive metals such as aluminum and copper. As demonstrated, GOs apparently represent a unique class of two-dimensional polymeric materials for potentially "all-carbon" nanocomposites, among others, which may find technological applications independent of those widely proclaimed for graphene sheets.

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.

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.