Alkalide-Assisted Direct Electron Injection for the Noninvasive n-Type Doping of Graphene.

Although the doping of graphene grown by chemical vapor deposition is crucial in graphene-based electronics, noninvasive methods of n-type doping have not been widely investigated in comparison with p-type doping methods. We developed a convenient and robust method for the noninvasive n-type doping of graphene, wherein electrons are directly injected from sodium anions into the graphene. This method involves immersing the graphene in solutions of [K(15-crown-5)2]Na prepared by dissolving a sodium-potassium (NaK) alloy in a 15-crown-5 solution. The n-type doping of the graphene was confirmed by downshifted G and 2D bands in Raman spectra and by the Dirac point shifting to a negative voltage. The electron-injected graphene showed no sign of structural damage, exhibited higher carrier mobilities than that of pristine graphene, and remained n-doped for over a month of storage in air. In addition, we demonstrated that electron injection enhances noncovalent interactions between graphene and metallomacrocycle molecules without requiring a linker, as used in previous studies, suggesting several potential applications of the method in modifying graphene with various functionalities.

Compartmentalized Arrays of Matrix Droplets for Quantitative Mass Spectrometry Imaging of Adsorbed Peptides.

Mass spectrometry imaging (MSI) based on matrix-assisted laser desorption/ionization (MALDI) provides information on the identification and spatial distribution of biomolecules. Quantitative analysis, however, has been challenging largely due to heterogeneity in both the size of the matrix crystals and the extraction area. In this work, we present a compartmentalized elastomeric stamp for quantitative MALDI-MSI of adsorbed peptides. Filling the compartments with matrix solution and stamping onto a planar substrate extract and concentrate analytes adsorbed in each compartment into a single analyte-matrix cocrystal over the entire stamped area. Walls between compartments help preserve spatial information on the adsorbates. The mass intensity of the cocrystals directly correlates with the surface coverage of analytes, which enables not only quantitative analysis but estimation of an equilibrium constant for the adsorption. We demonstrate via MALDI-MSI relative quantitation of peptides adsorbed along a microchannel with varying surface coverages.

Associations of lifestyle factors with phthalate metabolites, bisphenol A, parabens, and triclosan concentrations in breast milk of Korean mothers.

The toxicity of endocrine disruptors depends on the synergistic interactions of biological, environmental, and behavioral factors. The specific effects of diet, consumer product use, and behaviors, however, are debated in the literature, particularly with regard to endocrine disruptors found in breast milk. This study aimed to measure the levels of phthalate metabolites, bisphenol A, parabens, and triclosan in breast milk and to investigate their associations with various lifestyle factors. The breast milk samples as well as surveys were collected from 221 first-time mothers throughout South Korea and each sample was analyzed for the presence of 15 endocrine disruptors. Phthalate metabolites were detected in 5.4-83.3% of the samples, with median concentrations of 0.08-1.72 µg/L, while bisphenol A, parabens, and triclosan were detected in 25.8-88.2% of the samples, with median concentrations of 0.12-1.47 µg/L. High levels of endocrine disruptors were associated with frequent consumption of fish and cup noodles; the use of plastic and disposable food containers; the use of air fresheners, lotions and make-up; the purchase of new furniture; and socioeconomic status. We also observed the potential role of moderate walking activity on the reduction of these chemicals in breast milk. Our data provide evidence of the potential effects of diet, consumer products, and behavior on the presence of phthalate metabolites, bisphenol A, parabens, and triclosan in breast milk. Future studies should include community or regional impact on a mothers' exposure to endocrine disruptors, to assess the joint contribution of both individual and neighborhood factors.

Investigating the Effects of Spacing on Working Memory Training Outcome: A Randomized, Controlled, Multisite Trial in Older Adults.

OBJECTIVE: The majority of the population will experience some cognitive decline with age. Therefore, the development of effective interventions to mitigate age-related decline is critical for older adults' cognitive functioning and their quality of life. METHODS: In our randomized controlled multisite trial, we target participants' working memory (WM) skills, and in addition, we focus on the intervention's optimal scheduling in order to test whether and how the distribution of training sessions might affect task learning, and ultimately, transfer. Healthy older adults completed an intervention targeting either WM or general knowledge twice per day, once per day, or once every-other-day. Before and after the intervention and 3 months after training completion, participants were tested in a variety of cognitive domains, including those representing functioning in everyday life. RESULTS: In contrast to our hypotheses, spacing seems to affect learning only minimally. We did observe some transfer effects, especially within the targeted cognitive domain (WM and inhibition/interference), which remained stable at the 3-month follow-up. DISCUSSION: Our findings have practical implications by showing that the variation in training schedule, at least within the range used here, does not seem to be a crucial element for training benefits.

Packaging vertically aligned carbon nanotubes into a heat-shrink tubing for efficient removal of phenolic pollutants.

Owing to their extremely high surface-to-volume ratio, carbon nanotubes (CNTs) are excellent adsorbents for the removal of organic pollutants. However, retrieval or collection of the CNTs after adsorption in existing approaches, which utilize CNTs dispersed in a solution of pollutants, is often more challenging than the removal of pollutants. In this study, we address this challenge by packaging vertically aligned CNTs into a PTFE heat-shrink tubing. Insertion of CNTs into the tubing and subsequent thermal shrinkage densified the CNTs radially by 35% and also reduced wrinkles in the nanotubes. The CNT-based adsorption tube with a circular cross-section enabled both easy functionalization of CNTs and facile connection to a source of polluted water, which we demonstrated for the removal of phenolic compounds. We purified and carboxylated CNTs, by flowing a solution of nitric acid through the tubing, and obtained adsorption capacities of 115, 124, and 81.2 mg g-1 for 0.5 g L-1 of phenol, m-cresol, 2-chlorophenol, respectively. We attribute the high adsorption capacity of our platform to efficient adsorbate-CNT interaction within the narrow interstitial channels between the aligned nanotubes. The CNT-based adsorption tubes are highly promising for the simple and efficient removal of phenolic and other types of organic pollutants.

A Low-Energy Electron Beam Does Not Damage Single-Walled Carbon Nanotubes and Graphene.

Scanning electron microscopy (SEM) is a principal tool for studying nanomaterials, including carbon nanotubes and graphene. Imaging carbon nanomaterials by SEM, however, increases the disorder mode (D-mode) in their Raman spectra. Early studies, which relied on ambiguous ensemble measurements, claimed that the D-mode indicates damage to the specimens by a low-energy electron beam (e-beam). This claim has been accepted by the nanomaterials community for more than a decade without thorough examination. Here we demonstrate that a low-energy e-beam does not damage carbon nanomaterials. By performing measurements on single nanotubes, we independently examined the following factors: (1) the e-beam irradiation itself, (2) the e-beam-deposited hydrocarbon, and (3) the amorphous carbon deposited during synthesis of the material. We concluded that the e-beam-induced D-mode of both carbon nanotubes and graphene originates solely from the irradiated amorphous carbon and not from the e-beam itself or the hydrocarbon. The results of this study should help minimize potential ambiguities for researchers imaging a broad range of nanomaterials by electron microscopy.

Target metabolic profiling analysis of free amino acids in plasma as EOC/TBDMS derivatives by GC-SIM-MS.

Metabolic profiling analysis of free amino acids (AAs) in plasma (20 microL) was performed by gas chromatography-mass spectrometry in selected ion monitoring mode after ethoxycarbonyl/tert-butyldimethylsilyl derivatives. Characteristic fragment ions, including [M - 57](+) ions, permitted sensitive and selective detection of most of the AAs in the presence of co-extracted carboxylic acids, including free fatty acids, at much higher levels. The overall method was linear (r > or = 0.9991), reproducible (relative standard deviation = 2.3-8.8%) and accurate (relative error = -7.3-7.7%) with detection limits of 0.01-1.9 ng/mL. A total of 18 AAs, 15 protein AAs and three nonprotein AAs were quantitatively screened in a normal human plasma sample. This selective and simple method using a minimal sample volume was effective for the quantitation of plasma free AAs.