Interlaboratory comparison of centrifugal ultrafiltration with ICP-MS detection in a first-step towards methods to screen for nanomaterial release during certification of drinking water contact materials.

A key requirement for evaluating the safety of nano-enabled water treatment devices is measuring concentrations of insoluble nanomaterials released from devices into water that may be ingested by consumers. Therefore, there is a need for simple technique that uses commonly available commercial laboratory techniques to discriminate between nanoparticles and dissolved by-products of the nanomaterial (e.g., ionic metals). Such capabilities would enable screening for particulate or dissolved metals released into water from nanomaterial-containing drinking water contact materials (e.g., paint coatings) or devices (e.g., filters). This multi-laboratory study sought to investigate the use of relatively inexpensive centrifugal ultrafilters to separate nanoparticulate from ionic metal in combination with inductively-coupled plasma mass spectrometry (ICP-MS) detection. The accuracy, precision, and reproducibility for the proposed method were assessed using mixtures of nanoparticulate and ionic gold (Au) in a standard and widely utilized model water matrix (NSF International Standard 53/61). Concentrations for both ionic and nanoparticulate gold based upon measurements of Au mass in the initial solutions and Au permeating the centrifugal ultrafilters. Results across different solution compositions and different participating labs showed that ionic and nanoparticulate Au could be consistently discriminated with ppb concentrations typically resulting in <10 % error. A mass balance was not achieved because nanoparticles were retained on membranes embedded in plastic holders inside the centrifuge tubes, and the entire apparatus could not be acid and/or microwave digested. This was a minor limitation considering the ultrafiltration method is a screening tool, and gold concentration in the permeate indicates the presence of ionic metal rather than nanoforms. With further development, this approach could prove to be an effective tool in screening for nanomaterial release from water-system or device materials as part of third-party certification processes of drinking water compatible products.

Critical metal geochemistry in groundwaters influenced by dredged material.

This study investigated critical metal (CM) geochemistry including rare earth elements (REEs), Co, Ni, and Mn in groundwaters below and surrounding two dredged material placement facilities (DMPFs). Metal concentrations are elevated at both sites, spanning several orders of magnitude. The highest CM concentrations measured exceed many environments considered as aqueous resources (Co and Ni > 1 mg L-1, REEs > 3 mg L-1). Correlations between sulfur and iron, major cations, and CMs indicate that oxidation of sulfides present in the DM releases metals both directly from sulfide minerals and indirectly through acid dissolution of and/or desorption from additional minerals. REE fractionation patterns indicate that their mobility in the groundwaters may be influenced by interactions with silicate, carbonate, and phosphate minerals. Significant positive Gd and Eu anomalies were observed, which may be attributed to increased mobility of Eu2+ and anthropogenic Gd. Nanogeochemical analysis of filtered samples revealed several REE-bearing nanoparticulate (diameter < 100 nm) species, some of which co-occurred with aluminum, suggesting an (oxy)hydroxide or a clay mineral component. Further characterization of soluble and nano scale geochemical speciation is needed to fully assess the viability of CM recovery from DM-associated groundwater. CM recovery from DM-associated waters can provide a beneficial use, both offsetting costs associated with disposal, and supplementing domestic CM resources.

Evolution of hierarchy in bacterial metabolic networks.

Flow hierarchy is a useful way to characterize the movement of information and matter throughout a network. Hierarchical network organizations are shown to arise when there is a cost of maintaining links in the network. A similar constraint exists in metabolic networks, where costs come from reduced efficiency of nonspecific enzymes or from producing unnecessary enzymes. Previous analyses of bacterial metabolic networks have been used to predict the minimal nutrients that a bacterium needs to grow, its mutualistic relationships with other bacteria, and its major ecological niche. We use metabolic network inference to obtain metabolite flow graphs of 2935 bacterial metabolic networks and find that flow hierarchy evolves independently of modularity and other network properties. By inferring the ancestral metabolic networks and estimating the hierarchical character of the inferred network, we show that hierarchical structure first increased and later decreased over evolutionary history. Furthermore, hierarchical structure in the network is associated with slower growth rates; bacteria with hierarchy scores above the median grow on average 2.25 times faster than those with hierarchy scores below the median.

Robust gold nanorods stabilized by bidentate N-heterocyclic-carbene-thiolate ligands.

Although N-heterocyclic carbenes (NHCs) have demonstrated outstanding potential for use as surface anchors, synthetic challenges have limited their application to either large planar substrates or very small spherical nanoparticles. The development of a strategy to graft NHCs onto non-spherical nanomaterials, such as gold nanorods, would greatly expand their utility as surface ligands. Here, we use a bidentate thiolate-NHC-gold(I) complex that is easily grafted onto commercial cetyl trimethylammonium bromide-stabilized gold nanorods through ligand exchange. On mild reduction of the resulting surface-tethered NHC-gold(I) complexes, the gold atom attached to the NHC complex is added to the surface as an adatom, thereby precluding the need for reorganization of the underlying surface lattice upon NHC binding. The resulting thiolate-NHC-stabilized gold nanorods are stable towards excess glutathione for up to six days, and under conditions with large variations in pH, high and low temperatures, high salt concentrations, or in biological media and cell culture. We also demonstrate the utility of these nanorods for in vitro photothermal therapy.

Synthetic Lateral Metal-Semiconductor Heterostructures of Transition Metal Disulfides.

Lateral heterostructures with planar integrity form the basis of two-dimensional (2D) electronics and optoelectronics. Here we report that, through a two-step chemical vapor deposition (CVD) process, high-quality lateral heterostructures can be constructed between metallic and semiconducting transition metal disulfide (TMD) layers. Instead of edge epitaxy, polycrystalline monolayer MoS2 in such junctions was revealed to nucleate from the vertices of multilayered VS2 crystals, creating one-dimensional junctions with ultralow contact resistance (0.5 kΩ·µm). This lateral contact contributes to 6-fold improved field-effect mobility for monolayer MoS2, compared to the conventional on-top nickel contacts. The all-CVD strategy presented here hence opens up a new avenue for all-2D-based synthetic electronics.

Ultrafast Charge Transfer at a Quantum Dot/2D Materials Interface Probed by Second Harmonic Generation.

Hybrid quantum dot (QD)/transition metal dichalcogenide (TMD) heterostructures are attractive components of next generation optoelectronic devices, which take advantage of the spectral tunability of QDs and the charge and exciton transport properties of TMDs. Here, we demonstrate tunable electronic coupling between CdSe QDs and monolayer WS2 using variable length alkanethiol ligands on the QD surface. Using femtosecond time-resolved second harmonic generation (SHG) microscopy, we show that electron transfer from photoexcited CdSe QDs to single-layer WS2 occurs on ultrafast (50 fs to 1 ps) time scales. Moreover, in the samples exhibiting the fastest charge transfer rates (≤50 fs) we observed oscillations in the time-domain signal corresponding to an acoustic phonon mode of the donor QD, which coherently modulates the SHG response of the underlying WS2 layer. These results reveal surprisingly strong electronic coupling at the QD/TMD interface and demonstrate the usefulness of time-resolved SHG for exploring ultrafast electronic-vibrational dynamics in TMD heterostructures.

Phase-Modulated Degenerate Parametric Amplification Microscopy.

Second-order nonlinear optical interactions, including second-harmonic generation (SHG) and sum-frequency generation (SFG), can reveal a wealth of information about chemical, electronic, and vibrational dynamics at the nanoscale. Here, we demonstrate a powerful and flexible new approach, called phase-modulated degenerate parametric amplification (DPA). The technique, which allows for facile retrieval of both the amplitude and phase of the second-order nonlinear optical response, has many advantages over conventional or heterodyne-detected SHG, including the flexibility to detect the signal at either the second harmonic or fundamental field wavelength. We demonstrate the capabilities of this approach by imaging multigrain flakes of single-layer MoS2. We identify the absolute crystal orientation of each MoS2 domain and resolve grain boundaries with high signal contrast and sub-diffraction-limited spatial resolution. This robust all-optical method can be used to characterize structure and dynamics in organic and inorganic systems, including biological tissue, soft materials, and metal and semiconductor nanostructures, and is particularly well-suited for imaging in media that are absorptive or highly scattering to visible and ultraviolet light.

Reduced dielectric screening and enhanced energy transfer in single- and few-layer MoS2.

We report highly efficient nonradiative energy transfer from cadmium selenide (CdSe) quantum dots to monolayer and few-layer molybdenum disulfide (MoS2). The quenching of the donor quantum dot photoluminescence increases as the MoS2 flake thickness decreases with the highest efficiency (>95%) observed for monolayer MoS2. This counterintuitive result arises from reduced dielectric screening in thin layer semiconductors having unusually large permittivity and a strong in-plane transition dipole moment, as found in MoS2. Excitonic energy transfer between a zero-dimensional emitter and a two-dimensional absorber is fundamentally interesting and enables a wide range of applications including broadband optical down-conversion, optical detection, photovoltaic sensitization, and color shifting in light-emitting devices.

Pervasive antisense transcription is evolutionarily conserved in budding yeast.

Antisense transcription, or transcription on the opposite strand of the same genomic locus as another transcript, has been observed in many organisms, including yeast. Several antisense transcripts are known to be conserved across various species of yeast, and a few antisense transcripts are associated with functional regulation of the sense transcript. We detect antisense transcription from approximately 90% of protein-coding genes, and antisense transcription is generally associated with histone modifications indicative of a transcriptionally active state. The pattern of genome-wide antisense transcription in two species of budding yeast, Saccharomyces cerevisiae and S. paradoxus, is widely evolutionarily conserved: Antisense transcripts exhibit conserved expression levels and localization with respect to gene annotations. Regions of genes exhibiting conserved antisense transcription also show less sequence divergence than regions of genes without antisense transcription. These findings provide further support that widespread antisense transcription is functional in yeast, and expand the catalog of putative functional antisense transcripts to include nonpolyadenylated transcripts. Because antisense transcripts are less divergent in sequence than expected, they likely contain sequences important to their function.