Boosted Oxygen Evolution Reactivity by Igniting Double Exchange Interaction in Spinel Oxides.

A double-exchange interaction (DEI) was demonstrated to boost the oxygen evolution reaction (OER) in spinel oxides. DEI was ignited by synergistic actions of constructing nanoheterojunctions and creating oxygen vacancy (VO) in spinel NiCo2O4. DEI between octahedrally coordinated Ni and Co resulted in the generation of superior OER active centers Co(3-δ)+ and Ni3+. The multiple synergistic effects empower the electrocatalyst with exceptional OER activity, with an overpotential of 270 ± 3 mV at 10 mA/cm2 and a Tafel slope of 39 mV/dec, both of which are among the best values for NiCo2O4-based nanostructures, and even better than those for IrO2 and RuO2.

Study of the inorganic substitution in a functionalized UiO-66 metal-organic framework.

In this study the band gap modulation was studied in response to inorganic ion substitution within a thermally stable UiO-66 metal-organic framework (MOF). A combination of density functional theory prediction in conjunction with experimental predictions were used to map out the complete composition space for three inorganic ions (Zr, Ti, Hf) and three functional groups. The three functional groups include an amino group (NH2), a nitro group (NO2), and a hydrogenated case (H). The smallest band gap that experimentally determined was for a partially substituted UiO-66(Ti5Zr1)-NH2 resulting in 2.60 eV. Theoretical results indicated that Ti can be fully substituted within the lattice resulting in a predicted band gap as low as 1.62 eV. Modulation was a result of a mid-gap state introduced through the amino functionalization and HOMO shifting as a result of increased binding of the Ti-O-C bonds.

Solar hydrogen generation by a CdS-Au-TiO2 sandwich nanorod array enhanced with Au nanoparticle as electron relay and plasmonic photosensitizer.

This paper presents a sandwich-structured CdS-Au-TiO2 nanorod array as the photoanode in a photoelectrochemical cell (PEC) for hydrogen generation via splitting water. The gold nanoparticles sandwiched between the TiO2 nanorod and the CdS quantum dot (QD) layer play a dual role in enhancing the solar-to-chemical energy conversion efficiency. First, the Au nanoparticles serve as an electron relay, which facilitates the charge transfer between CdS and TiO2 when the CdS QDs are photoexcited by wavelengths shorter than 525 nm. Second, the Au nanoparticles act as a plasmonic photosensitizer, which enables the solar-to-hydrogen conversion at wavelengths longer than the band edge of CdS, extending the photoconversion wavelength from 525 to 725 nm. The dual role of Au leads to a photocurrent of 4.07 mA/cm(2) at 0 V (vs Ag|AgCl) under full solar spectrum irradiation and a maximum solar-to-chemical energy conversion efficiency of 2.8%. An inversion analysis is applied to the transient absorption spectroscopy data, tracking the transfer of electrons and holes in the heterostructure, relating the relaxation dynamics to the underlying coupled rate equation and revealing that trap-state Auger recombination is a dominant factor in interfacial charge transfer. It is found that addition of Au nanoparticles increases the charge-transfer lifetime, reduces the trap-state Auger rate, suppresses the long-time scale back transfer, and partially compensates the negative effects of the surface trap states. Finally, the plasmonic energy-transfer mechanism is identified as direct transfer of the plasmonic hot carriers, and the interfacial Schottky barrier height is shown to modulate the plasmonic hot electron transfer and back transfer. Transient absorption characterization of the charge transfer shows defect states cannot be ignored when designing QD-sensitized solar cells. This facile sandwich structure combines both the electrical and the optical functions of Au nanoparticles into a single structure, which has implications for the design of efficient solar-energy-harvesting devices.

Probing the Representational Structure of Regular Polysemy via Sense Analogy Questions: Insights from Contextual Word Vectors.

Regular polysemes are sets of ambiguous words that all share the same relationship between their meanings, such as CHICKEN and LOBSTER both referring to an animal or its meat. To probe how a distributional semantic model, here exemplified by bidirectional encoder representations from transformers (BERT), represents regular polysemy, we analyzed whether its embeddings support answering sense analogy questions similar to "is the mapping between CHICKEN (as an animal) and CHICKEN (as a meat) similar to that which maps between LOBSTER (as an animal) to LOBSTER (as a meat)?" We did so using the LRcos model, which combines a logistic regression classifier of different categories (e.g., animal vs. meat) with a measure of cosine similarity. We found that (a) the model was sensitive to the shared structure within a given regular relationship; (b) the shared structure varies across different regular relationships (e.g., animal/meat vs. location/organization), potentially reflective of a "regularity continuum;" (c) some high-order latent structure is shared across different regular relationships, suggestive of a similar latent structure across different types of relationships; and (d) there is a lack of evidence for the aforementioned effects being explained by meaning overlap. Lastly, we found that both components of the LRcos model made important contributions to accurate responding and that a variation of this method could yield an accuracy boost of 10% in answering sense analogy questions. These findings enrich previous theoretical work on regular polysemy with a computationally explicit theory and methods, and provide evidence for an important organizational principle for the mental lexicon and the broader conceptual knowledge system.

Inhibition of kinetic random-distribution in DNA Seesaw gates and biosensors for complete leakage prevention.

DNA nanomaterials have a wide application prospect in biomedical field, among which DNA computers and biosensors based on Seesaw-based DNA circuit is considered to have the most development potential. However, the serious leakage of Seesaw-based DNA circuit prevented its further development and application. Moreover, the existing methods to suppress leakage can't achieve the ideal effect. Interestingly, we found a new source of leakage in Seesaw-based DNA circuit, which we think is the main reason why the previous methods to suppress leakage are not satisfactory. Therefore, based on this discovery, we use DNA triplex to design a new method to suppress the leakage of Seesaw-based DNA circuit. Its ingenious design makes it possible to perfectly suppress the leakage of all sources in Seesaw-based DNA circuit and ensure the normal output of the circuit. Based on this technology, we have constructed basic Seesaw module, AND gate, OR gate, secondary complex circuits and DNA detector. Experimental results show that we can increase the working range of the secondary Seesaw-based DNA circuit by five folds and keep its normal output signal above 90%, and we can improve the LOD of the Seesaw-based DNA detector to 1/11 of the traditional one(1.8pM). More importantly, we successfully developed a detector with adjustable detection range, which can theoretically achieve accurate detection in any concentration range. We believe the established triplex blocking strategy will greatly facilitate the most powerful Seesaw based DNA computers and biosensors, and further promote its application in biological systems.

Solar hydrogen generation by nanoscale p-n junction of p-type molybdenum disulfide/n-type nitrogen-doped reduced graphene oxide.

Molybdenum disulfide (MoS2) is a promising candidate for solar hydrogen generation but it alone has negligible photocatalytic activity. In this work, 5-20 nm sized p-type MoS2 nanoplatelets are deposited on the n-type nitrogen-doped reduced graphene oxide (n-rGO) nanosheets to form multiple nanoscale p-n junctions in each rGO nanosheet. The p-MoS2/n-rGO heterostructure shows significant photocatalytic activity toward the hydrogen evolution reaction (HER) in the wavelength range from the ultraviolet light through the near-infrared light. The photoelectrochemical measurement shows that the p-MoS2/n-rGO junction greatly enhances the charge generation and suppresses the charge recombination, which is responsible for enhancement of solar hydrogen generation. The p-MoS2/n-rGO is an earth-abundant and environmentally benign photocatalyst for solar hydrogen generation.

Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor.

Plasmonic metal nanostructures have been incorporated into semiconductors to enhance the solar-light harvesting and the energy-conversion efficiency. So far the mechanism of energy transfer from the plasmonic metal to semiconductors remains unclear. Herein the underlying plasmonic energy-transfer mechanism is unambiguously determined in Au@SiO(2)@Cu(2)O sandwich nanostructures by transient-absorption and photocatalysis action spectrum measurement. The gold core converts the energy of incident photons into localized surface plasmon resonance oscillations and transfers the plasmonic energy to the Cu(2)O semiconductor shell via resonant energy transfer (RET). RET generates electron-hole pairs in the semiconductor by the dipole-dipole interaction between the plasmonic metal (donor) and semiconductor (acceptor), which greatly enhances the visible-light photocatalytic activity as compared to the semiconductor alone. RET from a plasmonic metal to a semiconductor is a viable and efficient mechanism that can be used to guide the design of photocatalysts, photovoltaics, and other optoelectronic devices.

Oxygen Evolution Reaction in Energy Conversion and Storage: Design Strategies Under and Beyond the Energy Scaling Relationship.

The oxygen evolution reaction (OER) is the essential module in energy conversion and storage devices such as electrolyzer, rechargeable metal-air batteries and regenerative fuel cells. The adsorption energy scaling relations between the reaction intermediates, however, impose a large intrinsic overpotential and sluggish reaction kinetics on OER catalysts. Developing advanced electrocatalysts with high activity and stability based on non-noble metal materials is still a grand challenge. Central to the rational design of novel and high-efficiency catalysts is the development and understanding of quantitative structure-activity relationships, which correlate the catalytic activities with structural and electronic descriptors. This paper comprehensively reviews the benchmark descriptors for OER electrolysis, aiming to give an in-depth understanding on the origins of the electrocatalytic activity of the OER and further contribute to building the theory of electrocatalysis. Meanwhile, the cutting-edge research frontiers for proposing new OER paradigms and crucial strategies to circumvent the scaling relationship are also summarized. Challenges, opportunities and perspectives are discussed, intending to shed some light on the rational design concepts and advance the development of more efficient catalysts for enhancing OER performance.

Word Senses as Clusters of Meaning Modulations: A Computational Model of Polysemy.

Most words in natural languages are polysemous; that is, they have related but different meanings in different contexts. This one-to-many mapping of form to meaning presents a challenge to understanding how word meanings are learned, represented, and processed. Previous work has focused on solutions in which multiple static semantic representations are linked to a single word form, which fails to capture important generalizations about how polysemous words are used; in particular, the graded nature of polysemous senses, and the flexibility and regularity of polysemy use. We provide a novel view of how polysemous words are represented and processed, focusing on how meaning is modulated by context. Our theory is implemented within a recurrent neural network that learns distributional information through exposure to a large and representative corpus of English. Clusters of meaning emerge from how the model processes individual word forms. In keeping with distributional theories of semantics, we suggest word meanings are generalized from contexts of different word tokens, with polysemy emerging as multiple clusters of contextually modulated meanings. We validate our results against a human-annotated corpus of polysemy focusing on the gradedness, flexibility, and regularity of polysemous sense individuation, as well as behavioral findings of offline sense relatedness ratings and online sentence processing. The results provide novel insights into how polysemy emerges from contextual processing of word meaning from both a theoretical and computational point of view.

Stepwise in situ synthesis and characterization of metallophthalocyanines@mesoporous matrix SBA-15 composites.

The successful in situ synthesis of metallophthalocyanines in mesoporous matrices is presented in this report. To overcome the high hydrophobicity of phthalocyanine (Pc) compounds in conventional wet chemical methods, a simple but effective route is developed to incorporate the metallophthalocyanines into the mesoporous matrix via an in situ reaction process between pre-loaded metal ions and 1,2-dicyanobenzene (DCB) introduced by chemical vapor deposition. The Pcs are not directly loaded into the pores, but the precursors of metallophthalocyanines (metal ions and small DCB molecules) are introduced stepwise into the pore channels, which are then used as 'micro-reactors" to produce incorporated MePcs by in situ reactions. The structural and optical characteristics of the as-synthesized composites are carefully investigated using X-ray diffraction, transmission electronic microscopy, scanning electronic microscopy, infrared and ultra violet spectra, and BET methods. The results show that the metallophthalocyanines disperse homogeneously in the mesopores, mostly as monomers, accompanied by a small number of dimers.

Photoelectrochemical overall water splitting with textured CuBi2O4 as a photocathode.

Nanotextured CuBi2O4 photocathodes have been developed for applications toward solar water splitting. Tailoring the CuBi2O4 photocathodes to yield a high photocurrent and a positively large onset potential demonstrates their applicability in a photoelectrochemical tandem cell for entirely solar-driven overall water splitting.

Functional evolution within a protein superfamily.

The ability to predict and characterize distributions of reactivities over families and even superfamilies of proteins opens the door to an array of analyses regarding functional evolution. In this article, insights into functional evolution in the Kazal inhibitor superfamily are gained by analyzing and comparing predicted association free energy distributions against six serine proteinases, over a number of groups of inhibitors: all possible Kazal inhibitors, natural avian ovomucoid first and third domains, and sets of Kazal inhibitors with statistically weighted combinations of residues. The results indicate that, despite the great hypervariability of residues in the 10 proteinase-binding positions, avian ovomucoid third domains evolved to inhibit enzymes similar to the six enzymes selected, whereas the orthologous first domains are not inhibitors of these enzymes on purpose. Hypervariability arises because of similarity in energetic contribution from multiple residue types; conservation is in terms of functionality, with "good" residues, which make positive or less deleterious contributions to the binding, selected more frequently, and yielding overall the same distributional characteristics. Further analysis of the distributions indicates that while nature did optimize inhibitor strength, the objective may not have been the strongest possible inhibitor against one enzyme but rather an inhibitor that is relatively strong against a number of enzymes.

Analysis of sequence-reactivity space for protein-protein interactions.

Sequence-reactivity space is defined by the relationships between amino acid type choices at some residue positions in a protein and the reactivities of the resulting variants. We are studying Kazal superfamily serine proteinase inhibitors, under substitution of any combination of residue types at 10 binding-region positions. Reactivities are defined by the standard free energy of association for an inhibitor against an enzyme, and we are interested in both the strength (the free energy value) and specificity (relative free energy values for one inhibitor against different enzymes). Characterizing the structure of such a space poses several interesting questions: (1) How many sequences achieve particular strength and specificity characteristics? (2) What is the best such sequence? (3) What are some nearly-as-good alternatives? (4) What are their common residue type characteristics (e.g., conservation and correlation)? Although these problems are all highly combinatorial in nature, this article develops an efficient, integrated mechanism to address them under a data-driven model that predicts reactivity for given sequences. We employ sampling and a novel deterministic distribution propagation algorithm, in order to determine both the reactivity distribution and sequence composition statistics; integer programming and a novel branch-and-bound search algorithm, in order to optimize sequences and enumerate near-optimal sequences; and correlation-based sequence decomposition, in order to identify sequence motifs. We demonstrate the value of our mechanism in analyzing the Kazal superfamily sequence-reactivity space, providing insights into the underlying biochemistry and suggesting hypotheses for further experimental consideration. In general, our mechanism offers a valuable tool for investigating the available degrees of freedom in protein design within a combined computational-experimental framework.

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

SnO2@CdS nanowire-quantum dots heterostructures: tailoring optical properties of SnO2 for enhanced photodetection and photocatalysis.

Rationally designed SnO2@CdS nanowire-quantum dots (QDs) heterostructures were realized by a wet-chemical method via hydroxide cluster growth mechanism on high crystalline quality SnO2 nanowires, which were synthesized by a vapor transport method. The heterostructures showed enhanced photon harvesting capability and photodetection sensitivity at visible regime than that of wide band gap homogeneous SnO2 nanowires, as characterized by UV-Vis absorption and photoconductivity measurements. In addition, the SnO2@CdS nanowire-QDs heterostructures showed enhanced photocatalytic activity by more than 109% in a conceptual demonstration of photodegradation of methylene blue solution. Our results suggest that the SnO2@CdS nanowire-QDs heterostructures exhibit considerable promise for highly sensitive visible-light photodetectors and highly efficient photocatalysis.

Plasmon-induced photonic and energy-transfer enhancement of solar water splitting by a hematite nanorod array.

Plasmonic metal nanostructures offer a promising route to improve the solar energy conversion efficiency of semiconductors. Here we show that incorporation of a hematite nanorod array into a plasmonic gold nanohole array pattern significantly improves the photoelectrochemical water splitting performance, leading to an approximately tenfold increase in the photocurrent at a bias of 0.23 V versus Ag|AgCl under simulated solar radiation. Plasmon-induced resonant energy transfer is responsible for enhancement at the energies below the band edge, whereas above the absorption band edge of hematite, the surface plasmon polariton launches a guided wave mode inside the nanorods, with the nanorods acting as miniature optic fibres, enhancing the light absorption. In addition, the intense local plasmonic field can suppress the charge recombination in the hematite nanorod photoanode in a photoelectrochemical cell. Our results may provide a general approach to overcome the low optical absorption and spectral utilization of thin semiconductor nanostructures, while further reducing charge recombination losses.

Differential mouse pulmonary dose and time course responses to titanium dioxide nanospheres and nanobelts.

Three anatase titanium dioxide (TiO(2)) nanoparticles (NPs) were prepared; nanospheres (NSs), short nanobelts (NB1), and long nanobelts (NB2). These NPs were used to investigate the effect of NP shape and length on lung toxicity. Mice were exposed (0-30 µg per mouse) by pharyngeal aspiration and pulmonary toxicity was assessed over a 112-day time course. Whole lung lavage data indicated that NB1- and NB2-exposed mice, but not NS-exposed mice, had significant dose- and time-dependent pulmonary inflammation and damage. Histopathological analyses at 112 days postexposure determined no interstitial fibrosis in any NS-exposed mice, an increased incidence in 30 µg NB1-exposed mice, and significant interstitial fibrosis in 30 µg NB2-exposed mice. At 112 days postexposure, lung burden of NS was decreased by 96.4% and NB2 by 80.5% from initial deposition levels. At 112 days postexposure, enhanced dark field microscopy determined that alveolar macro- phages were the dominant deposition site, but a fraction of NB1 and NB2 was observed in the alveolar interstitial spaces. For the 30 µg exposure groups at 112 days postexposure, confocal micro- scopy and immunofluorescent staining demonstrated that retained NB2 but not NS were present in the interstitium subjacent to the terminal bronchiole near the normal location of the smallest lymphatic capillaries in the lung. These lymphatic capillaries play a critical role in particle clearance, and the accumulation of NB2, but not NS, suggests possible impaired lymphatic clearance by the high aspect ratio particles. In summary, our data indicate that TiO(2) NP shape alters pulmonary responses, with severity of responses being ranked as NS < NB1 < NB2.

Photoelectrochemical performance enhanced by a nickel oxide-hematite p-n junction photoanode.

A p-n junction photoanode has been fabricated by depositing p-type NiO nanoparticles on the n-type hematite thin film. Such a photoanode is employed for a photoelectrochemical cell. NiO not only facilitates the extraction of accumulated holes from hematite via the p-n junction, but also lowers the barrier for oxygen evolution reaction.

Microsomal glutathione transferase 1 protects against toxicity induced by silica nanoparticles but not by zinc oxide nanoparticles.

Microsomal glutathione transferase 1 (MGST1) is an antioxidant enzyme located predominantly in the mitochondrial outer membrane and endoplasmic reticulum and has been shown to protect cells from lipid peroxidation induced by a variety of cytostatic drugs and pro-oxidant stimuli. We hypothesized that MGST1 may also protect against nanomaterial-induced cytotoxicity through a specific effect on lipid peroxidation. We evaluated the induction of cytotoxicity and oxidative stress by TiO(2), CeO(2), SiO(2), and ZnO in the human MCF-7 cell line with or without overexpression of MGST1. SiO(2) and ZnO nanoparticles caused dose- and time-dependent toxicity, whereas no obvious cytotoxic effects were induced by nanoparticles of TiO(2) and CeO(2). We also noted pronounced cytotoxicity for three out of four additional SiO(2) nanoparticles tested. Overexpression of MGST1 reversed the cytotoxicity of the main SiO(2) nanoparticles tested and for one of the supplementary SiO(2) nanoparticles but did not protect cells against ZnO-induced cytotoxic effects. The data point toward a role of lipid peroxidation in SiO(2) nanoparticle-induced cell death. For ZnO nanoparticles, rapid dissolution was observed, and the subsequent interaction of Zn(2+) with cellular targets is likely to contribute to the cytotoxic effects. A direct inhibition of MGST1 by Zn(2+) could provide a possible explanation for the lack of protection against ZnO nanoparticles in this model. Our data also showed that SiO(2) nanoparticle-induced cytotoxicity is mitigated in the presence of serum, potentially through masking of reactive surface groups by serum proteins, whereas ZnO nanoparticles were cytotoxic both in the presence and in the absence of serum.

Water-soluble superparamagnetic magnetite nanoparticles with biocompatible coating for enhanced magnetic resonance imaging.

Ultrasmall superparamagnetic Fe(3)O(4) nanoparticles (USIRONs) were synthesized by a novel, easily scalable chemical reduction of colloidal iron hydroxide under hydrothermal conditions. The average crystallite size (5.1 ± 0.5 nm) and good crystallinity of the samples were supported by HR-TEM analysis and the saturation magnetization value (47 emu g(-1)). Vitamin C, used as a chemical reducing agent, also served as a capping agent in the oxidized form (dehydroascorbic acid, DHAA) to impart nanoparticles with exceptional solubility and stability in water, PBS buffer, and cell culture medium. Detailed physicochemical analysis of the USIRON suspensions provided insight into the magnetic ordering phenomena within the colloid, arising from the formation of uniform clusters displaying a hydrodynamic size of 41 nm. Phantom experiments on the contrast agent (clinical 3 T MRI scanner) revealed an enhanced r(2)/r(1) ratio of 36.4 (r(1)= 5 s(-1) mM(-1) and r(2)= 182 s(-1) mM(-1)) when compared to the clinically approved agents. The potential of the DHAA-Fe(3)O(4) nanoparticles as negative contrast agents for MRI with optimal hydrodynamic size for extended blood circulation times was confirmed by strong contrast observed in T(2)- and T(2)*-weighted images. The cell tests performed with primary human immune-competent cells confirmed the excellent biocompatibility of USIRONs.