Vacancy Engineering for High-Efficiency Nanofluidic Osmotic Energy Generation.

Two-dimensional (2D) nanofluidic membranes have shown great promise in harvesting osmotic energy from the salinity difference between seawater and fresh water. However, the output power densities are strongly hampered by insufficient membrane permselectivity. Herein, we demonstrate that vacancy engineering is an effective strategy to enhance the permselectivity of 2D nanofluidic membranes to achieve high-efficiency osmotic energy generation. Phosphorus vacancies were facilely created on NbOPO4 (NbP) nanosheets, which remarkably enlarged their negative surface charge. As verified by both experimental and theoretical investigations, the vacancy-introduced NbP (V-NbP) exhibited fast transmembrane ion migration and high ionic selectivity originating from the improved electrostatic affinity of cations. When applied in a natural river water|seawater osmotic power generator, the macroscopic-scale V-NbP membrane delivered a record-high power density of 10.7 W m-2, far exceeding the commercial benchmark of 5.0 W m-2. This work endows the remarkable potential of vacancy engineering for 2D materials in nanofluidic energy devices.

Biomimetic Dendrite-Free Multivalent Metal Batteries.

Rechargeable multivalent metal (e.g., zinc (Zn) and aluminum (Al)) batteries are ideal choices for large-scale energy storage owing to their intrinsic low cost and safety. However, the poor compatibility between metallic anodes and electrolytes strongly hampers their practical applications. Herein, it is demonstrated that confining multivalent metals in a biomimetic scaffold (Bio-scaffold) can achieve highly efficient multivalent metal plating/stripping. This Bio-scaffold is well-tailored through the synergy of a parallel-aligned array of fractal copper branches and a CaTiO3 (CTO)-based coating layer. By virtue of this design strategy, the as-developed Bio-scaffold-based Zn- and Al-metal anodes exhibited dendrite-free morphologies with high reversibility and long lifespan, as well as excellent performance for Zn and Al full batteries. Theoretical modeling and experimental investigations reveal that the fractal copper array not only facilitates multivalent ion diffusion and electrolyte wetting but also effectively reduces the local current densities during cycling; Meanwhile, the CTO-based coating layer effectively blocks interfacial side reactions and enables a homogeneous ionic flux. This work opens a new avenue for developing multivalent metal batteries.

Sodium docusate as a cleaning agent for forward osmosis membranes fouled by landfill leachate wastewater.

Membrane cleaning is critical for economic and scientific reasons in wastewater treatment systems. Sodium docusate is a laxative agent and removes cerumen (ear wax). Docusate penetrates the hard ear wax, making it softer and easier to remove. The same concept could be applied to soften and remove fouling layers on the membrane surface. Once softened, the foulants can be easily flushed with water. This innovative approach can address the challenge of developing superior methods to mitigate membrane fouling and material degradation. In this study, we evaluated the efficiency of sodium docusate for cleaning fouled forward osmosis membranes with real landfill leachate wastewater. Experiments were conducted to examine the impact of dose rate, contact time, flow or static conditions, and process configuration (forward osmosis (FO) or pressure retarded osmosis (PRO) upon fouling created by landfill leachate dewatering. A remarkable (99%) flux recovery was achieved using docusate at a small concentration of only 0.1% for 30 min. Furthermore, docusate can also effectively restore flux with static cleaning without using pumps to circulate the cleaning solution. Furthermore, cleaning efficiency can be achieved at neutral pH compatible with most membrane materials. From an economic and energy-saving perspective, static cleaning can almost achieve the same cleaning efficiency as kinetic cleaning for fouled forward osmosis membranes without the expense of additional pumping energy compared to kinetic cleaning. Since pumping energy is a major contributor to the overall energy of the forward osmosis system, it can be minimized to a certain degree by using a static cleaning approach and can bring good energy savings when using larger membrane areas. Studies of the contact angle on the membrane surface indicated that the contact angle was decreased compared to the fouled membrane after cleaning (e.g. 70.3° to 63.2° or FO mode and static cleaning). Scanning Electron Microscopy revealed that the cleaning strategy was successful. Infrared Spectroscopy showed that a small amount of sodium docusate remained on the membrane surface. Docusate is more environmentally friendly than acid or alkaline solutions from an environmental perspective. Furthermore, the cleaning solution can be reused for several cycles without discarding it due to the surfactant properties of docusate.

Serosa-Mimetic Nanoarchitecture Membranes for Highly Efficient Osmotic Energy Generation.

Osmotic energy stored between seawater and freshwater is a clean and renewable energy source. However, developing high-efficiency and durable permselective membranes for harvesting osmotic energy remains a longstanding bottleneck. Herein, we report that a nanocomposite membrane with a biological serosa-mimetic structure can achieve high-performance osmotic energy generation through the coupling of two-dimensional (2D) sulfonated covalent organic framework (COF) nanosheets and anion-grafted aramid nanofibers (ANFs). As verified by theoretical calculations and experimental investigations, the 2D COF nanosheets not only provide abundant one-dimensional (1D)/2D nanofluidic channels to synergistically benefit an ultrafast ion migration but also enable high cation permselectivity via the covalently tethered anions. The grafted ANFs increase the mechanical strength of the membrane and further improve the ion diffusion/rectification. When it was applied in an osmotic power generator, the biomimetic membrane delivered a power density of 9.6 W m-2, far surpassing the commercial benchmark of 5.0 W m-2. This work could boost the viability of osmotic energy conversion toward a sustainable future.

Atomic-scale regulation of anionic and cationic migration in alkali metal batteries.

The regulation of anions and cations at the atomic scale is of great significance in membrane-based separation technologies. Ionic transport regulation techniques could also play a crucial role in developing high-performance alkali metal batteries such as alkali metal-sulfur and alkali metal-selenium batteries, which suffer from the non-uniform transport of alkali metal ions (e.g., Li+ or Na+) and detrimental shuttling effect of polysulfide/polyselenide anions. These drawbacks could cause unfavourable growth of alkali metal depositions at the metal electrode and irreversible consumption of cathode active materials, leading to capacity decay and short cycling life. Herein, we propose the use of a polypropylene separator coated with negatively charged Ti0.87O2 nanosheets with Ti atomic vacancies to tackle these issues. In particular, we demonstrate that the electrostatic interactions between the negatively charged Ti0.87O2 nanosheets and polysulfide/polyselenide anions reduce the shuttling effect. Moreover, the Ti0.87O2-coated separator regulates the migration of alkali ions ensuring a homogeneous ion flux and the Ti vacancies, acting as sub-nanometric pores, promote fast alkali-ion diffusion.

Localized Water-In-Salt Electrolyte for Aqueous Lithium-Ion Batteries.

Water-in-salt (WIS) electrolytes using super-concentrated organic lithium (Li) salts are of interest for aqueous Li-ion batteries. However, the high salt cost, high viscosity, poor wettability, and environmental hazards remain a great challenge. Herein, we present a localized water-in-salt (LWIS) electrolyte based on low-cost lithium nitrate (LiNO3 ) salt and 1,5-pentanediol (PD) as inert diluent. The addition of PD maintains the solvation structure of the WIS electrolyte, improves the electrolyte stability via hydrogen-bonding interactions with water and NO3 - molecules, and reduces the total salt concentration. By in situ gelling the LWIS electrolyte with tetraethylene glycol diacrylate (TEGDA) monomer, the electrolyte stability window can be further expanded to 3.0 V. The as-developed Mo6 S8 |LWIS gel electrolyte|LiMn2 O4 (LMO) batteries delivered outstanding cycling performance with an average Coulombic efficiency of 98.53 % after 250 cycles at 1 C.

Rapid fabrication of oxygen defective α-Fe2O3(110) for enhanced photoelectrochemical activities.

Defect engineering is increasingly recognized as a viable strategy for boosting the performance of photoelectrochemical (PEC) water splitting using metal oxide-based photoelectrodes. However, previously developed methods for generating point defects associated with oxygen vacancies are rather time-consuming. Herein, high density oxygen deficient α-Fe2O3 with the dominant (110) crystal plane is developed in a very short timescale of 10 minutes by employing aerosol-assisted chemical vapor deposition and pure nitrogen as a gas carrier. The oxygen-defective film exhibits almost 8 times higher photocurrent density compared to a hematite photoanode with a low concentration of oxygen vacancies which is prepared in purified air. The existence of oxygen vacancies improves light absorption ability, accelerates charge transport in the bulk of films, and promotes charge separation at the electrolyte/semiconductor interface. DFT simulations verify that oxygen-defective hematite has a narrow bandgap, electron-hole trapped centre, and strong adsorption energy of water molecules compared to pristine hematite. This strategy might bring PEC technology another step further towards large-scale fabrication for future commercialization.

Dendrite-Free Sodium Metal Batteries Enabled by the Release of Contact Strain on Flexible and Sodiophilic Matrix.

The formation of sodium (Na) dendrites during cycling has impeded the practical application of Na metal anodes. Herein, we developed a flexible graphene-based matrix, e.g., a porous reduced graphene oxide (PRGO) film, to support dendrite-free Na nucleation and plating, contributing to high-performance Na metal batteries. The PRGO film possessed outstanding merits of sodiophilicity and flexibility. The sodiophilic PRGO film enabled uniform Na nucleation in the initial electroplating stage. Furthermore, the flexible PRGO film with a small Young's modulus effectively alleviated the texture deformation of electrodeposited Na, leading to a compact and dendrite-free Na deposition layer. The well-maintained Na metal anodes on the PRGO film exhibited superior cyclability, high Coulombic efficiency, and improved energy density in both half-cell and full-cell testing. This work illustrates the great significance of mechanical properties of the supporting matrix for the Na electroplating, which provides a new strategy to develop high-performance dendrite-free Na metal batteries.

Insights into the roles of CMK-1 and OGT-1 in interstimulus interval-dependent habituation in Caenorhabditis elegans.

Habituation is a ubiquitous form of non-associative learning observed as a decrement in responding to repeated stimulation that cannot be explained by sensory adaptation or motor fatigue. One of the defining characteristics of habituation is its sensitivity to the rate at which training stimuli are presented-animals habituate faster in response to more rapid stimulation. The molecular mechanisms underlying this interstimulus interval (ISI)-dependent characteristic of habituation remain unknown. In this article, we use behavioural neurogenetic and bioinformatic analyses in the nematode Caenorhabiditis elegans to identify the first molecules that modulate habituation in an ISI-dependent manner. We show that the Caenorhabditis elegans orthologues of Ca2+/calmodulin-dependent kinases CaMK1/4, CMK-1 and O-linked N-acetylglucosamine (O-GlcNAc) transferase, OGT-1, both function in primary sensory neurons to inhibit habituation at short ISIs and promote it at long ISIs. In addition, both cmk-1 and ogt-1 mutants display a rare mechanosensory hyper-responsive phenotype (i.e. larger mechanosensory responses than wild-type). Overall, our work identifies two conserved genes that function in sensory neurons to modulate habituation in an ISI-dependent manner, providing the first insights into the molecular mechanisms underlying the universally observed phenomenon that habituation has different properties when stimuli are delivered at different rates.

Evolutionary Ancestry of Eukaryotic Protein Kinases and Choline Kinases.

The reversible phosphorylation of proteins catalyzed by protein kinases in eukaryotes supports an important role for eukaryotic protein kinases (ePKs) in the emergence of nucleated cells in the third superkingdom of life. Choline kinases (ChKs) could also be critical in the early evolution of eukaryotes, because of their function in the biosynthesis of phosphatidylcholine, which is unique to eukaryotic membranes. However, the genomic origins of ePKs and ChKs are unclear. The high degeneracy of protein sequences and broad expansion of ePK families have made this fundamental question difficult to answer. In this study, we identified two class-I aminoacyl-tRNA synthetases with high similarities to consensus amino acid sequences of human protein-serine/threonine kinases. Comparisons of primary and tertiary structures supported that ePKs and ChKs evolved from a common ancestor related to glutaminyl aminoacyl-tRNA synthetases, which may have been one of the key factors in the successful of emergence of ancient eukaryotic cells from bacterial colonies.

Prediction of 492 human protein kinase substrate specificities.

BACKGROUND: Complex intracellular signaling networks monitor diverse environmental inputs to evoke appropriate and coordinated effector responses. Defective signal transduction underlies many pathologies, including cancer, diabetes, autoimmunity and about 400 other human diseases. Therefore, there is high impetus to define the composition and architecture of cellular communications networks in humans. The major components of intracellular signaling networks are protein kinases and protein phosphatases, which catalyze the reversible phosphorylation of proteins. Here, we have focused on identification of kinase-substrate interactions through prediction of the phosphorylation site specificity from knowledge of the primary amino acid sequence of the catalytic domain of each kinase. RESULTS: The presented method predicts 488 different kinase catalytic domain substrate specificity matrices in 478 typical and 4 atypical human kinases that rely on both positive and negative determinants for scoring individual phosphosites for their suitability as kinase substrates. This represents a marked advancement over existing methods such as those used in NetPhorest (179 kinases in 76 groups) and NetworKIN (123 kinases), which consider only positive determinants for kinase substrate prediction. Comparison of our predicted matrices with experimentally-derived matrices from about 9,000 known kinase-phosphosite substrate pairs revealed a high degree of concordance with the established preferences of about 150 well studied protein kinases. Furthermore for many of the better known kinases, the predicted optimal phosphosite sequences were more accurate than the consensus phosphosite sequences inferred by simple alignment of the phosphosites of known kinase substrates. CONCLUSIONS: Application of this improved kinase substrate prediction algorithm to the primary structures of over 23, 000 proteins encoded by the human genome has permitted the identification of about 650, 000 putative phosphosites, which are posted on the open source PhosphoNET website (http://www.phosphonet.ca).