Exceptionally Fast Separation of Xylene Isomers with Zeolitic Nanotube Array Membranes.

The separation of xylene isomers is of vital importance in chemical industry but remains challenging due to their similar structure and overlapping physiochemical properties. Membrane-based separations using the zeolite MFI, graphene oxide, and metal-organic frameworks have been intensively studied for this application, but the performance is limited by the well-known rule that the filtrate permeance scales inversely with the membrane thickness. We propose a novel membrane design that is capable of breaking this rule, based on an array of recently discovered zeolite nanotubes. Each zeolite nanotube possesses a 3.6-nm-wide central channel, connecting to dense, uniform 0.8-nm-wide holes on its wall that act as selective pores. Comprehensive molecular dynamics simulations show that this membrane exhibits permeance exceeding current state-of-the-art membranes by at least an order of magnitude while simultaneously maintaining an acceptable selectivity. In particular, a thicker membrane featuring longer zeolite nanotubes exhibits a higher permeance due to the presence of more selective pores. The proposed membrane design is expected to be broadly applied to other gas separations and even desalination as long as zeolitic nanotubes with customized pores are available.

Strain Engineering of Twisted Bilayer Graphene: The Rise of Strain-Twistronics.

The layer-by-layer stacked van der Waals structures (termed vdW hetero/homostructures) offer a new paradigm for materials design-their physical properties can be tuned by the vertical stacking sequence as well as by adding a mechanical twist, stretch, and hydrostatic pressure to the atomic structure. In particular, simple twisting and stacking of two layers of graphene can form a uniform and ordered Moiré superlattice, which can effectively modulate the electrons of graphene layers and lead to the discovery of unconventional superconductivity and strong correlations. However, the twist angle of twisted bilayer graphene (tBLG) is almost unchangeable once the interlayer stacking is determined, while applying mechanical elastic strain provides an alternative way to deeply regulate the electronic structure by controlling the lattice spacing and symmetry. In this review, diverse experimental advances are introduced in straining tBLG by in-plane and out-of-plane modes, followed by the characterizations and calculations toward quantitatively tuning the strain-engineered electronic structures. It is further discussed that the structural relaxation in strained Moiré superlattice and its influence on electronic structures. Finally, the conclusion entails prospects for opportunities of strained twisted 2D materials, discussions on existing challenges, and an outlook on the intriguing emerging field, namely "strain-twistronics".

Nontrivial effects of geometric and charge defects on one-dimensional confined water.

Water confined within nanochannels with specific functionalities serves as the foundation for a variety of emerging nanofluidic applications. However, the structure and dynamics of the confined liquid are susceptibly influenced by practically hard-to-avoid defects, yet knowledge of this fact remains largely unexplored. Here, using extensive molecular dynamics simulations, we elucidate the significant influence of geometric and charge defects on one-dimensional confined water. We show that the two types of defects can both reshape the water density distribution by constraining the translocation of water molecules along the circumferential direction. In addition to structural alterations, collective translocation and rotation of water slabs arise during transportation under external pressure. Below the temperature threshold marking the initiation of liquid-solid transition, the geometric defect retards water diffusion through a pinning effect, while the charge defect induces an anti-freezing effect. The latter is attributed to the electrostatic interaction between the charge defect and water molecules that hinders the formation of a stable hydrogen bond network by disrupting molecular dipole orientation. Consequently, this behavior results in a reduction in the number and lifetime of hydrogen bonds within the phase transition interval. The distinct roles of the two types of defects could be utilized to control the structure and dynamics of confined liquids that may result in distinct functionalities for nanofluidic applications.

Near-Infrared Blinking Carbon Dots Designed for Quantitative Nanoscopy.

Blinking carbon dots (CDs) have attracted attention as a probe for single molecule localization microscopy (SMLM), yet quantitative analysis is limited because of inept blinking and low signal-to-noise ratio (SNR). Here we report the design and synthesis of near-infrared (NIR) blinking CDs with a maximum emission of around 750 nm by weaving a nitrogen-doped aromatic backbone with surplus carboxyl groups on the surface. The NIR-CDs allow conjugation to monovalent antibody fragments for labeling and imaging of cellular receptors as well as afford increases of 52% in SNR and 33% in localization precision over visible CDs. Analysis of fluorescent bursts allows for accurate counting of cellular receptors at the nanoscale resolution. Using NIR-CDs-based SMLM, we demonstrate oligomerization and internalization of programmed cell death-ligand 1 by a small molecule inhibitor for checkpoint blockade. Our NIR-CDs can become a generally applicable probe for quantitative nanoscopy in chemistry and biology.

Mechanism Regulating Self-Intercalation in Layered Materials.

Recent experimental breakthrough demonstrated a powerful synthesis approach for intercalating the van der Waals gap of layered materials to achieve property modulation, thereby opening an avenue for exploring new physics and devising novel applications, but the mechanism governing intercalant assembly patterns and properties remains unclear. Based on extensive structural search and energetics analysis by ab initio calculations, we reveal a Sabatier-like principle that dictates spatial arrangement of self-intercalated atoms in transition metal dichalcogenides. We further construct a robust descriptor quantifying that strong intercalant-host interactions favor a monodispersing phase of intercalated atoms that may exhibit ferromagnetism, while weak interactions lead to a trimer phase with attenuated or quenched magnetism, which further evolves into tetramer and hexagonal phases at increasing intercalant density. These findings elucidate the mechanism underpinning experimental observations and paves the way for rational design and precise control of self-intercalation in layered materials.

Deep-Learning-Enhanced Diffusion Imaging Assay for Resolving Local-Density Effects on Membrane Receptors.

G-protein-coupled receptor (GPCR) density at the cell surface is thought to regulate receptor function. Spatially resolved measurements of local-density effects on GPCRs are needed but technically limited by density heterogeneity and mobility of membrane receptors. We now develop a deep-learning (DL)-enhanced diffusion imaging assay that can measure local-density effects on ligand-receptor interactions in the plasma membrane of live cells. In this method, the DL algorithm allows the transformation of 100 ms exposure images to density maps that report receptor numbers over any specified region with ∼95% accuracy by 1 s exposure images as ground truth. With the density maps, a diffusion assay is further established for spatially resolved measurements of receptor diffusion coefficient as well as to express relationships between receptor diffusivity and local density. By this assay, we scrutinize local-density effects on chemokine receptor CXCR4 interactions with various ligands, which reveals that an agonist prefers to act with CXCR4 at low density while an inverse agonist dominates at high density. This work suggests a new insight into density-dependent receptor regulation as well as provides an unprecedented assay that can be applicable to a wide variety of receptors in live cells.

Symmetry Breaking and Anomalous Conductivity in a Double-Moiré Superlattice.

In a two-dimensional moiré superlattice, the atomic reconstruction of constituent layers could introduce significant modifications to the lattice symmetry and electronic structure at small twist angles. Here, we employ conductive atomic force microscopy to investigate a twisted trilayer graphene double-moiré superlattice. Two sets of moiré superlattices are observed. At neighboring domains of the large moiré, the current exhibits either 2- or 6-fold rotational symmetry, indicating delicate symmetry breaking beyond the rigid model. Moreover, an anomalous current appears at the "A-A" stacking site of the larger moiré, contradictory to previous observations on twisted bilayer graphene. Both behaviors can be understood by atomic reconstruction, and we also show that the measured current is dominated by the tip-graphene contact resistance that maps the local work function qualitatively. Our results reveal new insights of atomic reconstruction in novel moiré superlattices and opportunities for manipulating exotic quantum states on the basis of twisted van der Waals heterostructures.

Simultaneous Measurement of Refractive Index and Temperature Based on SMF-HCF-FCF-HCF-SMF Fiber Structure.

In this research, we proposed and experimentally verified a compact all-fiber sensor that can measure refractive index (RI) and temperature simultaneously. Two segments of hollow-core fiber (HCF) are connected to the two ends of the four-core fiber (FCF) as a beam splitter and a coupler, and then spliced with two sections of single-mode fibers (lead-in and lead-out SMF), respectively. The two hollow-core fibers can excite the higher-order modes of the four-core fiber and recouple the core modes and higher-order modes into the outgoing single-mode fiber, thereby forming inter-mode interference. The different response sensitivities of two interference dips to RI and temperature manifest that the proposed structure can achieve simultaneous measurement. From the experimental results, it can be seen that the maximum sensitivity of the sensor to RI and temperature is 275.30 nm/RIU and 94.4 pm/°C, respectively. When the wavelength resolution is 0.02 nm, the RI and temperature resolutions of the sensor are 7.74 × 10-5 RIU and 0.335 °C. The proposed dual-parameter optical sensor has the advantages of high sensitivities, good repeatability, simple fabrication, and structure. In addition, it has potential application value in multi-parameter simultaneous measurement.

Side-Polish Plastic Optical Fiber Based SPR Sensor for Refractive Index and Liquid-Level Sensing.

In this work, a simple side-polish plastic optical fiber (POF)-based surface plasmon resonance (SPR) sensor is proposed and demonstrated for simultaneous measurement of refractive index (RI) and liquid level. The effects of side-polish depths on the sensing performance were studied. The experimental results show that the SPR peak wavelength will be changed as the RI changes, and the SPR peak intensity will be changed with the liquid level variation. By monitoring the changes in peak wavelength and intensity, the RI and liquid level can be detected simultaneously. Experimental results show that an RI sensitivity of 2008.58 nm/RIU can be reached at an RI of 1.39. This sensor has the advantages of simple structure and low cost, which has a good prospect in the field of biochemical sensing.

Parathyroid Hormone-Like Hormone Induces Epithelial-to-Mesenchymal Transition of Intestinal Epithelial Cells by Activating the Runt-Related Transcription Factor 2.

Epithelial-to-mesenchymal transition (EMT) is a key contributor to fibroblast activation in fibrosis of multiple organs, including the intestine. Parathyroid hormone-like hormone (PTHLH) is an important factor in renal fibrosis and regulates several processes, including EMT. Herein, we investigated the role of PTHLH-induced EMT in intestinal fibrosis associated with Crohn disease. The expression levels of the EMT-related proteins, PTHLH, and parathyroid hormone receptor 1 (PTH1R) in intestinal tissues were determined by immunohistochemistry, and our results revealed that PTHLH and PTH1R were significantly elevated and associated with EMT marker expression. Moreover, neutralizing PTH1R and antagonizing PTHLH bioactivity prevented transforming growth factor-ß1-induced EMT. PTH1R can propagate the protein kinase A (PKA) signal and activate downstream nuclear transcription factors, including runt-related transcription factor 2 (Runx2). In addition, lentiviral vector-PTHLH-treated mice were highly sensitive to 2,4,6-trinitrobenzene sulfonic acid, and analysis of the PTHLH-PTH1R axis revealed the involvement of PKA-Runx2 in PTHLH-induced EMT. Our results indicate that PTHLH triggered EMT in intestinal epithelial cells through the PKA-Runx2 pathway, which might serve as a therapeutic target for intestinal fibrosis in Crohn disease.

Molecular Mechanism of Lipid Nanodisk Formation by Styrene-Maleic Acid Copolymers.

Experimental characterization of membrane proteins often requires solubilization. A recent approach is to use styrene-maleic acid (SMA) copolymers to isolate membrane proteins in nanometer-sized membrane disks, or so-called SMA lipid particles (SMALPs). The approach has the advantage of allowing direct extraction of proteins, keeping their native lipid environment. Despite the growing popularity of using SMALPs, the molecular mechanism behind the process remains poorly understood. Here, we unravel the molecular details of the nanodisk formation by using coarse-grained molecular dynamics simulations. We show how SMA copolymers bind to the lipid bilayer interface, driven by the hydrophobic effect. Due to the concerted action of multiple adsorbed copolymers, large membrane defects appear, including small, water-filled pores. The copolymers can stabilize the rim of these pores, leading to pore growth and membrane disruption. Although complete solubilization is not seen on the timescale of our simulations, self-assembly experiments show that small nanodisks are the thermodynamically preferred end state. Our findings shed light on the mechanism of SMALP formation and on their molecular structure. This can be an important step toward the design of optimized extraction tools for membrane protein research.

Parathyroid Hormone-Related Protein (1-40) Enhances Calcium Uptake in Rat Enterocytes Through PTHR1 Receptor and Protein Kinase Cα/ß Signaling.

BACKGROUND/AIMS: Parathyroid hormone-related protein (PTHrP) is implicated in regulating calcium homeostasis in vertebrates, including sea bream, chick, and mammals. However, the molecular mechanism underlying the function of PTHrP in regulating calcium transport is still not fully investigated. This study aimed to investigate the effect of PTHrP on the calcium uptake and its underlying molecular mechanism in rat enterocytes. METHODS: The rat intestinal epithelial cell line (IEC-6) was used. Calcium uptake was determined by using the fluo-4 acetoxymethyl ester fluorescence method. The expression levels of RNAs and proteins was assessed by RT-PCR and Western-blot, respectively. RESULTS: PTHrP (1-40) induced rapid calcium uptake in enterocytes in a dose-dependent manner. PTHrP (1-40) up-regulated parathyroid hormone 1 receptor (PTHR1) protein but not 1,25D3-MARRS receptor. Pre-treatment of anti- PTHR1 antibody abolished the PTHrP (1-40)-induced calcium uptake. PTHrP (1-40) significantly up-regulated four transcellular calcium transporter proteins, potential vanilloid member 6 (TRPV6), calbindin-D9k (CaBP-D9k), sodium-calcium exchanger 1 (NCX1) and plasma membrane calcium ATPase 1 (PMCA1), in a dose- and time-dependent manner. Pre-treatment with TRPV6 or CaBP-D9k antibodies or knockout of rat TRPV6 or CaBP-D9k markedly inhibited PTHrP (1-40)-induced calcium uptake, whereas inhibition of NCX or PMCA1 by antibodies or inhibitors had no effect on PTHrP(1-40)-induced calcium uptake. Furthermore, PTHrP (1-40) treatment up-regulated protein levels of protein kinase C (PKC α/ß) and protein kinase A (PKA). Pretreatment of PKC α/ß inhibitor (but not PKA inhibitor) inhibited PTHrP (1-40)-induced calcium uptake. CONCLUSION: PTHrP (1-40) stimulates calcium uptake via PTHR1 receptor and PKC α/ß signaling pathway in rat enterocytes, and calcium transporters TRPV6 and CaBP-D9k are necessary for this stimulatory effect.

Insertion of Neurotransmitters into a Lipid Bilayer Membrane and Its Implication on Membrane Stability: A†Molecular Dynamics Study.

The signaling molecules in neurons, called neurotransmitters, play an essential role in the transportation of neural signals, during which the neurotransmitters interact with not only specific receptors, but also cytomembranes, such as synaptic vesicle membranes and postsynaptic membranes. Through extensive molecular dynamics simulations, the atomic-scale insertion dynamics of typical neurotransmitters, including methionine enkephalin (ME), leucine enkephalin (LE), dopamine (DA), acetylcholine (ACh), and aspartic acid (ASP), into lipid bilayers is investigated. The results show that the first three neurotransmitters (ME, LE, and DA) are able to diffuse freely into both 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) membranes, and are guided by the aromatic residues Tyr and Phe. Only a limited number of these neurotransmitters are allowed to penetrate into the membrane, which suggests an intrinsic mechanism by which the membrane is protected from being destroyed by excessive inserted neurotransmitters. After spontaneous insertion, the neurotransmitters disturb the surrounding phospholipids in the membrane, as indicated by the altered distribution of components in lipid leaflets and the disordered lipid tails. In contrast, the last two neurotransmitters (ACh and ASP) cannot enter the membrane, but instead always diffuse freely in solution. These findings provide an understanding at the atomic level of how neurotransmitters interact with the surrounding cytomembrane, as well as their impact on membrane behavior.

Harvesting Energy from Atmospheric Water: Grand Challenges in Continuous Electricity Generation.

Atmospheric water is ubiquitous on earth and extensively participates in the natural water cycle through evaporation and condensation. This process involves tremendous energy exchange with the environment, but very little of the energy has so far been harnessed. The recently emerged hydrovoltaic technology, especially moisture-induced electricity, shows great potential in harvesting energy from atmospheric water and gives birth to moisture energy harvesting devices. The device performance, especially the long-term operational capacity, has been significantly enhanced over the past few years. Further development; however, requires in-depth understanding of mechanisms, innovative materials, and ingenious system designs. In this review, beginning with describing the basic properties of water, the key aspects of the water-hygroscopic material interactions and mechanisms of power generation are discussed. The current material systems and advances in promising material development are then summarized. Aiming at the chief bottlenecks of limited operational time, advanced system designs that are helpful to improve device performance are listed. Especially, the synergistic effect of moisture adsorption and water evaporation on material and system levels to accomplish sustained electricity generation is discussed. Last, the remaining challenges are analyzed and future directions for developing this promising technology are suggested.

Operationally stable perovskite solar modules enabled by vapor-phase fluoride treatment.

The ever-increasing power conversion efficiency of perovskite solar cells has illuminated the future of the photovoltaic industry, but the development of commercial devices is hampered by their poor stability. In this study, we report a scalable stabilization method using vapor-phase fluoride treatment, which achieves 18.1%-efficient solar modules (228 square centimeters) with accelerated aging-projected T80 lifetimes (time to 80% of efficiency remaining) of 43,000 ± 9000 hours under 1-sun illumination at 30°C. The high stability results from vapor-enabled homogeneous fluorine passivation over large-area perovskite surfaces, suppressing defect formation energy and ion diffusion. The extracted degradation activation energy of 0.61 electron volts for solar modules is comparable to that of most reported stable cells, which indicates that modules are not inherently less stable than cells and closes the cell-to-module stability gap.

Cascaded plastic optical fiber based SPR sensor for simultaneous measurement of refractive index and temperature.

A cascaded side-polish plastic optical fiber (POF) and FONTEX optical fiber based surface plasmon resonance (SPR) sensor is proposed for simultaneous measurement of refractive index (RI) and temperature. The side-polish POF and FONTEX optical fiber are connected by using the UV glue in a Teflon plastic tube. The SPR phenomenon can be excited at both of the side-polish region and the FONTEX fiber cladding. The polydimethylsiloxane (PDMS) is coated on the side-polish POF to get a temperature sensing channel. Due to the low RI sensitivity of the FONTEX optical fiber, the cascaded fiber sensor can obtain a broader RI measurement range with a low crosstalk. An RI sensitivity of 700 nm/RIU in the RI measurement range of 1.335-1.39 and a temperature sensitivity of -1.02 nm/°C measured in deionized water with a range of 20-60 °C are obtained. In addition, the cascaded POF based SPR sensor has potential application prospects in the field of biochemical sensing.

Graphene binding on black phosphorus enables high on/off ratios and mobility.

Graphene is one of the most promising candidates for integrated circuits due to its robustness against short-channel effects, inherent high carrier mobility and desired gapless nature for Ohmic contact, but it is difficult to achieve satisfactory on/off ratios even at the expense of its carrier mobility, limiting its device applications. Here, we present a strategy to realize high back-gate switching ratios in a graphene monolayer with well-maintained high mobility by forming a vertical heterostructure with a black phosphorus multi-layer. By local current annealing, strain is introduced within an established area of the graphene, which forms a reflective interface with the rest of the strain-free area and thus generates a robust off-state via local current depletion. Applying a positive back-gate voltage to the heterostructure can keep the black phosphorus insulating, while a negative back-gate voltage changes the black phosphorus to be conductive because of hole accumulation. Then, a parallel channel is activated within the strain-free graphene area by edge-contacted electrodes, thereby largely inheriting the intrinsic carrier mobility of graphene in the on-state. As a result, the device can provide an on/off voltage ratio of >103 as well as a mobility of ∼8000 cm2 V-1 s-1 at room temperature, meeting the low-power criterion suggested by the International Roadmap for Devices and Systems.

Exceptionally fast water desalination at complete salt rejection by pristine graphyne monolayers.

Desalination that produces clean freshwater from seawater holds the promise of solving the global water shortage for drinking, agriculture and industry. However, conventional desalination technologies such as reverse osmosis and thermal distillation involve large amounts of energy consumption, and the semipermeable membranes widely used in reverse osmosis face the challenge to provide a high throughput at high salt rejection. Here we find by comprehensive molecular dynamics simulations and first principles modeling that pristine graphyne, one of the graphene-like one-atom-thick carbon allotropes, can achieve 100% rejection of nearly all ions in seawater including Na(+), Cl(-), Mg(2+), K(+) and Ca(2+), at an exceptionally high water permeability about two orders of magnitude higher than those for commercial state-of-the-art reverse osmosis membranes at a salt rejection of ~98.5%. This complete ion rejection by graphyne, independent of the salt concentration and the operating pressure, is revealed to be originated from the significantly higher energy barriers for ions than for water. This intrinsic specialty of graphyne should provide a new possibility for the efforts to alleviate the global shortage of freshwater and other environmental problems.

Computational Advances of Protein/Neurotransmitter-membrane Interactions Involved in Vesicle Fusion and Neurotransmitter Release.

Vesicle fusion is of crucial importance to neuronal communication at neuron terminals. The exquisite but complex fusion machinery for neurotransmitter release is tightly controlled and regulated by protein/neurotransmitter-membrane interactions. Computational 'microscopies', in particular molecular dynamics simulations and related techniques, have provided notable insight into the physiological process over the past decades, and have made enormous contributions to fields such as neurology, pharmacology and pathophysiology. Here we review the computational advances of protein/neurotransmitter-membrane interactions related to presynaptic vesicle-membrane fusion and neurotransmitter release, and outline the in silico challenges ahead for understanding this important physiological process.

Growth Instability of 2D Materials on Non-Euclidean Surfaces.

Chemical growth of two-dimensional (2D) materials with controlled morphology is critical to bring their tantalizing properties to fruition. However, the growth must be on a substrate, which involves either intrinsic or intentionally introduced undulation, at a scale significantly larger than the materials thickness. Recent theory and experiments showed that 2D materials grown on a curved feature on substrates can incur a variety of topological defects and grain boundaries. Using a Monte Carlo method, we herein show that 2D materials growing on periodically undulated substrates with nonzero Gaussian curvature of practical relevance follow three distinct modes: defect-free conformal, defect-free suspension and defective conformal modes. The growth on the non-Euclidean surface can accumulate tensile stress that gradually lifts the materials from substrates and progressively turns the conformal mode into a suspension mode with increasing the undulation amplitude. Further enhancing the undulation can trigger Asaro-Tiller-Grinfield growth instability in the materials, manifested as discretely distributed topological defects due to strong stress concentration. We rationalize these results by model analyses and establish a "phase" diagram for guiding the control of growth morphology via substrate patterning. The undulation-induced suspension of 2D materials can help understand the formation of overlapping grain boundaries, spotted quite often in experiments, and guide how to avoid them.