Large-Scale, Vertically Aligned 2D Subnanochannel Arrays by a Smectic Liquid Crystal Network for High-Performance Osmotic Energy Conversion.

The osmotic energy, an abundant renewable energy source, can be directly converted to electricity by nanofluidic devices with ion-selective membranes. 2D nanochannels constructed by nanosheets possess abundant lateral interfacial ion-exchange sites and exhibit great superiority in nanofluidic devices. However, the most accessible orientation of the 2D nanochannels is parallel to the membrane surface, undoubtedly resulting in the conductivity loss. Herein, first vertically aligned 2D subnanochannel arrays self-assembled by a smectic liquid crystal (LC) network that exhibit high-performance osmotic energy conversion are demonstrated. The 2D subnanochannel arrays are fabricated by in situ photopolymerization of monomers in the LC phase. The as-prepared membrane exhibits excellent water-resistance and mechanical strength. The 2D subnanochannels with excellent cation selectivity and conductivity show high-performance osmotic energy conversion. The power density reaches up to about 22.5 W m-2 with NaCl solution under a 50-fold concentration gradient, which is among with ultrahigh power density. This membrane design concept provides promising applications in osmotic energy conversion.

Bioinspired light-driven chloride pump with helical porphyrin channels.

Halorhodopsin, a light-driven chloride pump, utilizes photonic energy to drive chloride ions across biological membranes, regulating the ion balance and conveying biological information. In the light-driven chloride pump process, the chloride-binding chromophore (protonated Schiff base) is crucial, able to form the active center by absorbing light and triggering the transport cycle. Inspired by halorhodopsin, we demonstrate an artificial light-driven chloride pump using a helical porphyrin channel array with excellent photoactivity and specific chloride selectivity. The helical porphyrin channels are formed by a porphyrin-core star block copolymer, and the defects along the channels can be effectively repaired by doping a small number of porphyrins. The well-repaired porphyrin channel exhibits the light-driven Cl- migration against a 3-fold concentration gradient, showing the ion pumping behavior. The bio-inspired artificial light-driven chloride pump provides a prospect for designing bioinspired responsive ion channel systems and high-performance optogenetics.

Anti-Entropy Aggregation of Minority Groups in Polymers: Design and Applications.

Minority groups are non-repeating units with very low content that inevitably exist in polymers. Typically, these minority groups are easily surrounded by the majority of repeating units and randomly dispersed, maximizing the entropy of minority groups. In the concept, anti-entropy aggregation (AEA) of minority groups is described, and different pathways are outlined. They are polymer crystallization-driven AEA, supramolecular interaction-induced AEA, phase separation-confined AEA, and hierarchical interactions-driven AEA. Typical applications of AEA materials are also presented, including fluorescence probes, self-healing materials, ion transporting regulation, and osmotic energy conversion. The concept of AEA is expected to inspire the fabrication of novel functional systems.

Ultra-mechanosensitive Chloride Ion Transport through Bioinspired High-Density Elastomeric Nanochannels.

Mechanosensitive ion channels play crucial roles in physiological activities, where small mechanical stimuli induce the membrane tension, trigger the ion channels' deformation, and are further transformed into significant electrochemical signals. Artificial ion channels with stiff moduli have been developed to mimic mechanosensory behaviors, exhibiting an electrochemical response by the high-pressure-induced flow. However, fabricating flexible mechanosensitive channels capable of regulating specific ion transporting upon dramatic deformation has remained a challenge. Here, we demonstrate bioinspired high-density elastomeric channels self-assembled by polyisoprene-b-poly4-vinylpyridine, which exhibit ultra-mechanosensitive chloride ion transport resulting from nanochannel deformation. The PI-formed continuous elastic matrix can transmit external forces into internal tensions, while P4VP forms transmembrane chloride channels that undergo dramatic deformation and respond to mechanical stimuli. The integrated and flexible chloride channels present a dramatic and stable electrochemical signal toward a low pressure of 0.2 mbar. This research first demonstrates the artificial mechanosensory chloride channels, which could provide a promising avenue for designing flexible and responsive channel systems.

Modulus watch: In situ determination of the gel modulus by timing the fluorescence color change.

The gel modulus, a key parameter for gel materials, is traditionally determined by cumbersome rheometer. Recently, probe technologies occur to meet the requirements of in situ determination. Till now, in situ and quantitatively testing of gel materials with unabridged structure informations still remains a challenge. Here, we provide a facile, in situ approach to determine the gel modulus, by timing the aggregation of a doped fluorescence probe. The probe shows green emission during aggregation and shifts to blue once it forms aggregates. The higher modulus of the gel, the longer probe's aggregation time. Furthermore, a quantitative correlation of gel modulus with the aggregation time is established. The in situ method not only facilitates the scientific researches in the field of gels, but also provides a new approach for spatiotemporal materials.

One Porphyrin Per Chain Self-Assembled Helical Ion-Exchange Channels for Ultrahigh Osmotic Energy Conversion.

Ion-exchange membranes (IEMs) convert osmotic energy into electricity when embedded in a reverse electrodialysis cell. IEMs with both high permselectivity and ionic conductivity are highly needed to increase the energy conversion efficiency. The ionic conductivity can be improved by increasing the content of immobile charge carriers, but it is always accompanied by undesirable permselectivity decrease due to excess swelling. Until now, breaking the permselectivity-conductivity tradeoff still has remained a challenge. Here, we demonstrate a membrane with the least ion-exchange capacity (∼10-2 mequiv g-1), generating an ultrahigh power density of 19.3 W m-2 at a 50-fold concentration ratio. The membrane is made of a porphyrin-core four-star block copolymer (p-BCP), forming the high-density helical porphyrin channels (∼1011 cm-2) under the synergistic effect of BCP self-assembly and porphyrin π-π stacking. The porphyrin channel shows high Cl- selectivity and high conductivity, benefiting high-performance osmotic energy conversion. This economic and facile membrane design strategy provides a promising approach to developing a new generation of IEMs.

Unconventional Dual Ion Selectivity Determined by the Forward Side of a Bipolar Channel toward Ion Flux.

Ion selectivity is an essential property of ion-selective membranes (ISMs). To date, all of the artificial ISMs have been reported to exhibit sole ion selectivity (SIS), either cation or anion selectivity. Here, we first demonstrate unconventional dual ion selectivity (DIS) in a bipolar channel membrane determined by the forward side toward ion flux. When the bipolar membrane meets the conditions of opposite ion selectivities and comparable resistance for both constructive layers, no matter which layer faces the ion flux, it functions as a selective layer and determines the selectivity of the whole membrane. The exploration of the unconventional DIS property inspires us to fabricate a new generation of ISMs, as well as other membranes for separation.

Large-scale, robust mushroom-shaped nanochannel array membrane for ultrahigh osmotic energy conversion.

The osmotic energy, a large-scale clean energy source, can be converted to electricity directly by ion-selective membranes. None of the previously reported membranes meets all the crucial demands of ultrahigh power density, excellent mechanical stability, and upscaled fabrication. Here, we demonstrate a large-scale, robust mushroom-shaped (with stem and cap) nanochannel array membrane with an ultrathin selective layer and ultrahigh pore density, generating the power density up to 22.4 W·m-2 at a 500-fold salinity gradient, which is the highest value among those of upscaled membranes. The stem parts are a negative-charged one-dimensional (1D) nanochannel array with a density of ~1011 cm-2, deriving from a block copolymer self-assembly; while the cap parts, as the selective layer, are formed by chemically grafted single-molecule-layer hyperbranched polyethyleneimine equivalent to tens of 1D nanochannels per stem. The membrane design strategy provides a promising approach for large-scale osmotic energy conversion.

Detecting topology freezing transition temperature of vitrimers by AIE luminogens.

Vitrimers are one kind of covalently crosslinked polymers that can be reprocessed. Topology freezing transition temperature (Tv) is vitrimer's upper limit temperature for service and lower temperature for recycle. However, there has been no proper method to detect the intrinsic Tv till now. Even worse, current testing methods may lead to a misunderstanding of vitrimers. Here we provide a sensitive and universal method by doping or swelling aggregation-induced-emission (AIE) luminogens into vitrimers. The fluorescence of AIE-luminogens changes dramatically below and over Tv, providing an accurate method to measure Tv without the interference of external force. Moreover, according to this method, Tv is independent of catalyst loading. The opposite idea has been kept for a long time. This method not only is helpful for the practical application of vitrimers so as to reduce white wastes, but also may facilitate deep understanding of vitrimers and further development of functional polymer materials.

Engineered Nanochannel Membranes with Diode-like Behavior for Energy Conversion over a Wide pH Range.

Electric eels can generate high potential bioelectricity because of the numerous electrocytes, where the cell membranes contain ion-selective channels. Net electric current is formed by the directional permeation of ions across the channels. Many nanofluidic devices have been designed for energy conversion. However, the challenge still remains of the fabrication of scalable ion-selective membranes with high power density. Inspired by the electric eels, we designed an asymmetric nanochannel membrane with diode-like ion transport behaviors, resulting in high performance energy conversion over a wide pH range. The nanochannel membranes were obtained from the polymeric nanochannels with carboxyl groups and the anodic alumina oxide (AAO) nanochannels bearing hydroxyl groups. At different pH conditions, the synergistic effect of the hybrid nanochannels ensured directional ion regulation, leading to energy conversion with high power density. The scalable, versatile nanochannel membranes have promising potential applications in the salinity gradient energy harvest from various sources.

Artificial NO and Light Cooperative Nanofluidic Diode Inspired by Stomatal Closure of Guard Cells.

Gas messenger molecule (NO) plays important roles in K+ nanochannels of guard cells by binding directly to the heme-containing enzymes. Inspired by this natural phenomenon, we developed artificial K+ nanochannels modified with ferroporphyrin, where NO triggered the nanochannels to turn "ON" states from the ferroporphyrin blocked "OFF" states. The mechanism relies on the fact that NO has higher affinity with ferroporphyrin compared to carboxyl groups on the nanochannel surface. The synergistic effect of the released carboxyl groups and the conically asymmetric shape leads the ion transportation to be diode-like. However, the nanofluidic diode properties vanished after illumination with light to remove NO from the ferroporphyrin-NO complex. This NO and light cooperative nanofluidic diode possesses excellent stability and reversibility, which shows great promise for use in gas detection and remote control of mass delivery.

Ultrathin and Ion-Selective Janus Membranes for High-Performance Osmotic Energy Conversion.

The osmotic energy existing in fluids is recognized as a promising "blue" energy source that can help solve the global issues of energy shortage and environmental pollution. Recently, nanofluidic channels have shown great potential for capturing this worldwide energy because of their novel transport properties contributed by nanoconfinement. However, with respect to membrane-scale porous systems, high resistance and undesirable ion selectivity remain bottlenecks, impeding their applications. The development of thinner, low-resistance membranes, meanwhile promoting their ion selectivity, is a necessity. Here, we engineered ultrathin and ion-selective Janus membranes prepared via the phase separation of two block copolymers, which enable osmotic energy conversion with power densities of approximately 2.04 W/m2 by mixing natural seawater and river water. Both experiments and continuum simulation help us to understand the mechanism for how membrane thickness and channel structure dominate the ion transport process and overall device performance, which can serve as a general guiding principle for the future design of nanochannel membranes for high-energy concentration cells.

Smooth Muscle Cell-Mimetic CO-Regulated Ion Nanochannels.

A CO-regulated ion nanochannel is demonstrated, which is inspired by the living activity of CO-induced smooth muscle vasodilation. The mechanism relies on the fact that CO has a higher affinity with ferroporphyrin compared to carboxyl groups on the surface of the nanochannels. The cooperation effect of the released carboxyl groups and the conical asymmetric shape leads the ion transportation to be diode-like.

Biomimetic Nanofluidic Diode Composed of Dual Amphoteric Channels Maintains Rectification Direction over a Wide pH Range.

pH-gated ion channels in cell membranes play important roles in the cell's physiological activities. Many artificial nanochannels have been fabricated to mimic the natural phenomenon of pH-gated ion transport. However, these nanochannels show pH sensitivity only within certain pH ranges. Wide-range pH sensitivity has not yet been achieved. Herein, for the first time, we provide a versatile strategy to increase the pH-sensitive range by using dual amphoteric nanochannels. In particular, amphoteric polymeric nanochannels with carboxyl groups derived from a block copolymer (BCP) precursor and nanochannels with hydroxyl groups made from anodic alumina oxide (AAO) were used. Due to a synergistic effect, the hybrid nanochannels exhibit nanofluidic diode properties with single rectification direction over a wide pH range. The novel strategy presented here is a scalable, low-cost, and robust alternative for the construction of large-area membranes for nanofluidic applications, such as the separation of biomolecules.

Draft genome sequence of Sphingomonas paucimobilis strain LCT-SP1 isolated from the Shenzhou X spacecraft of China.

Sphingomonas paucimobilis strain LCT-SP1 is a glucose-nonfermenting Gram-negative, chemoheterotrophic, strictly aerobic bacterium. The major feature of strain LCT-SP1, isolated from the Chinese spacecraft Shenzhou X, together with the genome draft and annotation are described in this paper. The total size of strain LCT-SP1 is 4,302,226 bp with 3,864 protein-coding and 50 RNA genes. The information gained from its sequence is potentially relevant to the elucidation of microbially mediated corrosion of various materials.

Biodegradation and Mineralization of Polystyrene by Plastic-Eating Mealworms: Part 1. Chemical and Physical Characterization and Isotopic Tests.

Polystyrene (PS) is generally considered to be durable and resistant to biodegradation. Mealworms (the larvae of Tenebrio molitor Linnaeus) from different sources chew and eat Styrofoam, a common PS product. The Styrofoam was efficiently degraded in the larval gut within a retention time of less than 24 h. Fed with Styrofoam as the sole diet, the larvae lived as well as those fed with a normal diet (bran) over a period of 1 month. The analysis of fecula egested from Styrofoam-feeding larvae, using gel permeation chromatography (GPC), solid-state (13)C cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) spectroscopy, and thermogravimetric Fourier transform infrared (TG-FTIR) spectroscopy, substantiated that cleavage/depolymerization of long-chain PS molecules and the formation of depolymerized metabolites occurred in the larval gut. Within a 16 day test period, 47.7% of the ingested Styrofoam carbon was converted into CO2 and the residue (ca. 49.2%) was egested as fecula with a limited fraction incorporated into biomass (ca. 0.5%). Tests with α (13)C- or ß (13)C-labeled PS confirmed that the (13)C-labeled PS was mineralized to (13)CO2 and incorporated into lipids. The discovery of the rapid biodegradation of PS in the larval gut reveals a new fate for plastic waste in the environment.

Biodegradation and Mineralization of Polystyrene by Plastic-Eating Mealworms: Part 2. Role of Gut Microorganisms.

The role of gut bacteria of mealworms (the larvae of Tenebrio molitor Linnaeus) in polystyrene (PS) degradation was investigated. Gentamicin was the most effective inhibitor of gut bacteria among six antibiotics tested. Gut bacterial activities were essentially suppressed by feeding gentamicin food (30 mg/g) for 10 days. Gentamicin-feeding mealworms lost the ability to depolymerize PS and mineralize PS into CO2, as determined by characterizing worm fecula and feeding with (13)C-labeled PS. A PS-degrading bacterial strain was isolated from the guts of the mealworms, Exiguobacterium sp. strain YT2, which could form biofilm on PS film over a 28 day incubation period and made obvious pits and cavities (0.2-0.3 mm in width) on PS film surfaces associated with decreases in hydrophobicity and the formation of C-O polar groups. A suspension culture of strain YT2 (10(8) cells/mL) was able to degrade 7.4 ± 0.4% of the PS pieces (2500 mg/L) over a 60 day incubation period. The molecular weight of the residual PS pieces was lower, and the release of water-soluble daughter products was detected. The results indicated the essential role of gut bacteria in PS biodegradation and mineralization, confirmed the presence of PS-degrading gut bacteria, and demonstrated the biodegradation of PS by mealworms.

Controlled directional water-droplet spreading on a high-adhesion surface.

Controlled directional spreading of a droplet on a smart high-adhesion surface was made possible by simply controlling anodic oxidation. The wettability gradient of the surface was controlled from 0.14 to 3.38° mm(-1) by adjusting the anodic oxidation conditions. When a water droplet made contact with the substrate, the droplet immediately spread in the direction of the wettability gradient but did not move in other directions, such as those perpendicular to the gradient direction, even when the surface was turned upside down. The spreading behavior was mainly controlled by the wettability gradient. Surfaces with a V- or inverse-V-shaped wettability gradient were also formed by the same method, and two droplets on these surfaces spread either toward or away from one another as designed. This method could be used to oxidize many conductive substrates (e.g., copper, aluminum) to form surfaces with variously shaped wettability gradients. It has potential for application in microfluidic devices.