Regulating Electrolyte Solvation Structures via Diluent-Solvent Interactions for Safe High-Voltage Lithium Metal Batteries.

Local high concentration electrolytes (LHCEs) have been proved to be one of the most promising systems to stabilize both high voltage cathodes and Li metal anode for next-generation batteries. However, the solvation structures and interactions among different species in LHCEs are still convoluted, which bottlenecks the further breakthrough on electrolyte development. Here, it is demonstrated that the hydrogen bonding interaction between diluent and solvent is crucial for the construction of LHCEs and corresponding interphase chemistries. The 2,2,2-trifluoroethyl trifluoromethane sulfonate (TFSF) is selected as diluent with the solvent dimethoxy-ethane (DME) to prepare a non-flammable LHCE for high voltage LMBs. This is first find that the hydrogen bonding interaction between TFSF and DME solvent tailors the electrolyte solvation structures by weakening the coordination of DME molecules to Li+ cations and allows more participation of anions in the first solvation shell, leading to the formation of aggregates (AGGs) clusters which are conducive to generating inorganic solid/cathodic electrolyte interphases (SEI/CEIs). The proposed TFSF based LHCE enables the Li||NCM811 (LiNi0.8 Mn0.1 O2 ) batteries to realize >80% capacity retention with a high average Coulombic efficiency of 99.8% for 230 cycles under aggressive conditions (NCM811 cathode: 3.4 mAh cm-2 , cut-off voltage: 4.4 V, and 20 µm Li foil).

Adaptive Escape of Pseudomonas aeruginosa by Application of Low-Amplitude Electric Pulses.

Marine antibiofouling using low-amplitude electric pulses (EP) is an energy-efficient and eco-friendly approach, but potential mechanisms for preventing biofouling remain unclear. In the present study, the 3D adhesion dynamics of a model microorganism─Pseudomonas aeruginosa (PAO1)─under low-amplitude cathodic EP were examined as a function of applying voltage and its duration (td). The results demonstrated that adhered bacteria escaped from the electrode surface even when EP was removed. The escaped bacteria ratio, induction period of escape, and duration of the detachment were influenced profoundly by EP amplitude but slightly by td when td ≥ 5 min. The acceleration of escaped PAO1 from the surface indicated that their flagellar motor was powered by EP. Particularly, EP enabled swimming bacteria to have adaptive motions that were sustainable and regulated by the gene rsmA. As a result, they had less accumulation near the surface. The propulsion of adhered bacteria and adaptive escape of swimming bacteria were enhanced in response to low-amplitude EP. Hence, low-amplitude and short-duration EP is promising for sustainable antibiofouling applications.

Capillary filling of star polymer melts in nanopores.

The topology of a polymer profoundly influences its behavior. However, its effect on imbibition dynamics remains poorly understood. In the present work, capillary filling (during imbibition and following full imbibition) of star polymer melts was investigated by molecular dynamics simulations with a coarse-grained model. The reversal of imbibition dynamics observed for linear-chain systems was also present for star polymers. Star polymers with short arms penetrate slower than the prediction of the Lucas-Washburn equation, while systems with long arms penetrate faster. The radius of gyration increases during confined flow, indicating the orientation and disentanglement of arms. In addition, the higher the functionality of the star polymer, the more entanglement points are retained. Besides, a stiff region near the core segments of the stars is observed, which increases in size with functionality. The proportion of different configurations of the arms (e.g., loops, trains, tails) changes dramatically with the arm length and degree of confinement but is only influenced by the functionality when the arms are short. Following full imbibition, the different decay rates of the self-correlation function of the core-to-end vector illustrate that arms take a longer time to reach the equilibrium state as the functionality, arm length, and degree of confinement increase, in agreement with recent experimental findings. Furthermore, the star topology induces a stronger effect of adsorption and friction, which becomes more pronounced with increasing functionality.

Jellyfish-inspired Polyurea Ionogel with Mechanical Robustness, Self-Healing, and Fluorescence Enabled by Hyperbranched Cluster Aggregates.

Ionogels are promising for soft iontronics, with their network structure playing a pivotal role in determining their performance and potential applications. However, simultaneously achieving mechanical toughness, low hysteresis, self-healing, and fluorescence using existing network structures is challenging. Drawing inspiration from jellyfish, we propose a novel hierarchical crosslinking network structure design for in situ formation of hyperbranched cluster aggregates (HCA) to fabricate polyurea ionogels to overcome these challenges. Leveraging the disparate reactivity of isocyanate groups, we induce the in situ formation of HCA through competing reactions, enhancing toughness and imparting the clustering-triggered emission of ionogel. This synergy between supramolecular interactions in the network and plasticizing effect in ionic liquid leads to reduced hysteresis of the ionogel. Furthermore, the incorporation of NCO-terminated prepolymer with dynamic oxime-urethane bonds (NPU) enables self-healing and enhances stretchability. Our investigations highlight the significant influence of HCA on ionogel performance, showcasing mechanical robustness including high strength (3.5 MPa), exceptional toughness (5.5 MJ m-3), resistance to puncture, and low hysteresis, self-healing, as well as fluorescence, surpassing conventional dynamic crosslinking approaches. This network design strategy is versatile and can meet the various demands of flexible electronics applications.

Anionic Hybrid Copolymerization of Sulfur with Acrylate: Strategy for Synthesis of High-Performance Sulfur-Based Polymers.

Copolymerization of elemental sulfur (S8) with vinyl monomers to develop new polymer materials is significant. Here, for the first time, we report the anionic hybrid copolymerization of S8 with acrylate at 25 °C, yielding a copolymer with short polysulfide segments; i.e., each of them consists of only one to four sulfur atoms. The formation of a longer polysulfide segment would be ceaselessly disrupted by carbon anions through the chain-transfer reaction. The copolymer of S8 with diacrylate was cross-linked and exhibited excellent mechanical properties, with an ultimate tensile strength as high as 10.7 MPa and a breaking strain of 22%. Furthermore, the introduction of tertiary amide groups to the copolymer enabled it not only to be reprocessed via press molding at room temperature but also to exhibit self-healing properties without external intervention. This study provides a facile strategy to synthesize high-performance sulfur-based copolymers under mild conditions.

Ionic-Wind-Enhanced Raman Spectroscopy without Enhancement Substrates.

Raman spectra are often masked by strong fluorescence, which severely hinders the applications of Raman spectroscopy. Herein, for the first time, we report ionic-wind-enhanced Raman spectroscopy (IWERS) incorporated with photobleaching (PB) as a noninvasive approach to detect fluorescent and vulnerable samples without a substrate. In this study, ionic wind (IW) generated by needle-net electrodes transfers charges to the sample surface in air on the scale of millimeters rather than nanometers in surface-enhanced Raman spectroscopy. Density functional theory calculations reveal that the ionic particles in IW increase the susceptibility of the sample molecules, thus enhancing the Raman signals. Meanwhile, the incorporation of IW with PB yields a synergistic effect to quench fluorescence. Therefore, this approach can improve the signal-to-noise ratio of Raman peaks up to three times higher than that with only PB. At the same time, IWERS can avoid sample pollution and destruction without substrates as well as high laser power. For archeological samples and a red rock as an analogue to Mars geological samples, IWERS successfully identified weak but key Raman peaks, which were masked by strong florescence. It suggests that IWERS is a promising tool for characterizations in the fields of archeology, planetary science, biomedicine, and soft matter.

Degradable Vinyl Polymers for Combating Marine Biofouling.

Marine organisms such as barnacle larvae and spores of algae adhere to underwater surfaces leading to marine biofouling. This phenomenon has numerous adverse impacts on marine industries and maritime activities. Due to the diversity of fouling organisms and the complexity of the marine environment, it is a huge challenge to combat marine biofouling, which limits the development and utilization of marine resources. Since the International Marine Organization banned the use of tributyltin self-polishing copolymer (SPC) coatings in 2008, the development of an environmentally friendly and efficient anti-biofouling polymer has been the most important task in this field. Tin-free SPC is a well-established and widely used polymer binder for anti-biofouling coating today. Being a nondegradable vinyl polymer, SPC exhibits poor anti-biofouling performance in static conditions. Even more, such nondegradable polymers were considered to be a source of microplastics by the International Union for the Conservation of Nature in 2019. Recently, numerous degradable polymers, which can form dynamic surface through main chain scission, have been developed for preventing marine biofouling in static conditions. Nevertheless, the regulation of their degradation and mechanical properties is limited, and they are also difficult to functionalize. A new polymer combining the advantages of vinyl polymers and degradable polymers is needed. However, such a combination is a challenge since the former are synthesized via free radical polymerization whereas the latter are synthesized via ring-opening polymerization.In this Account, we review our recent progress toward degradable vinyl polymers for marine anti-biofouling in terms of polymerization methods and structures and properties of polymers. First, we introduce the strategies for preparing degradable vinyl polymers with an emphasis on hybrid copolymerization. Then, we present the synthesis and performance of degradable and hydrolyzable polyacrylates, degradable polyurethanes with hydrolyzable side groups, and surface-fragmenting hyperbranched polymers. Polymers with degradable main chains and hydrolyzable side groups combine the advantages of SPC and degradable polymers, so they are degradable and functional. They are becoming new-generation polymers with great potential for preparing high-efficiency, long-lasting, environmentally friendly and broad-spectrum coatings to inhibit marine biofouling. They can also find applications in wastewater treatment, biomedical materials, and other fields.

Role of Surface Coverage of Sessile Probiotics in Their Interplay with Pathogen Bacteria Investigated by Digital Holographic Microscopy.

The adhesion of probiotics plays an important role in the gastrointestinal tract. Understanding the effect of the coverage of colonized probiotics on enteric pathogens is critical for the design of effective probiotic therapies. In the present work, we have investigated the adaptive behaviors of the intestinal pathogenic bacteria Enterobacter sakazakii (ES) near the surfaces coated with a probiotic─Lactobacillus rhamnosus GG (LGG) as a function of surface coverage ratio (CRLGG) by using a home-setup digital holographic microscopy. It shows that ES cells can adaptively sense LGG within a distance of 4.2 µm, even at CRLGG values as low as 0.05%. The growth inhibition of ES cells slightly varies with CRLGG, but the near-surface acceleration and accumulation of ES cells have much dependence on CRLGG. As CRLGG increases from 0.05 to 24.6%, the percentage of actively swimming ES, the motion bias, the acceleration, and the interplay duration do not linearly vary with CRLGG. Instead, each of them shows an extreme at CRLGG of 13.4%, corresponding to the chemotaxis behaviors of ES cells induced by diffusing stimuli (organic acids, bacteriocins, etc.) released from LGG, which showed an extreme concentration gradient at CRLGG = 13.4% by simulations. Our study clearly demonstrates that surface coverage of sessile probiotics profoundly influences their interplay with pathogen bacteria, which should be taken into account in designing probiotic therapies.

Mechanism Insights of Antibacterial Surfaces Coated with Dead Probiotics.

To understand the antimicrobial effect of surfaces fabricated with dead probiotics, we prepared surfaces decorated with dead probiotics Lactobacillus rhamnosus GG (LGG) with varied inactivation methods and explored their inhibitory interactions with Pseudomonas aeruginosa (PAO1). By combining several techniques, i.e., digital holographic microscopy (DHM), atomic force microscopy (AFM), RNA sequencing, and metabolomic analysis, we studied the three-dimensional (3D) swimming behaviors, surface adhesion, biofilm formation, and adaptive responses of PAO1 near such surfaces. The results show that planktonic PAO1 decreases their flick and reverse motions by downregulating the chemotaxis pathway and accelerates with less accumulation near dead LGG surfaces by upregulating the flagellar assembly pathway and decreasing cyclic adenosine monophosphate. Distinct from live siblings, the surfaces decorated with dead LGG show a significant reduction in adhesion strength with PAO1 and inhibit biofilm formation with more downregulated genes in the Pseudomonas quinolone signal and biofilm formation pathway. We demonstrate that the antibacterial ability of such surfaces stems from the gradually released lysate from the dead LGG that is unfavorable to PAO1 in close proximity. The releasing rate and order depend on the cell membrane integrity, which closely relates to the inactivation methods.

Fluorescent Visualization of Chemical Profiles across the Air-Water Interface.

Chemical transfer across the air-water interface is one of the most important geochemical processes of global significance. Quantifying such a process has remained extremely challenging due to the lack of suitable technologies to measure chemical diffusion across the air-water microlayer. Herein, we present a fluorescence optical system capable of visualizing the formation of the air-water microlayer with a spatial resolution of 10 µm and quantifying air-water diffusion fluxes using pyrene as a target chemical. We show for the first time that the air-water microlayer is composed of the surface microlayer in water (∼290 ± 40 µm) and a diffusion layer in air (∼350 ± 40 µm) with 1 µg L-1 of pyrene. The diffusion flux of pyrene across the air-water interface is derived from its high-resolution concentration profile without any pre-emptive assumption, which is 2 orders of magnitude lower than those from the conventional method. This system can be expanded to visualize diffusion dynamics of other fluorescent chemicals across the air-water interface and provides a powerful tool for furthering our understanding of air-water mass transfer of organic chemicals related to their global cycling.

Janus Effect of Lewis Acid Enables One-Step Block Copolymerization of Ethylene Oxide and N-Sulfonyl Aziridine.

One-step sequence-selective block copolymerization requires stringent catalytic control of monomers relative activity and enchainment order. It has been especially rare for An Bm -type block copolymers from simple binary monomer mixtures. Here, ethylene oxide (EO) and N-sulfonyl aziridine (Az) compose a valid pair provided with a bicomponent metal-free catalyst. Optimal Lewis acid/base ratio allows the two monomers to strictly block-copolymerize in a reverse order (EO-first) as compared with the conventional anionic route (Az-first). Livingness of the copolymerization facilitates one-pot synthesis of multiblock copolymers by addition of mixed monomers in batches. Calculation results reveal that a Janus effect of Lewis acid on the two monomers is key to enlarge the activity difference and reverse the enchainment order.

Cation-amino acid interactions: Implications for protein destabilization.

The mechanism for protein stabilization or destabilization has long been an open quest. In the present study, we have studied the interactions between amino acids and guanidinium (Gdm+)/ammonium (NH4+) ions by using low field nuclear magnetic resonance (LF-NMR), where Gdm+ and NH4+ are denaturant and stabilizer for proteins, respectively. It shows that Gdm+ favors to bind to the thiol group or the hydroxyl group on the side chain but weakly interacts with the α-carboxyl group. In contrast, NH4+ prefers to bind to the α-carboxyl group but slightly interacts with the thiol group or the hydroxyl group on the side chain of amino acids. 1HNMR reveals the hydrogen bonding between NH4+ and the α-carboxyl group, which is not involved in the interactions between Gdm+ and cysteine. Our study demonstrates that the strong interactions between the denaturant and the sulfur atom or the disulfide bond promote the direct binding of the denaturant toward proteins, leading to the destabilization.

Silicone Elastomer with Self-Generating Zwitterions for Antifouling Coatings.

Silicone elastomer-based fouling release coatings have been gaining increased attention in marine antibiofouling. However, the lack of fouling resistance limits their application. Introducing a zwitterionic polymer into silicone enhances its fouling resistance, but their incompatibility makes this challenging. In this work, a silicone elastomer with zwitterionic pendant chains has been prepared by grafting a telomer of tertiary carboxybetaine dodecafluoroheptyl ester ethyl acrylate (TCBF) and 3-mercaptopropyltriethoxysilane to the bis-silanol-terminated poly(dimethylsiloxane) (PDMS). The fluorocarbon groups drive the telomer onto the surface in the film formation process, while the TCBF groups hydrolyze and generate zwitterions on the surface, which is confirmed by attenuated total reflection infrared spectra analysis and water contact angle measurements. Bioassays using marine bacteria (Pseudomonas sp.) and diatoms (Navicula incerta) demonstrate that the antifouling efficacy is improved as the telomer content increases. The bacteria and diatom adhesion decreases by 95 and 81%, respectively, for the PDMS with 30 wt % telomer compared with the unmodified PDMS control. Meanwhile, the fouling release performance of PDMS is maintained with a pseudobarnacle removal strength of ∼0.1 MPa. This work provides a facile way to fabricate efficient silicone-based antifouling coatings.

Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles.

The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.

Method for 3D tracking behaviors of interplaying bacteria individuals.

Behaviors of platonic bacteria individuals are profoundly influenced by their interplay. However, probing such interplay still remains a challenge since identification and tracking of bacterial individuals becomes difficult as they come close and interact with each other. Herein, we report 3D tracking of the motions of multiple bacteria by using digital holographic microscopy (DHM), where the subtle 3D behaviors can be characterized as bacteria approach and run away from each other. An algorithm was developed to identify and recover the gap between 3D trajectory segments raising by the interruption from other bacteria through lateral image recognition and axial loalization utilizing cost function. We value the performance of the algorithm in terms of the statistics in trajectory length and correct rate. The study clearly shows how the interplaying Escherichia coli alter their motions.

A novel positive feedback loop of linc02042 and c-Myc mediated by YBX1 promotes tumorigenesis and metastasis in esophageal squamous cell carcinoma.

BACKGROUND: Long non-coding RNA (lncRNA) is a class of endogenous RNA with a length of more than 200 nucleotides, which is emerging as a pivotal player in cancer development and progression. However, the functional roles of many members in this class remain largely uncharacterized. In the present study, we explored the biological relevance of linc02042 in esophageal squamous cell carcinoma (ESCC). METHODS: qRT-PCR was used to detect the levels of linc02042 and c-Myc. Western blot was used to assess protein expression level. CCK-8 and Transwell assays were employed to test ESCC cell proliferation and invasion, respectively. The mice study including xenograft tumor and lung metastasis models was used to determine the role of linc02042 in vivo. RNA pull-down, ChIP and luciferase reporter assays were employed to test the relationship between linc02042, YBX1 and c-Myc. RESULTS: Linc02042 was found to be markedly upregulated in ESCC cell lines, tissues and plasma, and was closely correlated with malignant clinical features. Knockdown of linc02042 significantly inhibited ESCC cell viability and invasion in vitro as well as tumor growth and lung metastasis in vivo, whereas overexpression of linc02042 resulted in the opposite results. Mechanistically, linc02042 acted as a scaffold for YBX-1 binding to the 3'-UTR of c-Myc mRNA, leading to enhanced c-Myc mRNA stability, thereby facilitating ESCC growth and metastasis. Moreover, in turn, c-Myc was able to transcriptionally elevate linc02042 by directly binding to the E-box motif proximal to the transcription start site (TSS) of linc02042 promoter. Clinically, linc02042 was identified as an effective diagnostic and prognostic biomarker for ESCC patients, and its expression was strongly positively correlated with c-Myc expression in ESCC tissues. CONCLUSION: Our data suggest that linc02042 plays an important tumor-promoting role in ESCC, which lays a foundation for considering it as a potential target for ESCC patients.

Silicone-Based Fouling-Release Coatings for Marine Antifouling.

Marine biofouling profoundly influences marine industries and activities. It slows the speed and increases the fuel consumption of ships, corrodes offshore platforms, and blocks seawater pipelines. The most effective and economical antifouling approach uses coatings. Fouling-release coatings (FRCs) with low surface free energy and high elasticity weakly adhere to marine organisms, so they can be readily removed by the water shear force. FRCs have attracted increasing interest because they are biocide-free and hence ecofriendly. However, traditional silicone-based FRCs have weak adhesion to substrates, low mechanical strength, and low fouling resistance, limiting their applications. In recent years, many attempts have been made to improve their mechanical properties and fouling resistance. This review deals with the progress in the construction of high-performance silicone-based fouling-release surfaces.

Specific Ion Effects on the Enzymatic Degradation of Polymeric Marine Antibiofouling Materials.

It is expected that the widely dispersed ions in seawater would have strong influence on the performance of polymeric marine antibiofouling materials through the modulation of enzymatic degradation of the materials. In this work, poly(ε-caprolactone)-based polyurethane and poly(triisopropylsilyl methacrylate-co-2-methylene-1,3-dioxepane) have been employed as model systems to explore the specific ion effects on the enzymatic degradation of polymeric marine antibiofouling materials. Our study demonstrates that the specific ion effects on the enzymatic degradation of the polymer films are closely correlated with the ion-specific enzymatic hydrolysis of the ester. In the presence of different cations, the effectiveness of the enzyme to degrade the polymer films is dominated by the direct specific interactions between the cations and the negatively charged enzyme molecules. In the presence of different anions, the kosmotropic anions give rise to a high enzyme activity in the degradation of polymer films induced by the salting-out effect, whereas the chaotropic anions lead to a low enzyme activity in the degradation of the polymer films owing to the salting-in effect. This work highlights the opportunities available for the use of specific ion effects to modulate the enzymatic degradation of polymeric antibiofouling materials in the marine environment.

Investigation of Formation of Bacterial Biofilm upon Dead Siblings.

Biocides can effectively kill bacteria; however, whether the dead bacterial cells left on the surface influence the later growth of biofilm is unknown. In this study, we have cultured Pseudomonas aeruginosa (PAO1) biofilm on their dead siblings and have investigated their evolution by using magnetic force modulation atomic force microscopy (MF-AFM). The time dependence of the biofilm thickness indicates that the deposited dead siblings can slow down the growth of PAO1 biofilm. The biofilm growing on dead bacteria layers is softer in comparison with those upon alive siblings, as reflected by the static elastic modulus ( E) and dynamic stiffness ( kd) scaled to the disturbing frequency ( f) as kd = kd,0 fγ, where kd,0 is the scaling factor and γ is the power-law exponent. We reveal that the smaller population instead of the variation of extracellular polymeric substances (EPS) within the biofilm upon the dead siblings is responsible for the softer biofilm. The present study provides a better understanding of the biofilm formation, thus, making it significant for designing antimicrobial medical materials and antifouling coatings.