High-Performance Polyurea Improved by Reactive Nanocluster for Antibiofouling.

Polyurea has found applications in protective coatings. Yet, the too fast polymerization and lack of functions limit its application. Herein, we report a high-performance polyurea via the stepwise polymerization of an isocyanate (NCO)-terminated prepolymer consisting of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) (PPG-b-PEG-b-PPG) with a nanocluster synthesized via the hydrolysis of N-phenylaminomethyltriethoxysilane. Such a nanocluster contains low-reactivity secondary amines, so the polymerization of polyurea can be slowed down (over 1 h), which improves its wetting and adhesion to a substrate. The residual silanol groups on the nanocluster further increase the adhesion. Such polyurea exhibits high adhesion on various substrates, including glass, ceramic, steel, copper, titanium, wood, and natural rubber (∼2.35-14.64 MPa). Besides, the nanoclusters can cross-link the prepolymer into a tough network, endowing the polyurea with a high mechanical strength of ∼25 MPa, much higher than the traditional polyaspartic ester polyurea. On the other hand, the PEG segments enable the polyurea to have good fouling resistance against proteins (fibrinogen absorption was reduced by over 90%), bacteria (RBA of S. aureusE. coli and Pseudomonas sp. was less than 10%), as well as diatom (diatom density was less than 100 cells/mm2). The polyurea is expected to find applications in biomedical engineering and marine antifouling.

Sterically Hindered Oleogel-Based Underwater Adhesive Enabled by Mesh-Tailoring Strategy.

Underwater adhesives hold significant relevance in daily life and numerous industrial applications. Despite considerable efforts, developing scalable, high-performance underwater adhesives through a simple and effective method remains a formidable challenge. This study presents a novel mesh-tailoring strategy for in situ, rapid, and ultrastrong oleogel-based underwater adhesives (OUA), which comprises a highly crosslinked polyurethane network with a matching mesh size (≈2.22 nm) that precisely entraps bio-based epoxidized soybean oil (ESO) molecules (≈2.31 nm) by steric hindrance effect. This oleogel exhibits unprecedented robust mechanical properties (≈35 MPa) and maintains stability under extreme conditions, including high temperatures (100 °C), high pressures (30 MPa), and immersion in various solvents (water, ethanol, or ESO). In particular, this oleogel displays high hydrophobicity, rapid curing, and strong interface affinity, resulting in ultrahigh underwater adhesion strength (up to 2.13 MPa) and exceptional substrate universality. Moreover, the remarkable environmental adaptability and stability of OUA enable its use in harsh aqueous environments, including acidic/alkaline, saline, and extreme temperature solutions. The comprehensive capabilities of the OUA underscore its potential for building underwater structures, repairing leaky containers, and sealing broken submarine pipelines. This research establishes the foundation for the designing of next-generation underwater adhesives and offers fresh perspectives for exploring oleogel-based materials.

Intelligent anti-impact elastomers by precisely tailoring the topology of modular polymer networks.

High-performance elastomers are essential in daily life and various industrial sectors such as personal protection, soft electronics, and vibration control. Nevertheless, despite massive efforts, concurrently achieving ultrahigh flexibility and remarkable impact resistance continues to be elusive. Herein, we report an innovative modular construction strategy that employs a topology-tailoring polymer network consisting of stereoscopic (epoxy-oligosiloxane nanoclusters) and linear (amino-terminated polyurea) building blocks as independent modules to develop intelligent anti-impact elastomers via an epoxy-amine mechanism. By precisely tailoring the topology of building blocks, the elastomers demonstrate high flexibility and toughness, remarkable impact responsiveness and ultrahigh energy dissipation. Their anti-impact ability surpasses those of most common soft and rigid materials such as steel, plastic, rubber, foam, or even polyborosiloxane. Moreover, the elastomers are well-qualified for use in flexible display technologies, owing to their high transparency (>92% transmittance), exceptional fold-resistance (no creasing after 10 000 bends), and good thermal stability (no discoloration at 100 °C). Furthermore, the elastomers exhibit excellent versatility, enabling them to be combined with either soft or rigid materials to generate composites with ultrahigh puncture and ballistic resistance. This study offers a promising framework for the design and fabrication of intelligent anti-impact elastomers and provides valuable insights into the development of next-generation protective materials.

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).

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.

Beyond LiF: Tailoring Li2O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries.

The components and structures of the solid-electrolyte interphase (SEI) are critical for stable cycling of lithium metal batteries (LMBs). LiF has been widely studied as the dominant component of SEI, but Li2O, which has a much lower diffusion barrier for Li+, has rarely been investigated as the dominant component of SEI. The effect of Li2O-dominated SEI on electrochemical performance still remains elusive. Herein, an ultrastrong coordinated cosolvation diluent, 2,3-difluoroethoxybenzene (DFEB), is designed to modulate solvation structure and tailor Li2O-dominated SEI for stable LMBs. In the DFEB-based LHCE (DFEB-LHCE), DFEB intensively participates in the first solvation shell and synergizes with FSI- to tailor an Li2O-dominated inorganic-rich SEI which is different from the LiF-dominated SEI formed in conventional LHCE. Benefiting from this special SEI architecture, a high Coulombic efficiency (CE) of 99.58% in Li||Cu half cells, stable voltage profiles, and dense and uniform lithium deposition, as well as effective inhibition of Li dendrite formation in the symmetrical cell, are achieved. More importantly, the DFEB-LHCE can be matched with various cathodes such as LFP, NCM811, and S cathodes, and the Li||LFP full cell using DFEB-LHCE possesses 85% capacity retention after 650 stable cycles with 99.9% CE. Especially the 1.5 Ah practical lithium metal pouch cell achieves an excellent capacity retention of 89% after 250 cycles with a superb average CE of 99.93%. This work unravels the superiority of the Li2O-dominated SEI and the feasibility of tailoring SEI components through modulation of solvation structures.

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.

Chemoselectivity Streamlines the Approach to Linear and Y-Shaped Thiol-Polyethers Starting from Thiocarboxylic Acids.

Thiol-functionalized polyethers, especially poly(ethylene oxide) (PEO), have extensive applications in biomedicine and materials sciences. Herein, we report a simple one-pot synthesis of α-thiol-ω-hydroxyl polyethers through ring-opening polymerization (ROP) of epoxides using thiocarboxylic acid initiators followed by in situ aminolysis. The efficient and chemoselective metal-free Lewis pair catalyst avoids transthioesterification thus achieving well-controlled molar mass, low dispersity, and high end-group fidelity. Kinetic and calculation results demonstrated a fast-initiation mode of the ROP for the strong nucleophilicity of the thiocarboxylate anion and its weak interaction with Lewis acid. The method is expanded for α-thiol-ω-dihydroxyl (Y-shaped) PEO by virtue of the stability of thioester during the ROP. The thiol functionality in linear/Y-shaped PEO is further corroborated by the intensified interaction with gold surface and the resultant protein resistance behavior.

Molecular Weight Dependence of Surface Tension of Poly(ethylene oxide) Solution.

Surface tension plays a critical role in a wide range of fields such as adhesion, wetting, and capillarity. Herein, we combine experiments and molecular dynamics (MD) simulations to study the surface tension (γ) of poly(ethylene oxide) (PEO) solution as a function of its molecular weight (M). In experiments, we reveal that γ is scaled to M with |γ - γ∞| ∝ Mα up to a critical molecular weight (M*). Simulation with a coarse-grained polymer solution model shows that α decreases as the solvent quality becomes worse. The combination of the experiments and simulations reveal that α is slightly affected by PEO concentration. On the other hand, M* decreases as the solvent quality decreases or as the polymer concentration increases. Our study demonstrates that the surface tension of the polymer solution is determined by the adsorption of the polymer at the air-solution surface.

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.

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.

A monofluoride ether-based electrolyte solution for fast-charging and low-temperature non-aqueous lithium metal batteries.

The electrochemical stability window of the electrolyte solution limits the energy content of non-aqueous lithium metal batteries. In particular, although electrolytes comprising fluorinated solvents show good oxidation stability against high-voltage positive electrode active materials such as LiNi0.8Co0.1Mn0.1O2 (NCM811), the ionic conductivity is adversely affected and, thus, the battery cycling performance at high current rates and low temperatures. To address these issues, here we report the design and synthesis of a monofluoride ether as an electrolyte solvent with Li-F and Li-O tridentate coordination chemistries. The monofluoro substituent (-CH2F) in the solvent molecule, differently from the difluoro (-CHF2) and trifluoro (-CF3) counterparts, improves the electrolyte ionic conductivity without narrowing the oxidation stability. Indeed, the electrolyte solution with the monofluoride ether solvent demonstrates good compatibility with positive and negative electrodes in a wide range of temperatures (i.e., from -60 °C to +60 °C) and at high charge/discharge rates (e.g., at 17.5 mA cm-2). Using this electrolyte solution, we assemble and test a 320 mAh Li||NCM811 multi-layer pouch cell, which delivers a specific energy of 426 Wh kg-1 (based on the weight of the entire cell) and capacity retention of 80% after 200 cycles at 0.8/8 mA cm-2 charge/discharge rate and 30 °C.

Non-isocyanate Polyurethane Coating with High Hardness, Superior Flexibility, and Strong Substrate Adhesion.

Flexible hard coatings with strong adhesion are critical requirements for several foldable devices and marine applications; however, only a few such coatings have been reported. Herein, we report a non-isocyanate polyurethane (NIPU) coating prepared by the epoxy-oligosiloxane nanocluster-amine curing reaction and cyclic carbonate-amine polyaddition, where the former provides the coating with ceramic-like hardness and polymer-like flexibility while the latter polymerization results in NIPU with strong substrate adhesion. The coating is transparent (>92% transmittance), hard (5-7 H), and flexible (2 mm bending diameter). It has strong adhesion to various substrates including aluminum alloy, titanium, steel, glass, ceramic, epoxy, and polyethylene terephthalate (2-8 MPa), which can be attributed to the high density of polar groups in NIPU. Moreover, we can facilely endow the coating with anti-icing, self-cleaning, and anti-smudge capabilities by incorporating amine-terminated low-surface-tension polydimethylsiloxane (PDMS) to replace a part of the amine curing agent. Particularly, the mechanical properties of NIPU coatings are only slightly affected by the introduction of low-content PDMS since it intends to enrich on the surface. The novel coating has promising future for use in fields of foldable devices and marine applications.

Fundamentals of the Cathode-Electrolyte Interface in All-solid-state Lithium Batteries.

All-solid-state lithium batteries (ASSBs) enabled by solid-state electrolytes (SEs) including oxide-based and sulfide-based electrolytes have gained worldwide attention because of their intrinsic safety and higher energy density over conventional lithium-ion batteries (LIBs). However, despite the high ionic conductivity of advanced SEs, ASSBs still exhibit high overall internal resistance, the most significant contributor of which can be ascribed to the cathode-SE interfaces. This review seeks to clarify the critical issues regarding the cathode-SE interfaces, including fundamental principles and corresponding solutions. First, major issues concerning electro-chemo-mechanical instability between cathodes and SEs and their formation mechanisms are discussed. Then, specific problems in oxides and sulfides and various solutions and strategies toward interfacial modifications are highlighted. Efforts toward the characterization and analysis of cathode-SE interfaces with advanced techniques are also summarized. Finally, perspectives are offered on several problems demanding urgent solutions and the future development of SE applications and ASSBs.

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.