Liquid Polydimethylsiloxane Grafting to Enable Dendrite‐Free Li Plating for Highly Reversible Li‐Metal Batteries

Li‐metal is considered as the most promising anode material to advance the development of next‐generation energy storage devices owing to its unparalleled theoretical specific capacity and extremely low redox electrochemical potential. However, safety concerns and poor cycling retention of Li‐metal batteries (LMBs) caused by uncontrolled Li dendrite growth still limit their broad application. Herein, liquid polydimethylsiloxane (PDMS) terminated by –OCH₃ groups is proposed as a graftable additive to reinforce the anode dendrite suppression for LMBs. Such a grafting triggers the formation of a conformal hybrid solid electrolyte interphase (SEI) with increased fractions of LiF and Li–Si–O‐based moieties, which serve as a rigid barrier and ionic conductor for uniform Li‐ion flow and Li‐mass deposition. The grafting protected anode endows Li/Li symmetric cells with a long lifetime over 1800 h with a much smaller voltage gap (≈25 mV) between Li plating and stripping, than the naked anode. The coulombic efficiency values for Li/Cu asymmetric cells in carbonate electrolyte can reach up to 97% even at a high current density of 3 mA cm^?2 or high capacity up to 4 mAh cm^?2. The liquid PDMS additive shows advantage over solid siloxane additives with poor grafting ability in terms of Li surface compaction and SEI stabilization.     

Well‐Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

Low‐temperature anionic ring‐opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal‐free catalyst system, 3‐phenyl‐1‐propanol (PPA) (an initiator) and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris‐(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄) (a promoter) in order to obtain well‐defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring‐opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well‐defined linear AGE‐homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE‐homopolymer in a unimodal narrow molecular‐weight distribution. In this case, however, a side reaction (i.e., chain‐transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well‐defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post‐modification products are examined. Overall, this study demonstrates that a low‐temperature metal‐free anionic ROP using the PPA/t‐Bu‐P₄ catalyst system is suitable for the production of well‐defined linear AGE‐homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post‐modifications, nanostructures, and their applications.     

A Biodegradable Antigen Nanocapsule Promotes Anti-Tumor Immunity via the cGAS-STING Pathway

Materials-based antigen delivery systems can augment the immune response by improving antigen uptake in antigen-presenting cells, targeting lymph nodes, prolonging antigen exposure, enhancing cross-presentation, etc. Recent research revealed that some antigen carriers activate the innate immune pathways without additional adjuvant. Here, a vaccine delivery platform (antigen nanocapsules) constructed by a one-step in situ polymerization is reported, weaving a biodegradable polymer network around the antigen surface. This simple technology allowed us to study the immunomodulatory effect of various antigen carriers. An antigen nanocapsule (NC7) capable of inducing dendritic cell activation and cross-presentation is identified. Further mechanistic studies revealed that NC7 activated the cGAS-STING pathway in a cGAS-dependent manner. Moreover, the subcutaneously injected NC7 accumulated in the lymph nodes and elicited strong cytotoxic T cell immunity and T cell memory against established cancer. Collectively, the often-neglected immunomodulatory effect of various cationic antigen carriers, enabling potential application in cancer vaccines, is uncovered.     

A Facile Strategy for Preparing Self‐Healing Polymer Composites by Incorporation of Cationic Catalyst‐Loaded Vegetable Fibers

A two‐component healing agent, consisting of epoxy‐loaded microcapsules and an extremely active catalyst (boron trifluoride diethyl etherate, (C₂H₅)₂O · BF₃)), is incorporated into epoxy composites to provide the latter with rapid self‐healing capability. To avoid deactivation of the catalyst during composite manufacturing, (C₂H₅)₂O · BF₃ is firstly absorbed by fibrous carriers (i.e., short sisal fibers), and then the fibers are coated with polystyrene and embedded in the epoxy matrix together with the encapsulated epoxy monomer. Because of gradual diffusion of the absorbed (C₂H₅)₂O · BF₃ from the sisal into the surrounding matrix, the catalyst is eventually distributed throughout the composites and acts as a latent hardener. Upon cracking of the composites, the epoxy monomer is released from the broken capsules, spreading over the cracked planes. As a result, polymerization, triggered by the dispersed (C₂H₅)₂O · BF₃, takes place and the damaged sites are rebonded. Since the epoxy–BF₃ cure belongs to a cationic chain polymerization, the exact stoichiometric ratio of the reaction components required by other healing chemistries is no longer necessary. Only a small amount of (C₂H₅)₂O · BF₃ is sufficient to initiate very fast healing (e.g., a 76% recovery of impact strength is observed within 30 min at 20 °C).     

A Direct Approach to Organic/Inorganic Semiconductor Hybrid Particles via Functionalized Polyfluorene Ligands

Controlled Suzuki–Miyaura coupling polymerization of 7′‐bromo‐9′,9′‐dioctyl‐fluoren‐2′‐yl‐4,4,5,5‐tetramethyl‐[1,3,2]dioxaborolane initiated by bromo(4‐tert‐butoxycarbonylamino‐phenyl)(tri‐tert‐butylphosphine)palladium ( 1 ) or bromo(4‐diethoxyphosphoryl‐phenyl)(tri‐tert‐butylphosphine)palladium ( 2 ) yields functionalized polyfluorenes (M_n = 4 × 10³ g mol^?1, M_w/M_n < 1.2) with a single amine or phosphonic acid, respectively, end‐group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino‐functionalized polyfluorene ligands. Single particle micro‐photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.     

Superparamagnetic Twist‐Type Actuators with Shape‐Independent Magnetic Properties and Surface Functionalization for Advanced Biomedical Applications

Directed nanoparticle self‐organization and two‐photon polymerization are combined to enable three‐dimensional soft‐magnetic microactuators with complex shapes and shape‐independent magnetic properties. Based on the proposed approach, single and double twist‐type swimming microrobots with programmed magnetic anisotropy are demonstrated, and their swimming properties in DI‐water are characterized. The fabricated devices are actuated using weak rotating magnetic fields and are capable of performing wobble‐free corkscrew propulsion. Single twist‐type actuators possess an increase in surface area in excess of 150% over helical actuators with similar feature size without compromising the forward velocity of over one body length per second. A generic and facile combination of glycine grafting and subsequent protein immobilization exploits the actuator's increased surface area, providing for a swimming microrobotic platform with enhanced load capacity desirable for future biomedical applications. Successful surface modification is confirmed by FITC fluorescence.     

电子浆料用超微细玻璃粉的等离子体改性

以六甲基二硅氧烷为单体,利用高频等离子体在超微细低熔磷酸盐玻璃粉体表面聚合硅氧聚合物包覆薄膜。用水和粉体压片之间的接触角变化表征了等离子体工艺参数对粉体表面能的影响。结果表明改性后粉体配制电子浆料的细度、黏度、流变特性提高显著。改性后可以改变或控制超微细粉体的表面能大小,从而可调节电子浆料的流变性和印刷适性。     

SEL催化剂在淤浆法聚乙烯装置中的应用

在30万t/a Hostalen淤浆法聚乙烯生产装置中,采用国产SEL催化剂试生产了双峰聚乙烯薄膜料(牌号为HM-9455 F 1)。结果表明:试用SEL催化剂期间,装置运行平稳;SEL催化剂的组成、微观结构与参比催化剂(牌号为THT)相近;与参比催化剂相比,SEL催化剂的聚合活性提高了17%,氢气单耗和副产物蜡产量分别降低了6.6%,9.5%;由SEL催化剂生产的双峰聚乙烯薄膜料,粒径分布集中在>63～250μm。