A multifunctional electrolyte additive for zinc-ion capacitors with low temperature resistant and long lifespan

Aqueous zinc-ion capacitors (ZICs) are considered as potential candidates for next generation electrochemical energy storage devices due to their high safety and low cost.However,the existing aqueous ZICs usually have the problems of zinc dendrite growth and unsatisfactory performance at low temperature.Herein,an erythritol (Eryt) additive with inhibition of zinc dendrites and anti-freezing capability was introduced into the ZnSO4electrolyte.The experimental characterization and theoretical calculation confirm that the Eryt adsorbed on the surface of zinc anodes regulates the deposition orientation of Zn^(2+) and inhibits the formation of dendrites.It also reconstructs the solvation structure in the electrolyte to reduce water activity,enabling the electrolyte to have a lower freezing point for operation at low temperature.With the assistance of Eryt,the Zn||Zn symmetric cell exhibits a long cycle life of 2000 h,while the ZIC assembled with activated carbon (AC) cathode and zinc anode (Zn||AC) maintains a capacity retention of 98.2% after 30,000 cycles at a current density of 10 A g^(-1)(even after 10,000 cycles at-20°C,the capacity retention rate reached 94.8%.).This work provides a highly scalable,low-cost and effective strategy for the protection of the anodes of low-temperature aqueous ZICs.

Upcycling municipal solid waste to sustainable hydrogen via two-stage gasification-reforming

As global municipal solid waste(MSW)quantities continue to escalate,serious socio-environmental challenges arise,necessitating innovative solutions.Waste-to-hydrogen(WTH)via two-stage gasification-reforming(TSGR)presents an emergent technology for MSW upcycling,offering to ease waste management burdens and bolster the burgeoning hydrogen economy.Despite early initiatives to advance TSGR technology,a cohesive and critical analysis of cutting-edge knowledge and strategies to enhance hydrogen production remains lacking.This review aggregates literature on MSW upcycling to hydrogen via TSGR,with a focus on optimizing process control and catalytic efficiency.It underscores technological avenues to augment hydrogen output,curtail catalyst costs,and refine system performance.Particularly,the review illuminates the potential for integrating chemical and calcium looping into TSGR processes,identifying opportunities,and pinpointing challenges.The review concludes with a summary of the current state of techno-economic analysis for this technology,presenting outstanding challenges and future research directions,with the ultimate goal of transitioning WTH from theoretical to practical application.

Confining ultrahigh oxygen vacancy SnO_(2) nanocrystals into nitrogen-doped carbon for enhanced Li-ion storage kinetics and reversibility

Oxygen vacancies (V_(o)) engineering has been deemed to an effective tactic for enhancing Li-ion storage kinetics and reversibility of SnO_(2)-based anode materials.Herein,we demonstrated the confinement of ultrahigh V_(o)SnO_(2) nanocrystals into N-doped carbon frameworks to boost their high-rate and cycle life.Density functional theory (DFT) calculations reveal that abundant V_(o) in SnO_(2) facilitates the adsorption to Li-ion with remarkably increased carrier concentration.The 6.0 nm-sized SnO_(2) particles and the embedded design effectively stabilize the structural integrity during de-/lithiation.Meantime,the as-formed large hetero-interface also expedites the electron transfer.These merits guarantee its high-rate performance and superior cycling stability.Consequently,this sample exhibits a high capacity of 1368.9m Ah g^(-1)at 0.1 A g^(-1),and can still maintain 488.5 mAh g^(-1)at 10 A g^(-1)and a long life over 400 cycles at 5 A g^(-1)with 96.6%capacity retention,which is among the best report for Sn-contained anode materials.This work sheds light on ultrahigh Vo and structural design in conversion-type oxides for highperformance lithium-ion batteries (LIBs).

An Intelligent Manufacturing Platform of Polymers:Polymeric Material Genome Engineering

Polymeric materials with excellent performance are the foundation for developing high-level technology and advanced manufacturing.Polymeric material genome engineering(PMGE)is becoming a vital platform for the intelligent manufacturing of polymeric materials.However,the development of PMGE is still in its infancy,and many issues remain to be addressed.In this perspective,we elaborate on the PMGE concepts,summarize the state-of-the-art research and achievements,and highlight the challenges and prospects in this field.In particular,we focus on property estimation approaches,including property proxy prediction and machine learning prediction of polymer properties.The potential engineering applications of PMGE are discussed,including the fields of advanced composites,polymeric materials for communications,and integrated circuits.

Trilogy of drug repurposing for developing cancer and chemotherapy-induced heart failure co-therapy agent

Chemotherapy-induced complications,particularly lethal cardiovascular diseases,pose significant challenges for cancer survivors.The intertwined adverse effects,brought by cancer and its complication,further complicate anticancer therapy and lead to diminished clinical outcomes.Simple supplementation of cardioprotective agents falls short in addressing these challenges.Developing bifunctional co-therapy agents provided another potential solution to consolidate the chemotherapy and reduce cardiac events simultaneously.Drug repurposing was naturally endowed with co-therapeutic potential of two indications,implying a unique chance in the development of bi-functional agents.Herein,we further proposed a novel“trilogy of drug repurposing”strategy that comprises function-based,targetfocused,and scaffold-driven repurposing approaches,aiming to systematically elucidate the advantages of repurposed drugs in rationally developing bi-functional agent.Through function-based repurposing,a cardioprotective agent,carvedilol(CAR),was identified as a potential neddylation inhibitor to suppress lung cancer growth.Employing target-focused SAR studies and scaffold-driven drug design,we synthesized 44 CAR derivatives to achieve a balance between anticancer and cardioprotection.Remarkably,optimal derivative 43 displayed promising bi-functional effects,especially in various self-established heart failure mice models with and without tumor-bearing.Collectively,the present study validated the practicability of the“trilogy of drug repurposing”strategy in the development of bi-functional cotherapy agents.

Tungsten and phosphate polyanion co-doping of Ni-ultrahigh cathodes greatly enhancing crystal structure and interface stability

The Ni-ultrahigh cathode material is one of the best choices for further increasing energy-density of lithium-ion batteries(LIBs),but they generally suffer from the poor structure stability and rapid capacity fade.Herein,the tungsten and phosphate polyanion co-doped LiNi_(0.9)Co_(0.1)O_(2)cathode materials are successfully fabricated in terms of Li(Ni_(0.9)Co_(0.7))_(1-x)W_(x)O_(2-4y)(PO_(4))_(y) by the precursor modification and subsequent annealing.The higher bonding energy of W—O(672 kJ·mol^(-1))can extremely stabilize the lattice oxygen of Ni-rich oxides compared with Ni—O(391.6 kJ·mol^(-1))and Co—O(368 kJ·mol^(-1)).Meanwhile,the stronger bonding of Ni—(PO_(4)^(3-))vs.Ni—O could fix Ni cations in the transition metal layer,and hence suppressing the Li/Ni disorder during the charge/discharge process.Therefore,the optimized Li(Ni_(0.9)Co_(0.1))_(0.99)W_(0.01)O_(1.96)(PO_4)_(0.01)delivers a remarkably extended cycling life with 95.1%retention of its initial capacity of 207.4 mA·h·g^(-1)at 0.2 C after 200 cycles.Meantime,the heteroatoms doping does not sacrifice the specific capacity even at different rates.

Atomic Interface Catalytically Synthesizing SnP/CoP Hetero-Nanocrystals within Dual-Carbon Hybrids for Ultrafast Lithium-Ion Batteries

Tin phosphides are attractive anode materials for ultrafast lithium-ion batteries(LIBs)because of their ultrahigh Li-ion diffusion capability and large theoretical-specific capacity.However,difficulties in synthesis and large size enabling electrochemical irreversibility impede their applications.Herein,an in situ catalytic phosphorization strategy is developed to synthesize SnP/CoP hetero-nanocrystals within reduced graphene oxide(rGO)-coated carbon frameworks,in which the SnP relative formation energy is significantly decreased according to density functional theory(DFT)calculations.The optimized hybrids exhibit ultrafast charge/discharge capability(260 mA·h·g^(-1)at 50 A·g^(-1))without capacity fading(645 mA·h·g^(-1)at 2 A·g^(-1))through 1500 cycles.The lithiation/delithiation mechanism is disclosed,showing that the 4.0 nm sized SnP/CoP nanocrystals possess a very high reversibility and that the previously formed metallic Co of CoP at a relatively high potential accelerates the subsequent reaction kinetics of SnP,hence endowing them with ultrafast charge/discharge capability,which is further verified by the relative dynamic current density distributions according to the finite element analysis.

Superhydrophobic and mechanically robust polysiloxane composite coatings containing modified silica nanoparticles and PS-grafted halloysite nanotubes

Excellent mechanical properties are the prerequisite for the application of superhydrophobic polymer coatings.However,significantly improving the mechanical properties without affecting other properties such as hydrophobicity is a huge challenge.In this study,a superhydrophobic coating with excellent mechanical properties was prepared by spraying a mixture of polysiloxane resins based on three siloxane monomers,hexadecyltrimethoxysilane(HDTMS) modified nano-SiO_(2)particles(SiO_(2)-HDTMS) and polystyrene-grafted halloysite nanotubes(HNTs-PS).SiO_(2)-HDTMS dispersed homogeneously in polysiloxane coatings and the water contact angle of corresponding coating exceeding 150°,achieving superhydrophobicity.The SiO_(2)-HDTMS/HNTs-PS/polysiloxane composite coatings showed excellent abrasion resistance with the water coating contact angle remaining above 150°after 90 abrasion cycles,indicating that HNTs-PS can significantly improve the mechanical properties of the coating without affecting the hydrophobic properties of the coating.The achieved coating also exhibited excellent antifouling and acid and alkali corrosion resistance.This work provides a convenient and ecologically friendly method to prepare superhydrophobic polysiloxane composite coating with excellent mechanical properties,which is promising in the application of anti-fouling,anti-corrosion,and oil-water separation etc.

Construction of developmentally inspired periosteum-like tissue for bone regeneration

The periosteum, a highly vascularized thin tissue, has excellent osteogenic and bone regenerative abilities. The generation of periosteum-mimicking tissue has become a novel strategy for bone defect repair and regeneration, especially in critical-sized bone defects caused by trauma and bone tumor resection. Here, we utilized a bone morphogenetic protein-2(BMP-2)-loaded scaffold to create periosteum-like tissue(PT) in vivo, mimicking the mesenchymal condensation during native long bone development. We found that BMP-2-induced endochondral ossification plays an indispensable role in the construction of PTs. Moreover, we confirmed that BMP-2-induced PTs exhibit a similar architecture to the periosteum and harbor abundant functional periosteum-like tissue-derived cells(PTDCs), blood vessels, and osteochondral progenitor cells. Interestingly, we found that the addition of chondroitin sulfate(CS), an essential component of the extracellular matrix(ECM), could further increase the abundance and enhance the function of recruited PTDCs from the PTs and finally increase the regenerative capacity of the PTs in autologous transplantation assays, even in old mice. This novel biomimetic strategy for generating PT through in vivo endochondral ossification deserves further clinical translation.

A biomimetic and bioactive scaffold with intelligently pulsatile teriparatide delivery for local and systemic osteoporosis regeneration

Osteoporosis is one of the most disabling consequences of aging,osteoporotic fractures and higher risk of the subsequent fractures leading to substantial disability and deaths,indicating both local fractures healing and the early anti-osteoporosis therapy are of great significance.Teriparatide is strong bone formation promoter effective in treating osteoporosis,while side effects limit clinical applications.Traditional drug delivery is lack of sensitive and short-term release,finding a new non-invasive and easily controllable drug delivery to not only repair the local fractures but also improve total bone mass has remained a great challenge.Thus,bioinspired by the natural bone components,we develop appropriate interactions between inorganic biological scaffolds and organic drug molecules,achieving both loaded with the teriparatide in the scaffold and capable of releasing on demand.Herein,biomimetic bone microstructure of mesoporous bioglass,a near-infrared ray triggered switch,thermosensitive liposomes based on a valve,and polydopamine coated as a heater is developed rationally for osteoporotic bone regeneration.Teriparatide is pulsatile released from intelligent delivery,not only rejuvenating osteoporotic bone defect,but also presenting strong systemic anti-osteoporosis therapy.This biomimetic bone carrying novel drug delivery platform is well worth expecting to be a new promising strategy and clinically commercialized to help patients survive from the osteoporotic fracture.

Integrating trace Ti-doping and LiYO2-coating to stabilize Ni-rich cathodes for lithium-ion batteries

Ni-rich layered cathodes have become the promising candidates for the next-generation high-energy Liion batteries due to their high energy density and competitive cost.However,they suffer from rapidcapacity fading due to the structural and interfacial instability upon long-term operation.Herein,the Tidoped and LiYO2-coated Ni-rich layered cathode has been synthesized via a facile one-step sinteringstrategy,which significantly restrains the interfacial parasitic side reactions and enhances the structuralstability.Specifically,the trace Ti^(4+)doping greatly stabilizes the lattice oxygen and alleviates the Li/Nidisorder while the LiYO_(2) coating layer can prevent the erosion of the cathode by the electrolyte duringcycles.As a result,the Ti-NCM83@LYO delivers a high specific capacity of 135 mAh g^(-1) even at 10C andthere is almost no capacity loss at 1C for 100 cycles.This work provides a simple one-step dual-modification strategy to meet the commercial requirements of Ni-rich cathodes.

Nickel-Catalyzed Regiodivergent Acylzincation of Styrenes with Organozincs and CO

Transition metal-catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond.Recently,the incorporation of organometallic reagent with the CO gas as a nucleophilic acyl synthon could enable the acylmetallation reaction,which greatly increases the horizon of carbometallation chemistry.Herein,we report a nickel-catalyzed regiodivergent acylzincation of o-cyano cinnamate ester and o-cyano styrene,in which the cyano moiety intramolecularly captures zinc intermediates to trigger the tandem cyclization process.This protocol features mild conditions,broad substrate scope and excellent functional group tolerance,thus affording a diverse array of highly functionalized carbocyclic compounds.

Advances in electrode interface materials and modification technologies for brain-computer interfaces

Recent advances in neuroelectrode interface materials and modification technologies are reviewed. Brain-computer interface is the new method of human-computer interaction, which not only can realise the exchange of information between the human brain and external devices, but also provides a brand-new means for the diagnosis and treatment of brain-related diseases. The neural electrode interface part of brain-computer interface is an important area for electrical, optical and chemical signal transmission between brain tissue system and external electronic devices, which determines the performance of brain-computer interface. In order to solve the problems of insufficient flexibility, insufficient signal recognition ability and insufficient biocompatibility of traditional rigid electrodes, researchers have carried out extensive studies on the neuroelectrode interface in terms of materials and modification techniques. This paper introduces the biological reactions that occur in neuroelectrodes after implantation into brain tissue and the decisive role of the electrode interface for electrode function. Following this, the latest research progress on neuroelectrode materials and interface materials is reviewed from the aspects of neuroelectrode materials and modification technologies, firstly taking materials as a clue, and then focusing on the preparation process of neuroelectrode coatings and the design scheme of functionalised structures.

Different-shaped ligand mediating efficient structurally similar cage-to-cage transformation

The transformation of a Palladium-based metal-organic cage to a structurally similar one by direct ligand replacement usually leads to unwanted ligand scrambling. In this work, an intermediate ligand with different shape and basicity from the initial/final ones was introduced to avoid ligand scrambling to achieve the efficient indirect cage-to-similar-cage transformation. Compared with the direct transformation, the stepwise conversion has the advantages of high efficiency(93%) and simple workup.

Au(Ⅰ)-BSA nanocomposites with assembling-induced excitation-dependent multicolor emission for dynamic cell imaging

Excitation wavelength dependent(Ex-De) luminescent materials have attracted intense attention due to their great potential in multicolor bioimaging,dynamic anti-counterfeiting,and light emitting devices.However,it remains a formidable challenge to construct an Ex-De luminescent biomaterial with green starting materials,excellent biocompatibility,good water solubility,and multiple color emission for dynamic cell imaging.In this work,nanocomposites based on the facile self-assembly strategy of bovine serum albumin(BSA) and Au(Ⅰ)-complex are rationally designed and synthesized to simultaneously present Ex-De fluorescence(429–516 nm) and decent phosphorescence(~615 nm) in a dilute aqueous solution.Combinatory analyses of spectroscopic and microscopic results reveal that the luminescent mechanism of Au(Ⅰ)-BSA nanocomposites is cluster-induced Ex-De fluorescence and metal-to-ligand charge transition(MLCT) based phosphorescence.Importantly,based on the excellent biocompatibility,water-solubility and color-tunable emission over the entire visible region(360–800 nm),the Au(Ⅰ)-BSA nanocomposites are successfully used for cell imaging with multiple and switchable colors on demand.What is more,the solid tablets of Au(Ⅰ)-BSA nanoparticles showed pressure-responsive luminescence and decent room temperature phosphorescence.This work provides an assembling-induced emission strategy for the design of water-soluble,non-cytotoxic,and color-tunable luminescent biomaterials based on the composite of protein and Au nanoparticles.

Size-transformable nanoparticles with sequentially triggered drug release and enhanced penetration for anticancer therapy

There are several limitations to the application of nanoparticles in the treatment of cancer,including their low drug loading,poor colloidal stability,insufficient tumor penetration,and uncontrolled release of the drug.Herein,gelatin/laponite(LP)/doxorubicin(GLD)nanoparticles are developed by crosslinking LP with gelatin for doxorubicin delivery.GLD shows high doxorubicin encapsulation efficacy(99%)and strong colloidal stability,as seen from the unchanged size over the past 21 days and reduced protein absorption by 48-fold compared with unmodified laponite/doxorubicin nanoparticles.When gelatin from 115 nm GLD reaches the tumor site,matrix metallopeptidase-2(MMP-2)from the tumor environment breaks it down to release smaller 40 nm LP nanoparticles for effective tumor cell endocytosis.As demonstrated by superior penetration in both in vitro three-dimensional(3D)tumor spheroids(138-fold increase compared to the free drug)and in vivo tumor models.The intracellular low pH and MMP-2 further cause doxorubicin release after endocytosis by tumor cells,leading to a higher inhibitory potential against cancer cells.The improved anticancer effectiveness and strong in vivo biocompatibility of GLD have been confirmed using a mouse tumor-bearing model.MMP-2/pH sequentially triggered anticancer drug delivery is made possible by the logical design of tumor-penetrating GLD,offering a useful method for anticancer therapy.

A suture-free, shape self-adaptive and bioactive PEG-Lysozyme implant for Corneal stroma defect repair and rapid vision restoration

limitation of donor tissue shortage clinically. In addition, suturing-needed transplantation potentially causes postoperative complications. Herein, we design a PEG-Lysozyme injective hydrogel as a suture-free, shape self-adaptive, bioactive implant for corneal stroma defect repair. This implant experiences a sol-gel phase transition via an in situ amidation reaction between 4-arm-PEG-NHS and lysozyme. The physicochemical properties of PEG-Lysozyme can be tuned by the components ratio, which confers the implant mimetic corneal modulus and provides tissue adhesion to endure increased intraocular pressure. In vitro tests prove that the implant is beneficial to Human corneal epithelial cells growth and migration due to the bioactivity of lysozyme. Rabbit lamellar keratoplasty experiment demonstrates that the hydrogel can be filled into defect to form a shape-adaptive implant adhered to native stroma. The implant promotes epithelialization and stroma integrity, recovering the topology of injured cornea to normal. A newly established animal forging behavior test prove a rapid visual restoration of rabbits when use implant in a suture free manner. In general, this work provides a promising preclinical practice by applicating a self-curing, shape self-adaptive and bioactive PEG-Lysozyme implant for suture-free stroma repair.

Type I photosensitizer based on AIE chromophore tricyano-methylene-pyridine for photodynamic therapy

Image guided photodynamic therapy(PDT)combines fluorescence tracing and phototherapy,which can achieve a more accurate and effective treatment effect.However,traditional photosensitizers are limited by the aggregation-caused fluorescence quenching(ACQ)effect and low reactive oxygen species(ROS)generation in a hypoxic environment,resulting in poor imaging and treatment effect.Herein,we report a tricyano-methylene-pyridine(TCM)-based Type I aggregation-induced emission(AIE)photosensitizer(TCM-MBP),the strong elec-tron acceptance(D-A)effect extends the wavelength to near-infrared(NIR)region to reduce the autofluorescence interference,and oxygen atoms provide lone pair electrons to enhance the inter system crossing(ISC)rate,thereby promoting the generation of more triplet states to produce ROS.The AIE photosensitizer TCM-MBP exhibited low oxygen dependence,NIR emission,and higher ROS production compared to commercially avail-able Ce_(6) and RB.After encapsulation with DSPE-PEG 2000,TCM-MBP nanoparticles(TCM-MBP NPs)could penetrate to visualize cells and efficiently kill cancer cells upon light irradiation.This study provides an oxygen-independent AIE photosensitizer,which has great potential to replace the commercial ACQ photosensitizers.

Advantages and challenges of self-assembled monolayer as a hole-selective contact for perovskite solar cells

Charge-transporting layers(CTLs)are important in determining the performance and stability of perovskite solar cells(PSCs).Recently,there has been considerable use of self-assembled monolayers(SAMs)as charge-selective contacts,especially for hole-selective SAMs in inverted PSCs as well as perovskite involving tandem solar cells.The SAM-based charge-selective contact shows many advantages over traditional thin-film organic/inorganic CTLs,including reduced cost,low optical and electric loss,conformal coating on a rough substrate,simple deposition on a large-area substrate and easy modulation of energy levels,molecular dipoles and surface properties.The incorporation of various hole-selective SAMs has resulted in high-efficiency single junction and tandem solar cells.This topical review summarizes both the advantages and challenges of SAM-based charge-selective contacts,and discusses the potential direction for future studies.

Azobenzene-based ultrathin peptoid nanoribbons for the potential on highly efficient artificial light-harvesting

The development of artificial light-harvesting systems based on long-range ordered ultrathin organic nanomaterials(i.e., below3 nm), which were assembled from stimuli-responsive sequence-controlled biomimetic polymers, remains challenging. Herein,we report the self-assembly of azobenzene-containing amphiphilic ternary alternating peptoids to construct photo-responsive ultrathin peptoids nanoribbons(UTPNRs) with a thickness of ~2.3 nm and the length in several micrometers. The pendants hydrophobic conjugate stacking mechanism explained the formation of one-dimensional ultrathin nanostructures, whose thickness was highly dependent on the length of side groups. The photo-isomerization of azobenzene moiety endowed the aggregates with a reversible morphology transformation from UTPNRs to spherical micelles(46.5 nm), upon the alternative irradiation with ultraviolet and visible light. Donor of 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole(NBD) and acceptor of rhodamine B(RB) were introduced onto the hydrophobic and hydrophilic regions, respectively, to generate photocontrollable artificial light-harvesting systems. Compared with the spheres-based systems, the obtained NBD-UTPNRs@RB composite proved a higher energy transfer efficiency(90.6%) and a lower requirement of RB acceptors in water. A proof-ofconcept use as fluorescent writable ink demonstrated the potential of UTPNRs on information encryption.