Supramolecular phenolic network-engineered C-CeO_(2) nanofibers for simultaneous determination of isoniazid and hydrazine in biological fluids

Electrochemical sensing provides a powerful technological means for the therapeutic drug monitoring of drug-resistant tuberculosis but requires a functionalized electrode to capture the analytes and catalyze their redox reactions.Herein,we construct a nickel-tannic acid supramolecular network(Ni-TA)on the surface of electrospun-derived C-CeO_(2) nanofiber for the sensitive and simultaneous detection of isoniazid(INZ)and hydrazine(HYD).Mechanistic investigations demonstrate that Ni-TA is electronegative and hydrophilic,thus facilitating an efficient mass and electron transfer.Ni-TA/C-CeO_(2) has higher adsorption rate constants(0.091 g mg^(-1)h^(-1)for INZ,and 0.062 g mg^(-1)h^(-1)for HYD)than native C-CeO_(2)(0.075 g mg^(-1)h^(-1)for INZ,and 0.047 g mg^(-1)h^(-1)for HYD).Moreover,Ni-TA/C-CeO_(2)(56Ω)has lower charge transfer resistances than C-CeO_(2)(417Ω).Ni-TA/C-CeO_(2) performs low detection limits and wide linearity ranges for INZ(0.012μmol/L and 0.1-400μmol/L,respectively)and HYD(0.008μmol/L and 0.015-1420μmol/L,respectively),coupled with high selectivity,cycle stability and reproducibility.This research demonstrated the promising applications of Ni-TA/C-CeO_(2) by analyzing human-collected plasma and urine samples.

Liquid metal compartmented by polyphenol-mediated nanointerfaces enables high-performance thermal management on electronic devices

The exponentially increasing heat generation in electronic devices,induced by high power density and miniaturization,has become a dominant issue that affects carbon footprint,cost,performance,reliability,and lifespan.Liquid metals(LMs)with high thermal conductivity are promising candidates for effective thermal management yet are facing pump-out and surface-spreading issues.Confinement in the form of metallic particles can address these problems,but apparent alloying processes elevate the LM melting point,leading to severely deteriorated stability.Here,we propose a facile and sustainable approach to address these challenges by using a biogenic supramolecular network as an effective diffusion barrier at copper particle-LM(EGaIn/Cu@TA)interfaces to achieve superior thermal conduction.The supramolecular network promotes LM stability by reducing unfavorable alloying and fluidity transition.The EGaIn/Cu@TA exhibits a record-high metallic-mediated thermal conductivity(66.1 W m^(-1) K^(-1))and fluidic stability.Moreover,mechanistic studies suggest the enhanced heat flow path after the incorporation of copper particles,generating heat dissipation suitable for computer central processing units,exceeding that of commercial silicone.Our results highlight the prospects of renewable macromolecules isolated from biomass for the rational design of nanointerfaces based on metallic particles and LM,paving a new and sustainable avenue for high-performance thermal management.

Zinc finger-inspired peptide-metal-phenolic nanointerface enhances bone-implant integration under bacterial infection microenvironment through immune modulation and osteogenesis promotion

Orthopedic and dental implantations under bacterial infection microenvironment face significant challenges in achieving high-quality bone-implant integration. Designing implant coatings that incorporate both immune defense and anti-inflammation is difficult in conventional single-functional coatings. We introduce a multifunctional nanointerface using a zinc finger-inspired peptide-metal-phenolic nanocoating, designed to enhance implant osseointegration under such conditions. Abaloparatide (ABL), a second-generation anabolic drug for treating osteoporosis, can be integrated into the design of a zinc-phenolic network constructed on the implant surface (ABL@ZnTA). Importantly, the phenolic-coordinated Zn2+ ions in ABL@ZnTA can act as zinc finger motif to co-stabilize the configuration of ABL through multiple molecular interactions, enabling high bioactivity, high loading capacity (1.36 times), and long-term release (>7 days) of ABL. Our results showed that ABL@ZnTA can modulate macrophage polarization from the pro-inflammatory M1 towards the anti-inflammatory M2 phenotype, promoting immune osteogenesis with increased OCN, ALP, and SOD 1 expression. Furthermore, the ABL@ZnTA significantly reduces inflammatory fibrous tissue encapsulation and enhances the long-term stability of the implants, indicated by enhanced binding strength (6 times) and functional connectivity (1.5−3 times) in the rat bone defect model infected by S. aureus. Overall, our research offers a nano-enabled synergistic strategy that balances infection defense and osteogenesis promotion in orthopedic and dental implantations.

Catalytic hosts with strong adsorption strength for long shelf-life lithium-sulfur batteries under lean electrolyte

Low electrolyte/sulfur ratio(E/S)is an important factor in increasing the energy density of lithium-sulfur batteries(LSBs).Recently,the E/S has been widely lowered using catalytic hosts that can suppress“shuttle effect”during cycling by relying on a limited adsorption area.However,the shelf-lives of these cathodes have not yet received attention.Herein,we show that the selfdischarge of sulfur cathodes based on frequently-used catalytic hosts is serious under low E/S because the“shuttle effect”during storage process caused by polysulfides(PSs)disproportionation cannot be suppressed using a limited adsorption area.We further prove that the adsorption strength toward PSs,which is unfortunately weak in commonly-used catalytic hosts,is critical for effectively hindering the disproportionation of the PSs.Subsequently,to verify this conclusion,we prepare a sulfur-doped titanium nitride(S-TiN)catalytic array host.As the adsorption strength and catalytic activity of TiN can be improved by S doping simultaneously,the constructed S/S-TiN cathodes under a low E/S(6.5μL·mg−1)exhibit better shelf-life and cycle-stability than those of S/TiN cathodes.Our work suggests that enhancing the adsorption strength of catalytic hosts,while maintaining their function to reduce E/S,is crucial for practical LSBs.

A biologically stable, self-catalytic DNAzyme machine encapsulated by metal-phenolic nanoshells for multiple microRNA imaging

DNAzyme machines play critical roles in the fields of cell imaging, disease diagnosis, and cancer therapy. However, the applications of DNAzyme machines are limited by the nucleases-induced degradation,non-specific binding of proteins, and insufficient provision of cofactors. Herein, protected DNAzyme machines with different cofactor designs(referred to as Pro Ds) were nanoengineered by the construction of multifunctional metal-phenolic nanoshells to deactivate the interferential proteins, including nucleases and non-specific binding proteins. Moreover, the nanoshells not only facilitate the cellular internalization of Pro Ds but provide specific metal ions acting as cofactors of the designed DNAzymes. Cellular imaging results demonstrated that Pro Ds could effectively and simultaneously monitor multiple tumor-related micro RNAs in living cells. This facile and rapid strategy that encapsulates DNAzyme machines into the protective metal-phenolic nanoshells is anticipated to extend to a wide range of functional nucleic acidsbased biomedical applications.

Near infrared light-induced dynamic modulation of enzymatic activity through polyphenol-functionalized liquid metal nanodroplets

Dynamic manipulation of enzymatic activity is a challenging task for applications in chemical and pharmaceutical industries due to the difficult modification and variable conformation of various enzymes.Here, we report a new strategy for reversible dynamic modulation of enzymatic activity by near-infrared light-induced photothermal conversion based on polyphenol-functionalized liquid metal nanodroplets(LM). The metal-phenolic nanocoating not only provides colloidal stability of LM nanodroplets but also generates nanointerfaces for the assembly of various enzymes on the LM nanodroplets. Upon near infrared(NIR) irradiation, the localized microenvironmental heating through photothermal effect of the LM nanodroplets allows tailoring the enzymatic activity without affecting the bulk temperature. A library of functional enzymes, including proteinase K, glucoamylase, glucose oxidase, and Bst DNA polymerase, is integrated to perform a reversible control and enhanced activities even after five times of cycles, demonstrating great potential in bacterial fermentation, bacteriostasis, and target gene amplification.

A sustainable thermochemical conversion of animal biomass to N-heterocycles

The production of high-valued organonitrogen chemicals,especially N-heterocycles,requires artificial N_(2)fixation accompanied by the consumption of fossil resources.To avoid the use of these energy-and resource-intensive processes,we develop a sustainable strategy to convert nitrogen-rich animal biomass into N-heterocycles through a thermochemical conversion process(TCP)under atmospheric pressure.A high percentage of N-heterocycles(87.51%)were obtained after the TCP of bovine skin due to the abundance of nitrogen-containing amino acids(e.g.,glycine,proline,and L-hydroxyproline).Animal biomass with more diverse amino acid composition(e.g.,muscles)yielded higher concentrations of amines/amides and nitriles after TCP.In addition,by introducing catalysts(KOH for pyrrole and Al_(2)O_(3)for cyclo-Gly-Pro)to TCP,the production quantities of pyrrole and cyclo-Gly-Pro increased to 30.79 mg g^(-1)and 38.88 mg g^(-1),respectively.This approach can be used to convert the significant animal biomass waste generated annually from animal culls into valued organonitrogen chemicals while circumventing NH3-dependent and petro-chemical-dependent synthesis routes.

Advancing collagen-based biomaterials for oral and craniofacial tissue regeneration

The oral and craniofacial region consists of various types of hard and soft tissues with the intricate organization.With the high prevalence of tissue defects in this specific region,it is highly desirable to enhance tissue regeneration through the development and use of engineered biomaterials.Collagen,the major component of tissue extracellular matrix,has come into the limelight in regenerative medicine.Although collagen has been widely used as an essential component in biomaterial engineering owing to its low immunogenicity,high biocompatibility,and convenient extraction procedures,there is a limited number of reviews on this specific clinic sector.The need for mechanical enhancement and functional engineering drives intensive efforts in collagen-based biomaterials concentrating on therapeutical outcomes and clinical translation in oral and craniofacial tissue regeneration.Herein,we highlighted the status quo of the design and applications of collagen-based biomaterials in oral and craniofacial tissue reconstruction.The discussion expanded on the inspiration from the leather tanning process on modifications of collagen-based biomaterials and the prospects of multi-tissue reconstruction in this particular dynamic microenvironment.The existing findings will lay a new foundation for the optimization of current collagen-based biomaterials for rebuilding oral and craniofacial tissues in the future.

红球菌低分子量型腈水合酶的异源激活及激活子的结构域功能

腈水合酶激活子具有亚基自身交换伴随子或者金属离子伴随子的功能,能够辅助腈水合酶摄取金属离子,对于腈水合酶的活性表达必不可少。与腈水合酶自身相比,激活子的序列保守性低,研究其激活作用的特点,探索其结构与功能之间的关系,对于理解腈水合酶的成熟机制具有重要意义。将红球菌Rhodococcus rhodochrous J1低分子量型腈水合酶L-NHase分别与4种异源激活子组合共表达,测定异源激活子对L-NHase的激活作用,进一步对激活子进行序列分析和结构模拟,并研究关键结构域的功能。结果表明,4种异源激活子均能激活L-NHase,但激活后L-NHase的比酶活存在差异,激活子A对L-NHase的激活程度最高,激活后的L-NHase比酶活为出发酶的97.79%;激活子G对L-NHase的激活程度最低,激活后的L-NHase比酶活为出发酶的23.94%。激活子E和激活子G具有保守结构域TIGR03889,缺失其中部分序列会使两者的激活作用基本丧失。将激活子G的N端序列替换为激活子E的N端序列,并将激活子E的C端序列添加至激活子G的C端,能够使L-NHase的比酶活提高178.40%。激活子的激活作用具有普遍性和特异性,其保守结构域对激活作用至关重要,同时N端结构域和C端结构域也对激活作用产生重要影响。

Collagen-based materials in reproductive medicine and engineered reproductive tissues

Collagen,the main component of mammal skin,has been traditionally used in leather manufacturing for thousands of years due to its diverse physicochemical properties.Collagen is the most abundant protein in mammals and the main component of the extracellular matrix(ECM).The properties of collagen also make it an ideal building block for the engineering of materials for a range of biomedical applications.Reproductive medicine,especially human fertility preservation strategies and reproductive organ regeneration,has attracted significant attention in recent years as it is key in resolving the growing social concern over aging populations worldwide.Collagen-based biomaterials such as collagen hydrogels,decellularized ECM(dECM),and bioengineering techniques including collagen-based 3D bio-printing have facilitated the engineering of reproductive tissues.This review summarizes the recent progress in apply-ing collagen-based biomaterials in reproductive.Furthermore,we discuss the prospects of collagen-based materials for engineering artificial reproductive tissues,hormone replacement therapy,and reproductive organ reconstruction,aiming to inspire new thoughts and advancements in engineered reproductive tissues research.

Engineering microparticles based on solidified stem cell secretome with an augmented pro-angiogenic factor portfolio for therapeutic angiogenesis

Tissue (re)vascularization strategies face various challenges, as therapeutic cells do not survive long enough in situ, while the administration of pro-angiogenic factors is hampered by fast clearance and insufficient ability to emulate complex spatiotemporal signaling. Here, we propose to address these limitations by engineering a functional biomaterial capable of capturing and concentrating the pro-angiogenic activities of mesenchymal stem cells (MSCs). In particular, dextran sulfate, a high molecular weight sulfated glucose polymer, supplemented to MSC cul-tures, interacts with MSC-derived extracellular matrix (ECM) components and facilitates their co-assembly and accumulation in the pericellular space. Upon decellularization, the resulting dextran sulfate-ECM hybrid material can be processed into MIcroparticles of SOlidified Secretome (MIPSOS). The insoluble format of MIPSOS protects protein components from degradation, while facilitating their sustained release. Proteomic analysis demonstrates that MIPSOS are highly enriched in pro-angiogenic factors, resulting in an enhanced pro-angiogenic bioactivity when compared to naïve MSC-derived ECM (cECM). Consequently, intravital microscopy of full-thickness skin wounds treated with MIPSOS demonstrates accelerated revascularization and healing, far superior to the ther-apeutic potential of cECM. Hence, the microparticle-based solidified stem cell secretome provides a promising platform to address major limitations of current therapeutic angiogenesis approaches.

The role of extracellular matrix on unfavorable maternal-fetal interface:focusing on the function of collagen in human fertility

Extracellular matrix(ECM)is characterized as widespread,abundant,and pluripotent.Among ECM members,collagen is widely accepted as one of the most prominent components for its essential structural property that can provide a scaffold for other components of ECM and the rich biological functions,which has been extensively used in tissue engineering.Emerging evidence has shown that the balance of ECM degradation and remodeling is vital to regulations of maternal-fetal interface including menstrual cycling,decidualization,embryo implantation and pregnancy maintenance.Moreover,disorders in these events may eventually lead to failure of pregnancy.Although the improvement of assisted conception and embryo culture technologies bring hope to many infertile couples,some unfavorable outcomes,such as recurrent implantation failure(RIF),recurrent pregnancy loss(RPL)or recurrent miscarriage(RM),keep troubling the clinicians and patients.Recently,in vitro three-dimensional(3D)model mimicking the microenvironment of the maternal-fetal interface is developed to investigate the physiological and pathological conditions of conception and pregnancy.The progress of this technology is based on clarifying the role of ECM in the endometrium and the interaction between endometrium and conceptus.Focusing on collagen,the present review summarized the degradation and regulation of ECM and its role in normal menstruation,endometrium receptivity and unsatisfying events occurring in infertility treatments,as well as the application in therapeutic approaches to improve pregnancy outcomes.More investigations about ECM focusing on the maternal-fetal interface interaction with mesenchymal stem cells or local immunoregulation may inspire new thoughts and advancements in the clinical application of infertility treatments.

Alloyed nanostructures integrated metal-phenolic nanoplatform for synergistic wound disinfection and revascularization

New materials for combating bacteria-caused infection and promoting the formation of microvascular networks during wound healing are of vital importance.Although antibiotics can be used to prevent infection,treatments that can disinfect and accelerate wound healing are scarce.Herein,we engineer a coating that is both highly compatible with current wound dressing substrates and capable of simultaneously disinfecting and revascularizing wounds using a metal-phenolic nanoplatform containing an alloyed nanostructured architecture(Ag@Cu-MPNNC).The alloyed nanostructure is formed by the spontaneous co-reduction and catalytic disproportionation reaction of multiple metal ions on a foundation metal-phenolic supramolecular layer.This synergistic presence of metals greatly improves the antibacterial activity against both Gram-negative and Gram-positive pathogenic bacteria,while demonstrating negligible cytotoxicity to normal tissue.In infected rat models,the Ag@Cu-MPNNC could kill bacteria efficiently,promoting revascularization and accelerate wound closure with no adverse side effects in infected in vivo models.In other words,this material acts as a combination therapy by inhibiting bacterial invasion and modulating bio-nano interactions in the wound.

Collagen peptide provides Streptomyces coelicolor CGMCC 4.7172 with abundant precursors for enhancing undecylprodigiosin production

Effective and ecofriendly converting biomass to chemicals is important for sustainable engineering based on the foreseeable shortage of fossil resources.Undecylprodigiosin(UP)is a promising antibiotic,but the direct feeding of pure precursor amino acids makes it costly for large-scale production.Here,collagen peptide(CP),a renewable animal-derived biomass contains abundant precursor amino acids of UP.CP can act as carbon and nitrogen source for the growth of Streptomyces coelicolor CGMCC 4.7172.The plant biomasses including soybean meal,wheat bran,and malt extract were unsuitable for UP prodution.However,365.40µg/L UP was detected after 24 h in the media containing CP,and its highest concentration reached 1198.01µg/L.UP was also detected in the media containing meat hydrolysates of domestic animals,but its initial production time was delayed,and final concentration was lower than that in the medium containing CP only.Compared the fermentation performances of CP and other proteins,CP has a special superiority for UP production.These results revealed that UP biosynthesis may be dependent on amino acid availability of substrates and CP is beneficial for UP production because of its specific amino acid composition.