Enzymatic self-assembly/disassembly turns “ON”/“OFF” the mimetic hydrolytic activity of histidine nanofibers

Mimetic enzymes are devised as alternates or supplements of natural enzymes in broad fields but regulating their activities in a switchable manner remains challenging.Herein,we proposed an enzymatic self-assembly/disassembly strategy to address this issue.A peptide molecule Nap FFEYIH(YH) was rationally designed which,after self-assembling into nanofibers,lined up the histidine moieties to form active hydrolysis centers for mimicking hydrolase activity.Enzymatic dephosphorylation of Nap FFEYp IH(Yp H) by alkaline phosphatase to yield YH also turned “ON” the hydrolase activity.In turn,phosphorylation of YH by phosphokinase epidermal growth factor receptor to yield Yp H disassembled the nanofibers and thus turned the activity “OFF”.As such,the “ON”/“OFF” of the mimetic hydrolase activities could be regulated under physiological conditions through ALP/EGFR-mediated self-assembly/disassembly of histidine nanofibers.This work provides a feasible strategy for the on-demand fabrication of artificial enzymes with controllable and superior activities.

Multi-Objective Optimization of Multi-Product Parallel Disassembly Line Balancing Problem Considering Multi-Skilled Workers Using a Discrete Chemical Reaction Optimization Algorithm

This work investigates a multi-product parallel disassembly line balancing problem considering multi-skilled workers.A mathematical model for the parallel disassembly line is established to achieve maximized disassembly profit and minimized workstation cycle time.Based on a product’s AND/OR graph,matrices for task-skill,worker-skill,precedence relationships,and disassembly correlations are developed.A multi-objective discrete chemical reaction optimization algorithm is designed.To enhance solution diversity,improvements are made to four reactions:decomposition,synthesis,intermolecular ineffective collision,and wall invalid collision reaction,completing the evolution of molecular individuals.The established model and improved algorithm are applied to ball pen,flashlight,washing machine,and radio combinations,respectively.Introducing a Collaborative Resource Allocation(CRA)strategy based on a Decomposition-Based Multi-Objective Evolutionary Algorithm,the experimental results are compared with four classical algorithms:MOEA/D,MOEAD-CRA,Non-dominated Sorting Genetic Algorithm Ⅱ(NSGA-Ⅱ),and Non-dominated Sorting Genetic Algorithm Ⅲ(NSGA-Ⅲ).This validates the feasibility and superiority of the proposed algorithm in parallel disassembly production lines.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Hollow tubes constructed by carbon nanotubes self-assembly for CO_(2) capture

Carbon nanotubes(CNTs)have garnered significant attention in the fields of science,engineering,and medicine due to their numerous advantages.The initial step towards harnessing the potential of CNTs involves their macroscopic assembly.The present study employed a gentle and direct self-assembly technique,wherein controlled growth of CNT sheaths occurred on the metal wire’s surface,followed by etching of the remaining metal to obtain the hollow tubes composed of CNTs.By controlling the growth time and temperature,it is possible to alter the thickness of the CNTs sheath.After immersing in a solution containing 1 g/L of CNTs at 60℃ for 24 h,the resulting CNTs layer achieved a thickness of up to 60μm.These hollow CNTs tubes with varying inner diameters were prepared through surface reinforcement using polymers and sacrificing metal wires,thereby exhibiting exceptional attributes such as robustness,flexibility,air tightness,and high adsorption capacity that effectively capture CO_(2) from the gas mixture.

A Non-parametric Gradient-Based Shape Optimization Approach for Solving Inverse Problems in Directed Self-Assemblyof Block Copolymers

We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

Interaction betweenamylose,fattyacid,andβ-lactoglobulinto study multiplebiomacromoleculesself-assemblyandapplication

New concept for the development of supramolecular assemblies from intricate inter-actions between different classes of biomacromolecules(polysaccharides,proteins and lipids)is yet to come,due to their intrinsic chemical and structural complex-ity and incompatibility.Herein,we report an interaction mechanism among multiple biomacromolecules,and the structural and digestive properties of their assemblies using amylose(AM),lauric acid(LA),andβ-lactoglobulin(βLG)as exemplars.AM,LA,andβLG interact to form a water-soluble ternary complex through van der Waals forces between AM and LA and high affinity binding between AM andβLG,which can further assemble into uniform-sized,semi-crystalline nanospheres under certain thermodynamic conditions.These nanospheres are substantially resis-tant to amylolysis,thus can be well utilized by gut microbiota,including increasing short-chain fatty acid levels and shaping bacterial communities.Illustrating the com-plexation of AM,LA,andβLG and their assemblies from disorder to order,this work offers potential rationale of assemblies for multiple biomacromolecules driven by non-covalent interactions and substantial potentials for supramolecular biomaterials development.

A self-assembly/disassembly two-photo ratiometric fluorogenic probe for bacteria imaging

Fluorescence imaging has facilitated fluorescent probes to analyze the subcellular localization and dynamics of biological targets. In this paper, we reported a fluorogenic probe for bacteria imaging. The probe was an imidazolium-derived pyrene compound, which self-assembled to form nano-particles and the pyrene fluorescence was quenched by the aggregation effects. When the self-assembly nanoparticles interacted with anionic bacteria surfaces, synergistic effects of electrostatic interaction and hydrophobic force caused competing binding between bacteria surfaces and imidazoliums. This binding resulted in the disassembly of the aggregates to give fluorescence turn-on signal. Meanwhile, the probe bound bacteria surfaces and displayed both pyrene-excimer and pyrene-monomer fluorescence, which gave ratiometric signal. Then, fluorescent labeling by the probe enabled the two-photo ratiometric imaging of bacteria.

Combination therapy to overcome ferroptosis resistance by biomimetic self-assembly nano-prodrug

Ferroptosis has emerged as a potent form of no-apoptotic cell death that offers a promising alternative to avoid the chemoresistance of apoptotic pathways and serves as a vulnerability of cancer.Herein,we have constructed a biomimetic self-assembly nano-prodrug system that enables the co-delivery of gefitinib(Gefi),ferrocene(Fc)and dihydroartemisinin(DHA)for the combined therapy of both ferroptosis and apoptosis.In the tumor microenvironment,this nano-prodrug is able to disassemble and trigger drug release under high levels of GSH.Interestingly,the released DHA can downregulate GPX4 level for the enhancement of intracellular ferroptosis from Fc,further executing tumor cell death with concomitant chemotherapy by Gefi.More importantly,this nano-prodrug provides highly homologous targeting ability by coating related cell membranes and exhibits outstanding inhibition of tumor growth and metastasis,as well as no noticeable side-effects during treatments.This simple small molecular self-assembled nano-prodrug provides a new reasonably designed modality for ferroptosis-combined chemotherapy.

Efficient conversion of lignin waste and self-assembly synthesis of C@MnCo_(2)O_(4)for asymmetric supercapacitors with high energy density

Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications,such as the electrodes of supercapacitors;however,the improvement of their energy density remains a challenge.Here,we design a green and universal approach to prepare the composite electrode material,which is composed of lignin-phenolformaldehyde resins derived hierarchical porous carbon(LR-HPC)as conductive skeletons and the self-assembly manganese cobaltite(MnCo_(2)O_(4))nanocrystals as active sites.The synthesized C@MnCo_(2)O_(4)composite has an abundant porous structure and superior electronic conductivity,allowing for more charge/electron mass transfer channels and active sites for the redox reactions.The composite shows excellent electrochemical performance,such as the maximum specific capacitance of~726 mF cm^(-2)at 0.5 mV s^(-1),due to the significantly enhanced interactive interface between LR-HPC and MnCo_(2)O_(4)crystals.The assembled all-solid-state asymmetric supercapacitor,with the LR-HPC and C@MnCo_(2)O_(4)as cathode and anode,respectively,exhibits the highest volumetric energy density of 0.68 mWh cm^(-3)at a power density of 8.2 mW cm^(-3).Moreover,this device shows a high capacity retention ratio of~87.6%at 5 mA cm^(-2)after 5000 cycles.

Experimental Study on the Reduction Effect of Pit Texture on Disassembly Damage for Interference Fit

After remanufacturing disassembly,several kinds of friction damages can be found on the mating surface of interference fit.These damages should be repaired and the cost is closely related to the severity of damages.Inspired by the excellent performance of surface texture in wear reduction,5 shapes of pit array textures are added to the specimens’surface to study their reduction effect of disassembly damage for interference fit.The results of disassembly experiments show that the order of influence of texture parameters on disassembly damage is as follows:equivalent circle diameter of single texture,texture shape and texture surface density.The influence of equivalent circle diameter of single texture and texture shape are obviously more significant than that of texture surface density.The circular texture with a surface density of 30%and a diameter of 100μm shows an excellent disassembly damage reduction effect because of its perfect ability of abrasive particle collection.And the probability of disassembly damage formation and evolution is also relatively small on this kind of textured surface.Besides,the load-carrying capacity of interference fit with the excellent texture is confirmed by load-carrying capacity experiments.The results show that the load-carrying capacity of the excellent texture surface is increased about 40%compared with that of without texture.This research provides a potential approach to reduce disassembly damage for interference fit.

Analysis on the formation principle and present situation of nano phase state of multi-component self-assembly of traditional Chinese compound medicine decoction

Traditional Chinese medicine decoction is a complex polydispersed phase system containing real solution,colloid solution,emulsion and suspension.The compound decoction of traditional Chinese medicine has complex components,including saponins,alkaloids,polysaccharides,flavonoids,amino acids and so on,which can be self-assembled to form gels,fibers,micelles,vesicles and so on.The self-assembled nano-phase not only neutralizes the single drug and reduces the toxicity and side effects,but also has its own pharmacological effects,which complement each other to achieve synergistic effect,so as to achieve the role of drug supplement,which is of research significance.The formation principle,solubilization and synergism principle and characterization method of multi-component self-assembly of traditional Chinese medicine compound decoction are discussed in this paper.

Thick Electrodes of a Self-Assembled MXene Hydrogel Composite for High-Rate Energy Storage

Supercapacitors based on two-dimensional MXene(Ti_(3)C_(2)T_(z))have shown extraordinary performance in ultrathin electrodes with low mass loading,but usually there is a significant reduction in high-rate performance as the thickness increases,caused by increasing ion diffusion limitation.Further limitations include restacking of the nanosheets,which makes it challenging to realize the full potential of these electrode materials.Herein,we demonstrate the design of a vertically aligned MXene hydrogel composite,achieved by thermal-assisted self-assembled gelation,for high-rate energy storage.The highly interconnected MXene network in the hydrogel architecture provides very good electron transport properties,and its vertical ion channel structure facilitates rapid ion transport.The resulting hydrogel electrode show excellent performance in both aqueous and organic electrolytes with respect to high capacitance,stability,and high-rate capability for up to 300μm thick electrodes,which represents a significant step toward practical applications.

Supramolecular self-assembled nanoparticles for targeted therapy of myocardial infarction by enhancing cardiomyocyte mitophagy

Myocardial infarction accompanied by diabetes mellitus is accepted as the most seri-ous type of coronary heart disease,and among the current treatment strategies,the precise delivery of protective drugs for inhibiting cardiomyocyte apoptosis is still a challenge.In this study,we developed a biodegradable nanoparticles-based delivery system with excellent macrophage escape,cardiac targeting,and drug release prop-erties to achieve targeted therapy of myocardial infarction.Specifically,a copolymer of p(DMA–MPC–CD)combining self-adhesion,hydration lubrication,and targeting peptide binding site was successfully prepared by free radical copolymerization,and it was self-assembled on the surface of melatonin-loaded dendritic mesoporous silica nanoparticles(bMSNs)following the integration of adamantane-modified cardiac homing peptide(CHP)based on supramolecular host–guest interaction.Importantly,a hydration layer formed around the zwitterionic phosphorylcholine groups of the multifunctional nanoparticles,which was confirmed by the enhancement in hydra-tion lubrication and reduction in coefficient of friction,prevented the nanoparticles from phagocytosis by the macrophages.The in vivo bioluminescence imaging test indicated that the nanoparticles were endowed with satisfied cardiac targeting capa-bility,and the in vivo mice study demonstrated that the intravenous injection of drug-loaded nanoparticles(namely bMSNs–Mel@PDMC–CHP)effectively reduced cardiomyocyte apoptosis,alleviated myocardial interstitialfibrosis,and enhanced cardiac function.

Role of self-assembled molecules’anchoring groups for surface defect passivation and dipole modulation in inverted perovskite solar cells

Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication,low hysteresis effects,and high stability.Despite these advantages,their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite-electrode interface,particularly at the buried interface between the perovskite and transparent conductive oxide(TCO).Recent efforts in the perovskite community have focused on designing novel self-assembled molecules(SAMs)to improve the quality of the buried interface.However,a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces.This understanding is crucial,particularly in terms of identifying chemically active anchoring groups.In this study,we used the star SAM([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite-TCO interface.Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages.These groups fulfill three key criteria:they provide the greatest potential for defect passivation,exhibit stable adsorption with defects,and exert significant regulatory effects on interface dipoles.Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties,which effectively neutralize local charges near defects.Among various defect types,iodine vacancies are the easiest to passivate,whereas iodine-substituted lead defects are the most challenging to passivate.Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs,contributing to the ongoing development of more efficient inverted perovskite solar cells.

Factors resisting protein adsorption on hydrophilic/hydrophobic self-assembled monolayers terminated with hydrophilic hydroxyl groups

The hydroxyl-terminated self-assembled monolayer(OH-SAM),as a surface resistant to protein adsorption,exhibits substantial potential in applications such as ship navigation and medical implants,and the appropriate strategies for designing anti-fouling surfaces are crucial.Here,we employ molecular dynamics simulations and alchemical free energy calculations to systematically analyze the factors influencing resistance to protein adsorption on the SAMs terminated with single or double OH groups at three packing densities(∑=2.0 nm^(-2),4.5 nm^(-2),and 6.5 nm^(-2)),respectively.For the first time,we observed that the compactness and order of interfacial water enhance its physical barrier effect,subsequently enhancing the resistance of SAM to protein adsorption.Notably,the spatial hindrance effect of SAM leads to the embedding of protein into SAM,resulting in a lack of resistance of SAM towards protein.Furthermore,the number of hydroxyl groups per unit area of double OH-terminated SAM at ∑=6.5 nm^(-2) is approximately 2 to 3 times that of single OH-terminated SAM at ∑=6.5 nm^(-2) and 4.5 nm^(-2),consequently yielding a weaker resistance of double OH-terminated SAM towards protein.Meanwhile,due to the structure of SAM itself,i.e.,the formation of a nearly perfect ice-like hydrogen bond structure,the SAM exhibits the weakest resistance towards protein.This study will complement and improve the mechanism of OH-SAM resistance to protein adsorption,especially the traditional barrier effect of interfacial water.

Morphological Evolution of Self-Assembled Sodium Dodecyl Sulfate/Dodecyltrimethylammonium Bromide@Epoxy-β-Cyclodextrin Supramolecular Aggregates Induced by Temperature

Bio-based cyclodextrins(CDs)are a common research object in supramolecular chemistry.The special cavity structure of CDs can form supramolecular self-assemblies such as vesicles and microcrystals through weak interaction with guest molecules.The different forms of supramolecular self-assemblies can be transformed into each other under certain conditions.The regulation of supramolecular self-assembly is not only helpful to understand the self-assembly principle,but also beneficial to its application.In the present study,the self-assembly behavior of epoxy-β-cyclodextrin(EP-β-CD)and mixed anionic and cationic surfactant system(sodium dodecyl sulfate/dodecyltrimethylammonium bromide,SDS/DTAB)in aqueous solution was studied.Morphological and particle size characterization found that the SDS/DTAB@EP-β-CD complex,as the basic building unit,self-assembled into worm-like micelles at lower temperatures and vesicles at higher temperatures.Nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FT-IR)analysis revealed that the driving force for the formation of vesicles and worm-like micelles was the hydrogen bonds between EP-β-CD molecules,while water molecules played an important role in promoting vesicle formation between SDS/DTAB@EP-β-CD units.Herein,the mechanism of the morphologic transformation of SDS/DTAB@EP-β-CD supramolecular aggregates induced by temperature was elucidated by exploring the self-assembly process,which may provide an excellent basis for the development of delivery carriers.

Intelligent responsive self-assembled micro-nanocapsules:Used to delay gel gelation time

In the application of polymer gels to profile control and water shutoff,the gelation time will directly determine whether the gel can"go further"in the formation,but the most of the methods for delaying gel gelation time are complicated or have low responsiveness.There is an urgent need for an effective method for delaying gel gelation time with intelligent response.Inspired by the slow-release effect of drug capsules,this paper uses the self-assembly effect of gas-phase hydrophobic SiO_(2) in aqueous solution as a capsule to prepare an intelligent responsive self-assembled micro-nanocapsules.The capsule slowly releases the cross-linking agent under the stimulation of external conditions such as temperature and pH value,thus delaying gel gelation time.When the pH value is 2 and the concentration of gas-phase hydrophobic SiO_(2) particles is 10%,the gelation time of the capsule gel system at 30,60,90,and 120℃is12.5,13.2,15.2,and 21.1 times longer than that of the gel system without containing capsule,respectively.Compared with other methods,the yield stress of the gel without containing capsules was 78 Pa,and the yield stress after the addition of capsules was 322 Pa.The intelligent responsive self-assembled micronanocapsules prepared by gas-phase hydrophobic silica nanoparticles can not only delay the gel gelation time,but also increase the gel strength.The slow release of cross-linking agent from capsule provides an effective method for prolongating the gelation time of polymer gels.