pH-Responsive Host-Guest Complexation between a Water-soluble Pillar[7]Arene and a 2,7-Diazapyrenium Salt and Its Application in Controllable Self-assembly

A novel host-guest recognition motif based on a water-soluble pillar[7]arene （WP7） and a 2,7-diazapyrenium salt （DMDAP） was prepared. According to the integrated results of ^1H NMR, 2D NOESY, UV-vis spectroscopy and fluorescence titration experiments, we demonstrated that the molecular recognition of WP7 to DMDAP in water not only has high association constant but also has pH-responsiveness. Subsequently, we took advantage of this molecular recognition motif to fabricate a supra-amphiphile based on WP7 and an amphiphilic 2,7-diazapyrenium derivative DAPAC. Its controllable self-assembly in water was also investigated by means of TEM and DLS techniques.

Controllable self-assembly of parallel gold nanorod clusters by DNA origami

Herein we demonstrate the construction of three types of parallel gold nanorod(AuNR) clusters using a DNA origami rod(DOR) as the template. Based on the precise control over the position of capture strands on DOR, number and orientation of the AuNR clusters can be well engineered, as evidenced by biological transmission electron microscope(TEM). Importantly, the AuNR clusters exhibit chiroptical responses which are strongly affected by the number of AuNR on rod-like DNA origami.

An amphiphilic[2]biphenyl-extended pillar[6]arene:Synthesis,controllable self-assembly in water and application in cell-imaging

Synthesis and functionalization of novel macrocyclic host molecules are important topics in supramolecular chemistry.In this work,the first amphiphilic[2]biphenyl-extended pillar[6]arene(AM-[2]BP-ExP6)was designed and synthesized with poly(ethylene glycol)chains as the hydrophilic tails and a rigid cavity as the hydrophobic core.Due to its amphiphilic nature,AM-[2]BP-ExP6 could self-assemble to stable fibers in water.What’s more,AM-[2]BP-ExP6 could associate with quaternary ammonium modified tetraphenylethylene guest(QTPE)to form a 2:1 host-guest complex,accompanied by significant enhanced fluorescence.Interestingly,different like AM-[2]BP-ExP6,AM-[2]BP-ExP6⊃QTPE host-guest complex selfassembled into fluorescent particles with diameter about 310 nm,the obtained fluorescent particles can be further employed in living cell imaging.

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).

Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

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.

Controllable Condensation of Aromatics and Its Mechanisms in Carbonization

In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.

A Lightweight, Searchable, and Controllable EMR Sharing Scheme

Electronic medical records (EMR) facilitate the sharing of medical data, but existing sharing schemes suffer fromprivacy leakage and inefficiency. This article proposes a lightweight, searchable, and controllable EMR sharingscheme, which employs a large attribute domain and a linear secret sharing structure (LSSS), the computationaloverhead of encryption and decryption reaches a lightweight constant level, and supports keyword search andpolicy hiding, which improves the high efficiency of medical data sharing. The dynamic accumulator technologyis utilized to enable data owners to flexibly authorize or revoke the access rights of data visitors to the datato achieve controllability of the data. Meanwhile, the data is re-encrypted by Intel Software Guard Extensions(SGX) technology to realize resistance to offline dictionary guessing attacks. In addition, blockchain technology isutilized to achieve credible accountability for abnormal behaviors in the sharing process. The experiments reflectthe obvious advantages of the scheme in terms of encryption and decryption computation overhead and storageoverhead, and theoretically prove the security and controllability in the sharing process, providing a feasible solutionfor the safe and efficient sharing of EMR.

Electrically controllable spin filtering in zigzag phosphorene nanoribbon based normal–antiferromagnet–normal junctions

We investigated the electric controllable spin-filtering effect in a zigzag phosphorene nanoribbon(ZPNR) based normal–antiferromagnet–normal junction. Two ferromagnets are closely coupled to the edges of the nanoribbon and form the edge-to-edge antiferromagnetism. Under an in-plane electric field, the two degenerate edge bands of the edge-to-edge antiferromagnet split into four spin-polarized sub-bands and a 100% spin-polarized current can be easily induced with the maximal conductance 2e~2/h. The spin polarization changes with the strength of the electric field and the exchange field,and changes sign at opposite electric fields. The spin-polarized current switches from one edge to the other by reversing the direction of the electric field. The edge current can also be controlled spatially by changing the electric potential of the scattering region. The manipulation of edge current is useful in spin-transfer-torque magnetic random-access memory and provides a practical way to develop controllable spintronic devices.

Controllable thermal rectification design for buildings based on phase change composites

Phase-change material(PCM)is widely used in thermal management due to their unique thermal behavior.However,related research in thermal rectifier is mainly focused on exploring the principles at the fundamental device level,which results in a gap to real applications.Here,we propose a controllable thermal rectification design towards building applications through the direct adhesion of composite thermal rectification material(TRM)based on PCM and reduced graphene oxide(rGO)aerogel to ordinary concrete walls(CWs).The design is evaluated in detail by combining experiments and finite element analysis.It is found that,TRM can regulate the temperature difference on both sides of the TRM/CWs system by thermal rectification.The difference in two directions reaches to 13.8 K at the heat flow of 80 W/m^(2).In addition,the larger the change of thermal conductivity before and after phase change of TRM is,the more effective it is for regulating temperature difference in two directions.The stated technology has a wide range of applications for the thermal energy control in buildings with specific temperature requirements.

A matrix metalloproteinase-responsive hydrogel system controls angiogenic peptide release for repair of cerebral ischemia/reperfusion injury

Vascular endothelial growth factor and its mimic peptide KLTWQELYQLKYKGI(QK)are widely used as the most potent angiogenic factors for the treatment of multiple ischemic diseases.However,conventional topical drug delivery often results in a burst release of the drug,leading to transient retention(inefficacy)and undesirable diffusion(toxicity)in vivo.Therefore,a drug delivery system that responds to changes in the microenvironment of tissue regeneration and controls vascular endothelial growth factor release is crucial to improve the treatment of ischemic stroke.Matrix metalloproteinase-2(MMP-2)is gradually upregulated after cerebral ischemia.Herein,vascular endothelial growth factor mimic peptide QK was self-assembled with MMP-2-cleaved peptide PLGLAG(TIMP)and customizable peptide amphiphilic(PA)molecules to construct nanofiber hydrogel PA-TIMP-QK.PA-TIMP-QK was found to control the delivery of QK by MMP-2 upregulation after cerebral ischemia/reperfusion and had a similar biological activity with vascular endothelial growth factor in vitro.The results indicated that PA-TIMP-QK promoted neuronal survival,restored local blood circulation,reduced blood-brain barrier permeability,and restored motor function.These findings suggest that the self-assembling nanofiber hydrogel PA-TIMP-QK may provide an intelligent drug delivery system that responds to the microenvironment and promotes regeneration and repair after cerebral ischemia/reperfusion injury.

Research advances in enhanced coal seam gas extraction by controllable shock wave fracturing

With the continuous increase of mining in depth,the gas extraction faces the challenges of low permeability,great ground stress,high temperature and large gas pressure in coal seam.The controllable shock wave(CSW),as a new method for enhancing permeability of coal seam to improve gas extraction,features in the advantages of high efficiency,eco-friendly,and low cost.In order to better utilize the CSW into gas extraction in coal mine,the mechanism and feasibility of CSW enhanced extraction need to be studied.In this paper,the basic principles,the experimental tests,the mathematical models,and the on-site tests of CSW fracturing coal seams are reviewed,thereby its future research directions are provided.Based on the different media between electrodes,the CSW can be divided into three categories:hydraulic effect,wire explosion and excitation of energetic materials by detonating wire.During the process of propagation and attenuation of the high-energy shock wave in coal,the shock wave and bubble pulsation work together to produce an enhanced permeability effect on the coal seam.The stronger the strength of the CSW is,the more cracks created in the coal is,and the greater the length,width and area of the cracks being.The repeated shock on the coal seam is conducive to the formation of complex network fracture system as well as the reduction of coal seam strength,but excessive shock frequency will also damage the coal structure,resulting in the limited effect of the enhanced gas extraction.Under the influence of ground stress,the crack propagation in coal seam will be restrained.The difference of horizontal principal stress has a significant impact on the shape,propagation direction and connectivity of the CSW induced cracks.The permeability enhancement effect of CSW is affected by the breakage degree of coal seam.The shock wave is absorbed by the broken coal,which may hinder the propagation of CSW,resulting in a poor effect of permeability enhancement.When arranging two adjacent boreholes for CSW permeability enhancement test,the spacing of boreholes should not be too close,which may lead to negative pressure mutual pulling in the early stage of drainage.At present,the accurate method for effectively predicting the CSW permeability enhanced range should be further investigated.

Sensitivity of Marine Controllable Source Electromagnetic Soundings for Identifying Plume Migration in Offshore CO_(2) Storage

Offshore carbon dioxide(CO_(2)) storage is an effective method for reducing greenhouse gas emissions. However, when using traditional seismic wave methods to monitor the migration of sequestration CO_(2) plumes, the characteristics of wave velocity changes tend to become insignificant beyond a certain limit. In contrast, the controllable source electromagnetic method(CSEM) remains highly sensitive to resistivity changes. By simulating different CO_(2) plume migration conditions, we established the relevant models and calculated the corresponding electric field response characteristic curves, allowing us to analyze the CSEM's ability to monitor CO_(2) plumes. We considered potential scenarios for the migration and diffusion of offshore CO_(2) storage, including various burial depths, vertical extension diffusion, lateral extension diffusion,multiple combinations of lateral intervals, and electric field components. We also obtained differences in resistivity inversion imaging obtained by CSEM to evaluate its feasibility in monitoring and to analyze all the electric field(Ex, Ey, and Ez) response characteristics. CSEM has great potential in monitoring CO_(2) plume migration in offshore saltwater reservoirs due to its high sensitivity and accuracy. Furthermore, changes in electromagnetic field response reflect the transport status of CO_(2) plumes, providing an important basis for monitoring and evaluating CO_(2)transport behavior during storage processes.

Controllable Synthesis of Au NRs and Its Flexible SERS Optical Fiber Probe with High Sensitivity

The surface-enhanced Raman scattering(SERS) optical fiber probes were successfully prepared by self-assembling on polyelectrolyte multilayers. Gold nanorods(Au NRs) were used as SERS enhancement material to give excellent biological affinity and stability to the SERS optical fiber probes. Au NRs were synthesized by seed growth method. The synergistic effect between AgNO_(3) and surfactant was investigated, and the highest yield was found when AgNO_(3) was 500 uL. Meanwhile, different SERS optical fiber probes were obtained by selecting silane coupling agent, polyelectrolyte multilayer and graphene oxide(GO) to treat quartz fiber. It was found that the SERS optical fiber probes obtained by the self-assembled on polyelectrolyte multilayers method performed better than those by other methods. In addition, Mapping was combined with finite element simulation to analyze the electromagnetic field distribution at the fiber end face.The electromagnetic field distribution of Au NRs was investigated, the difference of electromagnetic field intensity around the Au NRs with different arrangements was compared, the strongest signal was obtained when the Au NRs were head-to-head. Finally, sensitivity of the optimized SERS optical fiber probes could reach 10^(-9)mol/L, with excellent stability and repeatability.

Advanced Functional Electromagnetic Shielding Materials:A Review Based on Micro‑Nano Structure Interface Control of Biomass Cell Walls

Research efforts on electromagnetic interference(EMI)shielding materials have begun to converge on green and sustainable biomass materials.These materials offer numerous advantages such as being lightweight,porous,and hierarchical.Due to their porous nature,interfacial compatibility,and electrical conductivity,biomass materials hold significant potential as EMI shielding materials.Despite concerted efforts on the EMI shielding of biomass materials have been reported,this research area is still relatively new compared to traditional EMI shielding materials.In particular,a more comprehensive study and summary of the factors influencing biomass EMI shielding materials including the pore structure adjustment,preparation process,and micro-control would be valuable.The preparation methods and characteristics of wood,bamboo,cellulose and lignin in EMI shielding field are critically discussed in this paper,and similar biomass EMI materials are summarized and analyzed.The composite methods and fillers of various biomass materials were reviewed.this paper also highlights the mechanism of EMI shielding as well as existing prospects and challenges for development trends in this field.

Thermo-controllable self-assembled structures of single-layer 4,4"-diamino-p-terphenyl molecules on Au(110)

Here we report the thermo-controllable self-assembled structures of single-layer 4, 4＇＇-diamino-p-terphenyl（DAT）molecules on Au（110）, which are investigated by scanning tunneling microscopy（STM） combined with density functional theory（DFT） based calculations. With the deposition of monolayer DAT molecules on Au（110） and subsequent annealing at 100℃, all DAT molecules adsorb on a（1×5） reconstructed surface with a ladder-like structure. After annealing the sample at about 200℃, STM images show three distinct domains, including DAT molecules on a（1×3） reconstructed surface, dehydrogenated molecules with two hydrogen atoms detached from one amino group（–2H-DAT） on a（1×5）reconstructed surface and dehydrogenated molecules with four hydrogen atoms detached from two amino groups（–4HDAT） on a（1×3） reconstructed surface through N–Au bonds. Furthermore, after annealing the sample to 350℃, STM image shows only one self-assembled structure with –4H-DAT molecules on a（1×3） reconstructed surface. Relative STM simulations of different self-assembled structures show excellent agreements with the experimental STM images at different annealing temperatures. Further DFT calculations on the dehydrogenation process of DAT molecule prove that the dehydrogenation barrier on a（1×5） reconstructed surface is lower than that on（1×3） one, which demonstrate the experimental results that the formation temperature of a（1×3） reconstructed surface is higher than that of a（1×5） one.