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.

Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

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.

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.

Nano/Micro-Structural Supramolecular Biopolymers: Innovative Networks with the Boundless Potential in Sustainable Agriculture

Sustainable agriculture plays a crucial role in meeting the growing global demand for food while minimizing adverse environmental impacts from the overuse of synthetic pesticides and conventional fertilizers.In this context,renewable biopolymers being more sustainable offer a viable solution to improve agricultural sustainability and production.Nano/micro-structural supramolecular biopolymers are among these innovative biopolymers that are much sought after for their unique features.These biomaterials have complex hierarchical structures,great stability,adjustable mechanical strength,stimuli-responsiveness,and self-healing attributes.Functional molecules may be added to their flexible structure,for enabling novel agricultural uses.This overview scrutinizes how nano/micro-structural supramolecular biopolymers may radically alter farming practices and solve lingering problems in agricultural sector namely improve agricultural production,soil health,and resource efficiency.Controlled bioactive ingredient released from biopolymers allows the tailored administration of agrochemicals,bioactive agents,and biostimulators as they enhance nutrient absorption,moisture retention,and root growth.Nano/micro-structural supramolecular biopolymers may protect crops by appending antimicrobials and biosensing entities while their eco-friendliness supports sustainable agriculture.Despite their potential,further studies are warranted to understand and optimize their usage in agricultural domain.This effort seeks to bridge the knowledge gap by investigating their applications,challenges,and future prospects in the agricultural sector.Through experimental investigations and theoretical modeling,this overview aims to provide valuable insights into the practical implementation and optimization of supramolecular biopolymers in sustainable agriculture,ultimately contributing to the development of innovative and eco-friendly solutions to enhance agricultural productivity while minimizing environmental impact.

Active straining engineering on self-assembled stacked Ni-based hybrid electrode for ultra-low overpotential

Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.

Au@Ag Core-shell Nanorods Self-assembled on Polyelectrolyte Multilayers for Ultra-High Sensitivity SERS Fiber Probes

We demonstrated a chemical process in the fabrication of a SERS fiber probe with an ultrahigh sensitivity.The synthesis was carried out by preparing Au@Ag core-shell nanorods (Au@Ag-NRs) selfassembled on polyelectrolyte (PE) multilayers,for which Au@Ag-NRs were controlled by adjusting the silver layer thickness.The effect of silver layer thickness of Au@Ag-NRs on the SERS performance of the fiber probe was investigated.The SERS fiber probe shows the best performance when the silver layer thickness is controlled at 8.57 nm.Under the condition of optimizing silver layer thickness,the fiber probe exhibits ultra-high sensitivity (i e,10^(-10) M crystalline violet,CV),good reproducibility (i e,RSD of 3.5%) and stability.Besides,electromagnetic field distribution of the SERS fiber probe was also investigated.The strongest enhancement is found within the core of fiber,whereas a weakened electromagnetic field exists in the fiber cladding layer.The SERS fiber probe can be a good candidate in ultra-trace detection for biomedical and environmental areas.

Mechanism of N-octadecyl-N′-maleoyl-L-phenylalanine self-assembled into supramolecular structures

N-Octadecyl-N1-maleoyl-L-phenylalanine （ODMA-L-Phe） was synthesized through the condensation, deprotection and acid- ylation reaction of BOC-L-phenylalanine, octadecylamine and maleic anhydride. ODMA-L-Phe can self-assemble in some organic solvents and turned them into thermally reversible physical supramolecular organogels. The morphology of ODMA-L-Phe aggregates was characterized by polarized optical microscopy （POM） and field emission scanning electron microscope （FE-SEM）. The aggregates of ODMA-L-Phe were needle-like fibrils with diameters of approximately 100-200 nm. The mechanism of ODMA- L-Phe self-assembly in organic solvents was investigated using XH NMR and circular dichroism （CD）. The results indicated that hydrogen bonding was one of the main driving forces for the self-assembly of ODMA-L-Phe.

Structure and Mechanical Properties of Waterborne Polyurethane-based Composites Filled with Self-assembled Supramolecular Nanoplatelets

New composites of waterborne polyurethane （WPU） as a matrix were prepared by incorporating rigid supramolecular nanoplatelets （SNs） as filler, which were self-assembled by the selective inclusion of β-cyclodextrin （β-CD） onto poly（propylene oxide） （PPO） segment in the poly（ethylene oxide）- block-PPO-block-poly（ethylene oxide） （PEO-b-PPO-b-PEO）. It is worth noting that, when the loading level of SN is lower than 3wt%, the SNs with moderate PEO length result in the simultaneous increase in strength, elongation and Young＇s modulus in contrast with neat WPU. If there is no stretching free PEO chain, both strength and elongation decrease in spite of an increase in Young＇s modulus. However, too long PEO chains result in the decrease of mechanical performances while the relatively higher loading-level of SNs also inhibits the enhancement of strength and elongation.

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.

Supramolecular polymer-based gel fracturing fluid with a double network applied in ultra-deep hydraulic fracturing

A gel based on polyacrylamide,exhibiting delayed crosslinking characteristics,emerges as the preferred solution for mitigating degradation under conditions of high temperature and extended shear in ultralong wellbores.High viscosity/viscoelasticity of the fracturing fluid was required to maintain excellent proppant suspension properties before gelling.Taking into account both the cost and the potential damage to reservoirs,polymers with lower concentrations and molecular weights are generally preferred.In this work,the supramolecular action was integrated into the polymer,resulting in significant increases in the viscosity and viscoelasticity of the synthesized supramolecular polymer system.The double network gel,which is formed by the combination of the supramolecular polymer system and a small quantity of Zr-crosslinker,effectively resists temperature while minimizing permeability damage to the reservoir.The results indicate that the supramolecular polymer system with a molecular weight of(268—380)×10^(4)g/mol can achieve the same viscosity and viscoelasticity at 0.4 wt%due to the supramolecular interaction between polymers,compared to the 0.6 wt%traditional polymer(hydrolyzed polyacrylamide,molecular weight of 1078×10^(4)g/mol).The supramolecular polymer system possessed excellent proppant suspension properties with a 0.55 cm/min sedimentation rate at 0.4 wt%,whereas the0.6 wt%traditional polymer had a rate of 0.57 cm/min.In comparison to the traditional gel with a Zrcrosslinker concentration of 0.6 wt%and an elastic modulus of 7.77 Pa,the double network gel with a higher elastic modulus(9.00 Pa)could be formed only at 0.1 wt%Zr-crosslinker,which greatly reduced the amount of residue of the fluid after gel-breaking.The viscosity of the double network gel was66 m Pa s after 2 h shearing,whereas the traditional gel only reached 27 m Pa s.

Enhanced Ion-Selective Diffusion Achieved by Supramolecular Interaction for High Thermovoltage and Thermal Stability

Thermoelectric(TE)generators capable of converting thermal energy into applicable electricity have gained great popularity among emerging energy conversion technologies.Biopolymer-based ionic thermoelectric(i-TE)materials are promising candidates for energy conversion systems because of their wide sources,innocuity,and low manufacturing cost.However,common physically crosslinked biopolymer gels induced by single hydrogen bonding or hydrophobic interaction suffer from low differential thermal voltage and poor thermodynamic stability.Here,we develop a novel i-TE gel with supramolecular structures through multiple noncovalent interactions between ionic liquids(ILs)and gelatin molecular chains.The thermopower and thermoelectric power factor of the ionic gels are as high as 2.83 mV K-1 and 18.33μW m^(-1)K^(-2),respectively.The quasi-solid-state gelatin-[EMIM]DCA i-TE cells achieve ultrahigh 2 h output energy density(E_(2h)=9.9 mJ m^(-2))under an optimal temperature range.Meanwhile,the remarkable stability of the supramolecular structure provides the i-TE hydrogels with a thermal stability of up to 80℃.It breaks the limitation that biopolymer-based i-TE gels can only be applied in the low temperature range and enables biopolymer-based i-TE materials to pursue better performance in a higher temperature range.

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.

Construction and Properties of the Me_(10)Q[5]/2,7-diaminofluorenedihydrochloride Supramolecular Hydrogel

Compared to traditional polymer hydrogels,supramolecular hydrogels exhibits superior reversibility and stimulus response due to the instantaneous and reversible nature of non-covalent bonds.In this paper,we utilized the host-guest exclusion interaction between Decamethylcucurbit[5]uril(Me_(10)Q[5])and the 2,7-diaminofluorenedihydrochloride(DAF·HCl)to construct a Q[n]-based hydrogel system.The composition,structure,and properties of the hydrogel were compre-hensively characterized using rheometer,nuclear magnetic resonance,scanning electron microscope.This cost-effective and straightforward hydrogel synthesis method paves the way for the scalable production of practical and commercially viable Q[n]-based hydrogels.