Corona Chains Research Articles

Scaling Relationship of Complex Coacervate Core Micelles: Role of Core Block Stretching.

The scaling relationship of complex coacervate core micelles (C3Ms) has been investigated experimentally and theoretically. The C3Ms are formed by mixing two oppositely charged block copolyelectrolyte solutions (i.e., AB + AC system) and are characterized by small-angle neutron (SANS) and X-ray scattering (SAXS). Scaling relationships for micellar structure parameters, including core radius, total radius, corona thickness, and aggregation number, all with respect to the core block length, are determined. A scaling theory is also proposed by minimizing the free energy per chain, leading to four regimes depending on the core and corona chain conformations. Although the corona block is significantly longer than the core block, the structure of our C3Ms is consistent with that of the crew-cut I regime. A highly swollen core by water enables the core blocks to be stretched significantly and corona chains to be minimally overlapped.

Block Copolymer-Templated Au@CdSe Core-Satellite Nanostructures with Solvent-Dependent Optical Properties

In the present work, we report the fabrication and characterization of well-defined core-satellite nanostructures. These nanostructures comprise block copolymer (BCP) micelles, containing a single gold nanoparticle (AuNP) in the core and multiple photoluminescent cadmium selenide (CdSe) quantum dots (QDs) attached to the micelle's coronal chains. The asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP was employed to develop these core-satellite nanostructures in a series of P4VP-selective alcoholic solvents. The BCP micelles were first prepared in 1-propanol and subsequently mixed with AuNPs, followed by gradual addition of CdSe QDs. This method resulted in the development of spherical micelles that contained a PS/Au core and a P4VP/CdSe shell. These core-satellite nanostructures, developed in different alcoholic solvents, were further employed for the time-resolved photoluminescence analysis. It was found that solvent-selective swelling of the core-satellite nanostructures tunes the distance between the QDs and AuNPs and modulates their Förster resonance energy transfer (FRET) behavior. The average lifetime of the donor emission varied from 12.3 to 10.3 nanoseconds (ns) with the change in the P4VP-selective solvent within the core-satellite nanostructures. Furthermore, the distances between the donor and acceptor were also calculated using efficiency measurements and corresponding Förster distances. The resulting core-satellite nanostructures hold promising potential in various fields, such as photonics, optoelectronics, and sensors that utilize the FRET process.

Supramolecular Networks Obtained by Block Copolymer Self-Assembly in a Polymer Matrix: Crystallization Behavior and Its Effect on the Mechanical Response

In recent years, there has been growing interest in the study of supramolecular networks obtained by self-assembly of amphiphilic molecules due to their responsive behavior to different external stimuli. The possibility of embedding supramolecular networks into polymer matrices opens access to a new generation of functional polymers with great potential for various applications. However, very little is known about how the dynamics of the supramolecular network is affected by diffusional and topological limitations imposed by the polymer matrix. In this work, we investigate the behavior of supramolecular networks embedded into a rubbery polymer. Crystallization-driven self-assembly of a poly(ethylene-block-ethylene oxide) (PE-b-PEO) diblock copolymer was used to generate supramolecular networks in dimethacrylate monomers, which were then photopolymerized at room temperature. PE-b-PEO self-assembles into nanoribbons with a semicrystalline PE core bordered by coronal chains of PEO, and the nanoribbons, in turn, bundle into lamellar aggregates with an average stacking period of around 45 nm. The nanoribbons are interconnected through crystalline nodes in a 3D network structure. Small-angle X-ray scattering experiments show that the polymer matrix preserves the structure of the supramolecular network and avoids its disintegration when the material is heated above the melting temperature of PE cores. Successive self-nucleation and annealing studies reveal that the polymer matrix does not influence the crystallization–melting processes of PE, which take place through the interconnected cores of the supramolecular network. In contrast, the matrix imposes strong effects of topological confinement on the crystallization of PEO, limiting the dimensions of the crystalline lamellae that can be formed. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network. This behavior was also characterized by shape memory cyclic tests.

Effects of ionic strength and ion-specificity on the interface behavior of PDMAEMA-b-PLMA-b-POEGMA triblock terpolymer

Ion-specificity on the stretching degree of diblock copolymers containing poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) at the air/water interface has previously been proved to be inconsistent with the Hofmeister series. In this work, the aggregation behavior of an amphiphilic linear triblock terpolymer poly[2-(dimethylamino)ethyl methacrylate]-block-poly(lauryl methacrylate)-block-poly[oligo(ethylene glycol) methacrylate] (PDMAEMA-b-PLMA-b-POEGMA) on the aqueous subphase with different ionic strengths and ion species (salts) was studied, and the morphologies of its Langmuir−Blodgett (LB) films were explored. At the air/water interface, the terpolymer tends to form surface micelles composed of hydrophobic PLMA cores and mixed hydrophilic coronas of PDMAEMA and POEGMA. Under acidic conditions with low ionic strength, the hydrophilic PDMAEMA blocks of the terpolymer are almost completely electrostatic screened. With the increase of subphase ionic strength, the surface pressure−molecular area isotherms of the terpolymer monolayers at the air/water interface gradually move to large areas due to the increased interfacial stretching degree of POEGMA blocks resulting from the increased salting-out effect and interfacial steric hindrance of PDMAEMA blocks. The hysteresis degrees of the terpolymer monolayers in the presence of salts in the subphase are larger than that in the absence of salt. Under alkaline conditions, the isotherms of the terpolymer monolayers move to large areas with the increase of salt concentration because the introduction of salt makes the hydrophilic blocks more stretched. The experimental results show that the relationship between their interfacial stretching degrees of two kinds of hydrophilic blocks and the types of salt in solution is inconsistent with the Hofmeister series. This may be due to tethering of the corona chains on the hydrophobic core and the configurational constrains (crowding phenomena) induced within the mixed micelle corona. Under different subphase conditions, the LB films of the terpolymer show isolated circular micelles due to the mutual repulsions of the long hydrophilic PDMAEMA and POEGMA blocks.

Role of Competitive Crystallization Kinetics in the Formation of 2D Platelets with Distinct Coronal Surface Patterns via Seeded Growth.

Low dispersity 2D platelet micelles with controllable surface patterns were prepared by seeded-growth/living crystallization-driven self-assembly (CDSA) of block copolymer/homopolymer (BCP/HP) blends of poly(ferrocenyldimethylsilane)-b-poly(2-vinyl pyridine) (PFS-b-P2VP) and PFS. The precise morphology was found to be dependent on the proportion of the P2VP corona block, which can be efficiently controlled by changing the molar concentration ratio of PFS-b-P2VP/PFS, (cB/cH)t, as well as their relative rates of crystallization, (GB/GH)t. In the case where their molar concentration ratio was comparable to their crystallization rate ratio, platelets with a uniform distribution of P2VP coronal chains were formed. In other cases, as the concentration ratio increased (or decreased) during the living CDSA process, hierarchical structures were formed, including chain-like assemblies consisting of end-to-end linked rectangular platelets and fusiform (tapered) micelles. (GB/GH)t was adjusted by tuning the degree of polymerization of the crystallizable PFS core-forming block and the BCP block ratio and by varying the terminus of the HP or changing the solvent used. Furthermore, the open edge of the platelets remained active for further growth, which permitted control of the morphology and dimensions of the platelets. Interestingly, in cases where the molar concentration ratio was lower than the crystallization rate ratio, growth rings were observed after two or more living CDSA steps. This study on the formation of platelet micelles by living CDSA of BCP/HP blends under kinetic control offers a considerable scope for the design of 2D polymer nanomaterials with controlled shape and surface patterns.

AIE-Active, Stimuli-Responsive Fluorescent 2D Block Copolymer Nanoplatelets Based on Corona Chain Compression.

Aggregation-induced emission (AIE) represents a powerful tool in nanoscience as a result of enhanced luminescence in the condensed state. Although AIEgenic materials have been utilized in a wide range of applications, well-defined self-assembled nanoparticles with tailorable and uniform dimensions and morphology remain challenging to access. Herein, we use the seeded growth, living crystallization-driven self-assembly (CDSA) method to prepare size-tunable and uniform AIE-active 2D nanoplatelets from amphiphilic block copolymer (BCP) precursors with a crystallizable core-forming block and a corona-forming block to which tetraphenylethene (TPE) groups were covalently grafted as AIE-active pendants. The nanoplatelets were formed as a result of a solvophobicity-induced 1D to 2D morphology preference change, which accompanied the seeded growth of a BCP with a quaternized corona-forming block bearing the TPE luminogen. The 2D nanoplatelets exhibited a solvent-responsive fluorescent emission, and examples with coronas containing homogeneously distributed AIE-active TPE groups and Hg(II)-capturing thymine units exhibited excellent performance as proof-of-concept "turn-on" sensors for Hg(II) detection with a rapid response, high selectivity, and a low detection limit (5-125 × 10-9 M, i.e., 1-25 ppb). The fluorescence intensity was found to be nonlinear with respect to analyte concentration and to increase with the area of the nanoplatelet. This behavior is consistent with a cooperative mechanism based on changes in the steric compression of the corona chains, which gives rise to a restriction of the intramolecular motion (RIM) effect.

Photo-healable ion gel with high mechanical property, fatigue resistance and shear resistance using a coumarin group containing diblock copolymer in an ionic liquid

Ion gels, polymer networks swollen with ionic liquid (IL), are ideal materials for application in flexible electronic devices. It remains a challenge to fabricate an ion gel with photo-healing, high mechanical properties, fatigue resistance and shear resistance. Herein, a well-defined diblock copolymer polystyrene-b-poly(methyl acrylate-r-7-(2′-methacryloyloyloxyethoxy)-4-methylcoumarin) (PS-b-P(DMA-r-MAOEMC), brief name: SMM, PS: IL-phobic segment and P(DMA-r-MAOEMC): IL-philic segment) was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. For comparison, a random copolymer P(DMA-r-MAOEMC) (MM) also be prepared. In dilute solution, the SMM can form spherical micelles with PS-core surrounded by P(DMA-r-MAOEMC) corona chains in an IL, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfone)amide ([C2mim][NTf2]). In a suitable polymer concentration, the SMM and MM can form ion gels in [C2mim][NTf2] under 365 nm UV light irradiation through photo-dimerization of coumarin groups in corona MM polymer chains of spherical micelles and photo-dimerization of coumarin groups in MM random polymer chains, respectively. Compared with the MM ion gel, the SMM ion gel has high mechanical properties, shear resistance and relatively high fatigue resistance. Under 254 nm UV light irradiation, photo-induced gel to jammed micelles transition for the SMM ion gel and photo-induced gel to sol transition for the MM ion gel occur due to photo-cleavage of dimer in polymer chains. Photo-induced jammed micelles - gel transition for the SMM ion gel and photo-induced sol - gel transition for the MM ion gel are reversible by alternating 365 nm and 254 nm UV light irradiation, whereby photo-healable materials can be fabricated. Compared to the MM ion gel, the SMM ion gel has high photo-healing efficiency. The electrochemical property of the SMM ion gel can be recovered completely after photo-healing.

Block copolymer self-assembly: Polydisperse corona-forming blocks leading to uniform morphologies

<h2>Summary</h2> Bottom-up block copolymer (BCP) self-assembly involving crystallization of the core-forming block can lead, via a multistep protocol, to a range of uniform structures. One normally works with polymers of narrow molecular weight distribution, at low concentrations, and several steps are necessary because one has to separate the nucleation and growth steps. Here, we show that BCPs with polydisperse corona chains enable one to obtain a broad range of uniform structures in a single pot via a single heating-cooling-aging process, in which the nature of the structures is determined by the solvents and the annealing temperature. Most of the sample dissolves upon heating, but a fraction of the components in the mixture with the smallest corona/core block ratio persists as crystallites and, upon cooling, nucleates the growth of the more soluble components. Remarkably, this one-pot self-assembly can be scaled up to a concentration of 12% w/w, opening the door to useful applications.

Dendritic Micelles with Controlled Branching and Sensor Applications.

Although micelles derived from the solution self-assembly of amphiphilic molecules and polymers have been prepared with a wide variety of shapes, examples with well-defined branched structures have remained elusive. We describe a divergent, directed self-assembly approach to low dispersity dendritic micelles with a high degree of structural perfection and tailorable branch numbers and generations. We use block copolymer amphiphiles as precursors and a crystallization-driven seeded growth approach whereby the termini of fiber-like micelles function as branching sites. Different dendrimeric generations are accessible by adjusting the ratio of added unimers to pre-existing seed micelles where the branch positions are determined by the reduced coronal chain grafting density on the surface of the micelle crystalline core. We demonstrate the spatially defined decoration of the assemblies with emissive nanoparticles and utility of the resulting hybrids as fluorescent sensors for anions where the dendritic architecture enables ultrahigh sensitivity.

Probing Thermoresponsive Polymerization-Induced Self-Assembly with Variable-Temperature Liquid-Cell Transmission Electron Microscopy

Summary We directly initiate and visualize the formation of polymeric nanomaterials via variable-temperature liquid-cell transmission electron microscopy (VT-LCTEM). With temperature control in the liquid cell, reversible addition-fragmentation chain transfer polymerization was thermally initiated, leading to the formation of amphiphilic block copolymers that assemble upon dispersion polymerization-induced self-assembly (PISA). In combination with traditional ex situ analyses, VT-LCTEM enabled not only the characterization of the nanoparticles in situ but also the observation of a thermal phase transition. Critically, because these assemblies form from thermoresponsive components, any temperature changes during sample preparation and analysis can alter morphologies, necessitating direct in situ characterization of reaction progression. We believe that the findings and the technique described herein will lead to unprecedented possibilities for the development and characterization of self-organizing soft matter.

Understanding the Dissolution and Regrowth of Core-Crystalline Block Copolymer Micelles: A Scaling Approach

Living crystallization-driven self-assembly in solution has proven to be an excellent method to prepare core-crystalline micelles with an exquisite control over their size and morphology. While numerous studies have been performed to test their assembly in various media for potential applications, their stability under different stimuli remains yet to be established. In the present study, we performed light scattering and transmission electron microscopy experiments to investigate the effect of concentration on the self-seeding of core-crystalline one-dimensional (1D) seed crystallites with a long corona forming block. As previously reported, the seed crystallites dissolve much easier at low concentrations than at relatively high concentrations. We also observe that for all concentrations, the micelle width broadens during annealing. To explain these results, we developed a model based on a scaling approach. We show that the growth of ribbon-like core-crystalline micelles depends on the distance between the corona chains grafted on the micelle core, the thickness of the core, and, more surprisingly, on the number of chains constituting the core. This scaling approach also allowed us to explain how the interactions between the corona-forming block and the solvent influence the behavior of the seed crystallites at different annealing temperatures and concentrations. This model should thus prove very useful to understand and predict the effect of different media and stimuli on the size, morphology, and stability of core-crystalline micelles.

Liquid crystal block copolymer micelles with aggregation-induced emission from corona chains

Aggregation-induced emission (AIE) is a very useful tool to study the self-assembly process of block copolymers. However, most of the studies have been focused on the AIE process of the micelle core block. In this study, a typical AIEgen tetraphenylethylene (TPE) was introduced into the corona-forming block of the liquid crystal diblock copolymer. Although the coronal chains were still soluble in solution and the TPE group content was very low, due to the highly crowded and stretched chains, there was significant fluorescence emission after micellization. This provides a new research direction for the AIE process of diblock polymers and is of great significance for the study of the star micelle models.

PH-Controlled Hierarchical Assembly/Disassembly of Multicompartment Micelles in Water.

Multicompartment micelles (MCMs) have become attractive drug delivery systems as they allow the separate storage of two or more incompatible cargos in their core compartments (e.g., drugs and dyes for imaging). A recent hierarchical self-assembly process for hydrophobic terpolymers in organic solvents showed the ability to form very homogeneous MCM populations, yet the transfer of this process into water requires a better understanding of the formation mechanism and influence of chain mobility during assembly. Here, the synthesis of a linear poly(oligo(ethylene glycol) methacrylate)-block-poly(benzyl acrylate)-block-poly(4-vinylpyridine) (POEGMA-b-PBzA-b-P4VP) triblock terpolymer by reversible addition-fragmentation chain transfer (RAFT) polymerization is reported as well as its step-wise assembly into MCMs in water with POEGMA corona, PBzA patches, and P4VP core. Reversible assembly/disassembly of the MCMs is investigated through protonation/deprotonation of the P4VP core. Interestingly, the low glass transition temperature (Tg ) of the hydrophobic PBzA middle block causes MCMs to directly disassemble into molecularly dissolved chains instead of patchy micelles due to mechanical stress from electrosteric repulsion of the protonated P4VP corona chains. In addition, pH resistant MCMs are created by core-crosslinking and fluorescent properties are added by covalent anchoring of fluorescent dyes via straightforward click chemistry.

Scattering Form Factor of Block Copolymer Micelles with Corona Chains Discretely Distributed on the Core Surface.

Small-angle scattering is a powerful tool to investigate micellar structure, and a model form factor proposed by Pedersen and Gerstenberg [Pedersen, J. S.; Gerstenberg, M. Macromolecules 1996, 29, 1363-1365] has been used quite frequently to analyze experimentally obtained scattering data of block copolymer micelles. Their model consists of a spherical core and the Gaussian corona chains attached to the core surface; the corona chains are considered to be approximately continuously (evenly) distributed on the core surface. In this paper, we present a micellar form factor model in which the corona chains are discretely distributed on the core surface. Our proposed discrete model was found to deviate from the Pedersen-Gerstenberg model as well as another model [Svaneborg, C.; Pedersen, J. S. Phys. Rev. E 2001, 64, R01802.], which incorporates the approximate interference effect between the corona chains, in conditions in which the scattering from the corona chains is stronger than that from a core with lower number density of the corona chains.

Controlled Synthesis of Gold Nanoparticles in Copolymers Nanomolds by X-ray Radiolysis.

We show by X-ray and neutron small-angle scattering that gold nanoparticles with controlled sizes and morphologies can be obtained by the metallic reduction of AuCl4- ions trapped in 3D organic molds by X-ray radiolysis. The molds are spherical frozen micelles of polystyrene-b-poly(dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) block copolymer in acidic aqueous solution with a PS spherical core surrounded by a corona of PDMAEMA chains in good solvent. The behavior of micelles is controlled by the [AuCl4-]/[DMAEMA] ratio RAuCl4-/DMAEMA. At low gold concentration, AuCl4- ions condense on the positively charged DMAEMA moieties without changing the behavior of the PDMAEMA chains. At intermediate gold concentration, the ions induce a progressive contraction of the corona's chains and dehydration of micelles. At large gold concentration, the corona becomes a fully dry phase loaded with gold ions, which induces micelle aggregation. Radiolysis of the solution by an intense X-ray beam produces different types of gold nanoparticles with respect to RAuCl4-/DMAEMA and irradiation time. At RAuCl4-/DMAEMA = 0.033, irradiation produces in the first step gold clusters in the micelle corona which in the second step merge to form nanoparticles of a similar size to that of the micelle. Conversely, at RAuCl4-/DMAEMA = 0.33, micelles do not operate as templates but only as nucleation zones and large nanoparticles grow outside the micelles.

A rheo-optical study on the linear viscoelasticity and molecular dynamics of block copolymer solutions forming hexagonal close-packed cylindrical domains

The linear viscoelastic properties of block copolymer solutions forming hexagonal close-packed cylindrical domains and their relaxation dynamics were investigated by using a rheo-optical method based on simultaneous measurements of stress and strain-induced birefringence. The sample solution is composed of a PS-b-PI diblock copolymer and a mixed solvent of DOP and SALACOS 913, which are a neutral solvent for both PS and PI and a highly selective solvent for PI, respectively. The copolymer concentration was fixed, and the DOP fraction of the mixed solvent was increased to change the domain structure from a hexagonal close-packed cylindrical structure to a spherical structure. The sign of the complex strain-optical coefficient, which is the complex ratio of the oscillatory strain-induced birefringence to the strain, varied with frequency, indicating that the viscoelastic relaxation spectra include multiple relaxation modes. Four relaxation modes were successfully estimated with the aid of the modified stress-optical rule. The four modes were assigned to (1) reorientation of corona chains, (2) reorientation of core chains, (3) deformation of domains, and (4) reorientation of grains. The intrinsic birefringence of the cylindrical structure was found to be 1.7 × 10−5. By assuming entropic stress of grain reorientation, the grain size was estimated to be ~0.2 μm from the viscoelastic intensity. The linear viscoelastic properties of block copolymer solutions forming hexagonal close-packed cylindrical domains were investigated by using a rheo-optical method. Based on the modified stress-optical rule, the complex shear modulus was separated to four relaxation modes. Considering the sign and magnitude of the stress-optical coefficient associated with each mode, the four modes were assigned to (1) reorientation of corona chains, (2) reorientation of core chains, (3) deformation of domains, and (4) reorientation of grains. The results were compared with those for spherical domains.

Aggregation-induced emission from the crowded coronal chains of block copolymer micelles

Aggregation-induced emission (AIE) was triggered via the spatial confinement in the coronal chains in block copolymers upon micellization, even with very low content of AIE groups attached, and this could be used to monitor the self-assembly process.

Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles.

The application of dilute solutions of polyelectrolyte complex (PEC) micelles for delivering therapeutic nucleic acids into disease sites has gained momentum. This Letter reports a detailed characterization of PEC micelles in dilute solutions including their internal structures and the determination of the interparticle interactions. The polymer concentration ranges from 0.1 to 0.5 wt %, a regime where micelle-micelle interactions are infrequent. We employ synchrotron small-angle X-ray scattering (SAXS) to simultaneously probe the morphology, internal structure, and radius of gyration (Rg) of the self-assemblies formed by charged diblock polyelectrolytes and homopolyelectrolytes. The emerging appearance of the structure factor in SAXS profiles with the increasing polymer concentration demonstrates the presence of the repulsive intermicellar correlations, which is further confirmed by the differences between the "reciprocal Rg" estimated by Guinier approximation and the "real space Rg" determined by pair distribution functions. We find that the soft corona chains tethered on the surface of phase-separated complex domains are compressed when micelles come closeto thepointwhere a hard-sphere interaction takes over. These findings contribute to the fundamental understanding of the structure and space-filling constraints in the complexation-driven self-assemblies and advance the rational design of cationic polymer-based nonviral gene delivery vectors.

Visualizing Nanoscale Coronal Segregation in Rod-Like Micelles Formed by Co-Assembly of Binary Block Copolymer Blends.

Mixed micelles formed by co-assembly of pairs of block copolymers (BCPs) can develop novel morphologies and generate useful properties not accessible from homomicelles. For micelles consisting of two different polymers in the corona, identifying the location of the corona chains is a critical part of morphology characterization. Coronal segregation in mixed micelle is often characterized by transmission electron microscopy in combination with selective staining of individual polymers. In this study, Karstedt's catalyst is used for selective Pt(0)-olefin coordination staining of polyisoprene (PI) and poly(methylvinylsiloxane) (PMVS) corona chains in the presence of poly(dimethylsiloxane) (PDMS) corona chains in cylindrical mixed micelles with a crystalline poly(ferrocenyldimethylsilane) (PFS) core. Previous experiments using OsO4 as a stain did not enable visualization of nanoscale coronal segregation in mixed micelles obtained from co-assembly of PFS-b-PI and PFS-b-PDMS, as well as PFS-b-PMVS and PFS-b-PDMS.

Self-Healing Micellar Ion Gels Based on Multiple Hydrogen Bonding.

Ion gels, composed of macromolecular networks filled by ionic liquids (ILs), are promising candidate soft solid electrolytes for use in wearable/flexible electronic devices. In this context, the introduction of a self-healing function would significantly improve the long-term durability of ion gels subject to mechanical loading. Nevertheless, compared to hydrogels and organogels, the self-healing of ion gels has barely investigated been because of there being insufficient understanding of the interactions between polymers and ILs. Herein, a new class of supramolecular micellar ion gel composed of a diblock copolymer and a hydrophobic IL, which exhibits self-healing at room temperature, is presented. The diblock copolymer has an IL-phobic block and a hydrogen-bonding block with hydrogen-bond-accepting and donating units. By combining the IL and the diblock copolymer, micellar ion gels are prepared in which the IL phobic blocks form a jammed micelle core, whereas coronal chains interact with each other via multiple hydrogen bonds. These hydrogen bonds between the coronal chains in the IL endow the ion gel with a high level of mechanical strength as well as rapid self-healing at room temperature without the need for any external stimuli such as light or elevated temperatures.