Physical Cross-linkage Research Articles

Achieving Near-Infrared Phosphorescence Supramolecular Hydrogel Based on Amphiphilic Bromonaphthalimide Pyridinium Hierarchical Assembly.

Phosphorescent supramolecular hydrogels are currently a prevalent topic for their great promise in various photonic applications. Herein, an efficient near-infrared (NIR) phosphorescence supramolecular hydrogel is reported via the hierarchical assembly strategy in aqueous solution, which is fabricated from amphiphilic bromonaphthalimide pyridinium derivative (G), exfoliated Laponite (LP) nanosheets, and polymeric polyacrylamide (PAAm). Initially, G spontaneously self-aggregates into spherical nanoparticles covered with positively charged pyridinium units and emits single fluorescence at 410nm. Driven by electrostatic interactions with negatively charged nanosheets, the nanoparticles subsequently function as the cross-linked binders and coassemble with LP into supramolecular hydrogels with an engendered red room-temperature phosphorescence (RTP) up to 620nm. Benefiting from hydrogen-bonding interactions-mediated physical cross-linkage, the further introduction of PAAm not only significantly elevates the mechanical strength of the hydrogels showing fast self-healing capability, but also increases phosphorescence lifetime from 2.49to 4.20ms, especially generating phosphorescence at even higher temperature (τ 363 K = 2.46ms). Additionally, efficient RTP energy transfer occurs after doping a small amount of organic dye heptamethine cyanine (IR780) as an acceptor into hydrogels, resulting in a long-lived NIR emission at 823nm with a high donor/acceptor ratio, which is successfully applied for cell labeling in the NIR window.

Modification of Physio-Mechanical Properties of Chitosan-Based Films via Physical Treatment Approach

The premise of this work is the modification of the properties of chitosan-based film for possible use in food packaging applications. The biofilm was prepared via thermal and mechanical treatment through blending polymers with chitosan using Polyvinyl Alcohol (PVA) and loading different types of chemical agents, i.e., citric acid (CA), succinic acid (SA), and tetraethoxysilane (TEOS). The modification was carried out under high-speed homogenization at elevated temperature to induce physical cross-linkage of chitosan polymer chains without a catalyst. The findings showed that PVA improved the chitosan films' Tensile strength (TS) and elongation at break (Eb). The presence of chemicals caused an increase in the film strength for all samples prepared, in which a 5% w/w of chemical in the optimum composition CS/PVA (75/25) provided the maximum strength, namely, 33.9 MPa, 44.0 MPa, and 41.9 MPa, for CA-5, SA-5, and TEOS-5, respectively. The chemical agents also increased the water contact angles for all tested films, indicating that they promoted hydrophobicity. The chemical structure analysis showed that, by incorporating three types of chemical agents into the CS/PVA blend films, no additional spectral bands were found, indicating that no covalent bonds were formed. The thermal properties showed enhancement in melting peak and degradation temperature of the blend films, compared to those without chemical agents at the optimum composition. The X-ray diffraction patterns exhibited that PVA led to an increasing crystallization tendency in the blend films. The morphological observation proved that no irregularities were detected in CS/PVA blend films, representing high compatibility with both polymers.

A Polyvinyl Alcohol-Tannic Acid Gel with Exceptional Mechanical Properties and Ultraviolet Resistance.

Design and preparation of gels with excellent mechanical properties has garnered wide interest at present. In this paper, preparation of polyvinyl alcohol (PVA)-tannic acid (TA) gels with exceptional properties is documented. The crystallization zone and hydrogen bonding acted as physical crosslinkages fabricated by a combination of freeze-thaw treatment and a tannic acid compound. The effect of tannic acid on mechanical properties of prepared PVA-TA gels was investigated and analyzed. When the mass fraction of PVA was 20.0 wt% and soaking time was 12 h in tannic acid aqueous solution, tensile strength and the elongation at break of PVA-TA gel reached 5.97 MPa and 1450%, respectively. This PVA-TA gel was far superior to a pure 20.0 wt% PVA hydrogel treated only with the freeze-thaw process, as well as most previously reported PVA-TA gels. The toughness of a PVA-TA gel is about 14 times that of a pure PVA gel. In addition, transparent PVA-TA gels can effectively prevent ultraviolet-light-induced degradation. This study provides a novel strategy and reference for design and preparation of high-performance gels that are promising for practical application.

Organic-inorganic composite polyurethane vitrimers with high toughness, self-healing ability and recyclability

Polyurethanes (PUs) have become a class of promising and popular materials in households and industries due to its versatility in chemistry. The combination of self-healing ability, reprocessability with high strength and great toughness for PUs is highly desired in the practical applications, which remains a challenge as the mechanisms for the above properties are normally conflictive. Herein, we proposed a novel concept of PU vitrimers with superb mechanical properties, improved solvent resistance and excellent recyclability. Specifically, linear PUs with maleimide pendant groups was covalently crosslinked with the dithiol-bearing boronic ester cross-linker through thiol-ene “click” chemistry reaction, forming a self-healable and recyclable PU vitrimer network. Furthermore, 2-ureido-4-[1H]-pyrimidione (UPy) motifs capable of forming quadruple hydrogen bonds as the physical cross-linkages were successfully introduced into the vitrimer network, significantly enhancing the mechanical properties. Finally, 2.5 wt% of SiO2 nanofillers functionalized with UPy motifs (SiO2-UPy) were added into the polymer matrices to further improve the mechanical properties of PU vitrimers. Due to the strong interfacial interactions via H-bonds between SiO2-UPy nanofillers and UPy motifs in the PU chains, the PU vitrimer composites exhibited excellent comprehensive performance, including high strength (∼60 MPa) and great toughness (520 MJ m−3) without sacrificing the elongation at break (∼2500 %), excellent self-healing ability and recyclability. Overall, this study offers a strategy to achieve comprehensive enhancement of mechanical properties as well as self-healing/recycling ability with the incorporation of dynamic covalent and non-covalent bonds, which would forward the broad applications of PUs in various industrial scenarios.

Physical Cross-Linkage Constructed Supramolecular Conductive Hydrogel as Sustainable and Remolded Epidermal Electronics

To balance the comprehensive requirements of toughness, mechanical strength, rapid self-healing, and high conductivity in supramolecular hydrogels toward wearable devices still remain a tough challenge. This paper presents a simple one-step method to construct supramolecular conductive hydrogels (SCHs) through multilevel electrostatic and coordination interactions between amphoteric polymers and metal ions, which are revealed by the density functional theory (DFT) and noncovalent interaction (NCI) analysis. The SCHs integrate stretchability (more than 1500% and 110 kPa), self-healing, remoldability, large strain sensor (0–500%), and long-term monitoring of motion and electrocardiogram (ECG) with decent conductivity (∼2.5 S/m). The self-healing and remolding of SCHs suffer from temperature dependence. Meanwhile, it is worth noting that the remolded SCHs (R-SCHs) retained all of the properties of the original SCHs (O-SCHs), such as conductivity, intelligent sensing, health monitoring, and so on, indicating that the SCHs constructed in physical cross-linking could achieve sustainable recycling in flexible electronics and smart soft materials.

Transparent, High-Strength, and Shape Memory Hydrogels from Thermo-Responsive Amino Acid-Derived Vinyl Polymer Networks.

Herein, the formation of unique shape-memory hydrogels that are composed of thermo-responsive amino-acid-derived vinyl polymer networks is reported; these are readily prepared by radical copolymerization of N-acryloyl glycinamide with commercially available cross-linkers, namely, methylenebis(acrylamide) and poly(ethylene glycol) diacrylate. These hydrogels are transparent (>90% transmittance at 600 nm) and are comprised of 97-70 wt% water. Furthermore, these contain both chemical and physical cross-linkages that are based on the multiple hydrogen bonds attained via amino acid units; this composition is aimed at generating opposing stimuli-responsive characters, namely, chemically stable and thermo-sensitive properties. A cooperative interplay of these two networks enables the hydrogels to exhibit a decent mechanical toughness (breaking strength ≈0.3 MPa and breaking elongation >600%) and a shape fix/memory capability. The temporary shape is easily fixed by cooling at 4 °C after deformation at high temperature, and it instantly recovers its original shape through reheating. Furthermore, a multi-shape memory effect is achieved by incorporating the pH-responsive N-acryloyl alanine unit into the hydrogel system as a comonomer; in this system, three distinct shapes can be fixed through temperature and pH manipulations. This facilely attainable shape memory hydrogel has significant potential in various fields, such as soft actuators, sensors, and biomedical materials.

Strain-induced structural and dynamic changes in segmented polyurethane elastomers

Polyurethane elastomers have been widely used in the industry and daily life due to their versatile physical and chemical properties. Therefore, a fundamental understanding of the structures and dynamics at a molecular level will provide piercing insights into the precise design and application of new polyurethane materials. In this study, we mainly focused on investigating the strain-induced structural and dynamic changes in a typical polyurethane elastomer composed of poly(ε-caprolactone) (PCL) and 4,4′-diphenylmethylene diisocyanate (MDI) as the soft and hard segments, respectively. Obvious strain-hardening phenomenon was observed during the mechanical tensile test, and a systematic comparison was performed on the fractured and pristine samples. DSC results revealed that the crystallization of PCL chains was still going on after the sample was fractured, and the crystallite structures became stable after physical aging at 25 °C for two days. 1H solid-state nuclear magnetic resonance (NMR) experiment was further employed to determine the fraction of mobile PCL chains that were converted to crystallites during stretching. Besides, the microphase separation was also significantly enhanced in the fractured sample. The mobility of amorphous PCL chains was largely reduced due to the strain-induced crystallization of nearby PCL segments, as revealed by the 1H magic-sandwich echo (MSE) NMR experiments. 1H multiple quantum (MQ) NMR experiments also quantitatively revealed the strain-induced orientation of amorphous PCL chains in the fractured sample, indicating that the PCL crystallites were acting as the physical cross-linkages to prevent the contraction of the elongated PCL chains when the sample is fractured.

(Invited) Toward “Infinite Origami” Polymer

This paper describes development of a foldable and shape-memory polymer toward “infinite origami” based on synergy of morphological, sacrificial, and chemical cross-linkages. The basis of the topological cross-linkage is a cyclopolymerization of a bisacrylate monomer forming 19-membered rings. Radical copolymerization of the bisacrylate, acrylonitrile, and 2-ethylexylacrylate in the presence of axis polymers bearing PEG repeating units gave transparent films. The Young’s modulus of a film is as high as 200 MPa, while the film is foldable below Tg. The cyclopolymerization is accompanied by inclusion of the axis polymers forming topological cross-linkages for ductility. The nature of the initial hardness is the dipolar-dipolar interaction of the nitrile groups cross-linking the polymer chains physically and reversibly. The physical cross-linkage may be sacrificially broken to lose energy for fracture, while can be regenerated after heating. Figure 1

Spontaneous stacking of purple membranes during immobilization with physical cross-linked poly(vinyl alcohol) hydrogel with retaining native-like functionality of bacteriorhodopsin

We previously discovered the correlation between light-induced chromophore color change of a photo-receptor membrane protein bacteriorhodopsin (bR) and its two-dimensional crystalline state in the membrane. To apply this phenomenon to a novel optical memory device, it is necessary that bR molecules are immobilized as maintaining their structure and functional properties. In this work, a poly(vinyl alcohol) (PVA) hydrogel with physical cross-linkages (hydrogen bonds between PVA chains) that resulted from repeated freezing-and-thawing (FT) cycles was used as an immobilization medium. To investigate the effects of physically cross-linked PVA gelation on the structure and function of bR in purple membranes (PMs), spectroscopic techniques were employed against PM/PVA immobilized samples prepared with different FT cycle numbers. Visible circular dichroism spectroscopy strongly suggested PM stacking during gelation. X-ray diffraction data also indicated the PM stacking as well as its native-like crystalline lattice even after gelation. Time-resolved absorption spectroscopy showed that bR photocycle behaviors in PM/PVA immobilized samples were almost identical to that in suspension. These results suggested that a physically cross-linked PVA hydrogel is appropriate for immobilizing membrane proteins in terms of maintaining their structure and functionality.

Fabricating ternary hydrogels of P(AM-co-DMAEMA)/PVA/β-CD based on multiple physical crosslinkage

Ternary hydrogels composed of poly[acrylamide-co-2-(dimethylamino)ethyl methacrylate] [P(AM-co-DMAEMA)], poly(vinyl alcohol) (PVA) and β-cyclodextrin (β-CD) were fabricated based on the multiple physical interactions such as inclusion complexation, hydrogen bonding and polymer crystallinity, and exhibited high storage modulus. To illustrate the individual role of each physical interaction, symmetrical investigation has been performed. P(AM-co-DMAEMA)s with two compositions, prepared by radical polymerization at −20 °C below the freezing point of reaction medium of water, were served as the inclusion guest for the inclusion host of β-CD. The inclusion complex between dimethylaminoethyl group of DMAEMA and β-CD was identified through 2D NOESY NMR spectroscopy. Hydrogen bonding between each pairs of hydrogel components was confirmed with FTIR analysis and contributed the second form of crosslinkage. Under freezing polymerization and further freezing-thawing treatment, PVA component tended to crystallize to serve as the third type of physical crosslinkage, which was recognized with X-ray diffraction. Rheological and thermo-gravimetrical analysis was used to inspect the modulus and thermal stability of the hydrogels, respectively. Three hydrogels of P(AM-co-DMAEMA)/PVA-g-β-CD, P(AM-co-DMAEMA)/PVA/β-CD and P(AM-co-DMAEMA)/PVA were synthesized under the same condition to make the comparison. The whole results disclosed the strong dependence of hydrogel properties on the hydrogel components, reflecting the synergistic effects of different physical crosslinkages for the formation of those physical hydrogels.

Well-Defined Polypropylene/Polypropylene-Grafted Silica Nanocomposites: Roles of Number and Molecular Weight of Grafted Chains on Mechanistic Reinforcement.

Grafting terminally functionalized polypropylene (PP) to nanofillers provides well-defined PP-based nanocomposites plausibly featured with a physical cross-linkage structure. In this paper, a series of PP-grafted silica nanoparticles (PP-g-SiO2) were synthesized by varying the number of grafted chains per silica particle, and influences of the number and the molecular weight of grafted chains were studied on physical properties of PP/PP-g-SiO2 nanocomposites. We found that only 20–30 chain/particle was sufficient to exploit benefits of the PP grafting for the nanoparticle dispersion, the nucleation, and the Young’s modulus. Meanwhile, the yield strength was sensitive to both of the number and the molecular weight of grafted PP: Grafting longer chains at a higher density led to greater reinforcement.

Effects of ionic substitution on physical properties, and crystallization rates of, poly(oxyethylene-b-butylene adipate) ionomers

Poly(oxyethylene-b-butylene adipate) ionomers (POBAis) were synthesized and the relationship between the nature of the ionic subsistent and the non-isothermal crystallization behavior and physical properties of the ionomer was evaluated. Non-isothermal crystallization analyses confirmed that additional ionic groups on POBA prevented chain diffusion and slowed the crystallization process. Mechanical analyses demonstrated that ionomers with an additional 2.5mol% of ionic substituents exhibited enhanced mechanical strength, as a result of strong physical cross-linkages between polymer chains. This effect was reversed with an excess of ionic groups, due to preferential intramolecular ion pair associations. It was thus concluded that optimization of the ionic group content could be used to tailor the physical properties and crystallization rates of poly(oxyethylene-b-butylene adipate) ionomers.

Structure development in electrospun fibres of gelatin

Gelatin fibres have been successfully electrospun from water by heating a gelatin solution above the sol-gel transition temperature, and allowing cooling in a controlled environment as the fibres are produced. The development of structure with in these fibres is monitored using wide angle x-ray scattering, in this way the presence of the triple helix structure, which provides the physical cross-linkages in the gel could be probed. There is clear evidence that these structures are obtained in gelatin electrospun from aqueous solutions. In contrast fibres electrospun from a solution of gelatin in glacial acetic acid, showed no evidence of the triple helix structure.

A Novel Polymeric Ionomer as a Potential Biomaterial: Crystallization Behavior, Degradation, and In-Vitro Cellular Interactions

To evaluate the potential of polyester-based ionomers as biomaterials, we have characterized them in terms of crystallization behavior, degradation, and in-vitro cellular interactions. The polymers used are poly(butylene succinate)-based ionomers (PBSis) with 1 to 5 mol-% dimethyl 5-sodium sulfoisophthalate. Even a few incorporated ionic groups significantly decreases the folding surface energy, indicating that folding into crystalline lamellae is more difficult for chains restricted by ionic aggregates. Transmission electron microscopy (TEM) does not reveal any distinct aggregation of ionic clusters following hydrolytic degradation, which suggests that the physical crosslinkage due to ionic interactions is vulnerable to hydrolysis. The in-vitro cellular interactions of polyester-based ionomers is assessed by the culture of human dermal fibroblasts with PBSi extracts or in direct contact with the PBSi films. Cells on PBSi films and in their extracts exhibit appropriate specific growth rates and normal metabolic function regardless of the incorporated ionic content compared with poly[(D,L-lactic acid)-co-(glycolic acid)] (75:25, PLGA), which is well known to be biocompatible. The cells growing on PBSi films spread to a sufficient extent, displaying relatively active filopodial growth, as compared to that of parent PBS. These results suggest that the conspicuous topology and hydrophilic nature of the ionomer surface affect cellular interactions, and that this ionomer therefore has potential applications as a biomaterial.

Polycarbonate-based conductive film prepared by coating DBSA-doped PEDOT/sorbitol

A series of conductive polycarbonate films (CPCFs) were prepared by spin coating with an ethanol-based coating solution comprised of dodecylbenzenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT)/sorbitol. The variation of CPCF surface resistivity was then measured as a function of temperature. CPCF surface resistivity decreased as sorbitol content increased, with the minimum values in the temperature range 175–185 °C. Furthermore, the CPCF-1.6 exhibited significantly improved thermal stability with respect to surface resistivity even at 175 °C. FT-IR analysis indicated that, after thermal treatment, hydrogen bonds arising from the hydroxy groups of sorbitol or hydroxypropyl cellulose and carbonyl groups of polycarbonate were established. The combination of surface resistivity data and FT-IR analysis suggests that the introduction of sorbitol accompanied with thermal treatment allows the PEDOT chains to undergo favorable inter-chain interactions leading to charge transfer and physical cross-linkage via hydrogen bonding.

Block copolymer of trans‐polyisoprene and urethane segment: Crystallization behavior and morphology

AbstractA new type of urethane segmented copolymer was prepared from hydroxyl‐terminated trans‐polyisoprene (HTTPI) and toluene diisocyanate (TDI). The structures of the copolymer were characterized by FTIR and GPC. Crystalline properties of trans‐polyisoprene (TPI) segments were investigated using WAXD and DSC techniques. The crystals of TPI segments are inclined to exist in low‐melting form (LM). The melting temperature of TPI shifts to a lower temperature as the urethane segment was introduced. DMA studies show that, when TPI crystals were at the melting state, the storage modulus of the copolymer depended on the content of urethane segment. The hard segment here serves as physical crosslinkage. Nonisothermal crystallization kinetics of TPI segment was studied on the basis of the Ozawa equation. It was found that the hard segment suppresses the crystallization of the TPI segment. Morphology of two‐phase separation was observed in the copolymer by SEM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2286–2294, 2004

Preparation and properties of transparent cellulose hydrogels

AbstractHighly transparent cellulose hydrogels with physical crosslinkage were prepared from nonaqueous organic cellulose solutions and viscose by coagulating and regenerating cellulose in an aqueous solution containing a water‐miscible organic solvent. Nonaqueous organic cellulose solutions used were LiCl/dimethylacetamide, paraformaldehyde/dimethyl sulfoxide, and triethylammonium chloride/dimethyl sulfoxide. Preparation conditions and physical properties of the transparent cellulose hydrogels were studied. The transparency of the cellulose hydrogels depended on the composition of the aqueous solution containing the organic solvent. Furthermore, transparent cellulose hydrogels from viscose showed high tensile strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3020–3025, 2003

Hydrophobicity of fluoro‐containing physical crosslinkage domains in hydrophobically modified poly(acrylic acid) gels

AbstractA series of hydrophobically modified poly(acrylic acid) gels were prepared by the radical copolymerization of acrylic acid and small amounts of hydrophobic comonomers, 2‐(N‐ethylperfluorooctane‐sulfoamido)ethyl methacrylate and lauryl acrylate, in tert‐butanol. The effects of the fractions and species of hydrophobes on hydrophobic association were determined. The hydrophobic association within the hydrophobically modified gels was proven with measurements of swelling and fluorescence as well as Fourier transform infrared spectroscopy. Fluorocarbon‐modified hydrogels showed stronger hydrophobicity than hydrocarbon‐modified hydrogels. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1236–1244, 2002

Thermoreversible gelation of biodegradable poly(ε-caprolactone) and poly(ethylene glycol) multiblock copolymers in aqueous solutions

The multiblock copolymers composed of poly(ethylene glycol)s (PEGs) and biodegradable poly(ε-caprolactone)s (PCLs) were synthesized through one-step condensation copolymerization with hexamethylene diisocyanate (HDI) as a coupling agent. The typical phase diagram of these multiblock copolymers in aqueous solution displayed a critical gel concentration (CGC) and an upper phase-transition temperature, which were mainly determined by the PEG/PCL block ratio, the PEG or PCL block lengths and the molecular weight. With decreasing PEG/PCL block ratio, the CGC decreased with an elevated sol–gel transition temperature on account of the enhanced hydrophobicity. The HDI/Diols ratio was used to control the molecular weight. At high molecular weights, the CGC decreased, related to the enhanced aggregation of PCL blocks and physical crosslinkage between PCL block domains due to the increased number of PCL blocks in each molecule. For the sample containing the long PCL 2000 block ( M n, 2000), the CGC dropped dramatically due to the high hydrophobicity and the poor compatibility between PCL and PEG. The dynamic phase transition process was observed by combining optical microscopy (OM) and differential scanning calorimetry (DSC) in a certain heating/cooling rate. Finally, a possible phase separation-induced gelation mechanism is suggested.

Structural and rheological properties of methacrylamide modified gelatin hydrogels.

Dynamic shear oscillation measurements at small strain were used to characterize the viscoelastic properties and related differences in the molecular structure of hydrogels based on gelatin methacrylamide. Gelatin was derivatized with methacrylamide side groups and was subsequently cross-linked by radical polymerization via photoinitiation. The light treatment of methacrylamide gelatin solutions resulted in the production of hydrogel films with high storage modulus (G'). Mechanical spectra and thermal scanning rheology of the obtained hydrogels are described. The temperature scan of the network below and above melting point of gelatin allowed us to identify the respective contributions of chemical and physical cross-linkage to the hydrogel elastic modulus. The results indicate that the rheological properties of the gelatin-based hydrogels can be controlled by the degree of substitution, polymer concentration, initiator concentration, and UV irradiation conditions.