Photo‐reversible polyurethane (PU) coatings based on coumarin diol (CD) are obtained. Initially, pre‐polymers based on different amounts of coumarin (5, 15, and 25 mol%) and 1,6‐hexamethylene diisocyanate are prepared to obtain PUs with a large incorporation of CD and high molecular weight. The pre‐polymer is posterior reacted with poly(ε‐caprolactone) diol (PCL‐diol), either with molecular weight = 530 or 2000 g mol–1. The thermal stabilities of the PUs are studied using thermogravimetric analysis. Polymers with a higher content of CD present higher stability. The thermal transitions and the mechanical response are analyzed using differential scanning calorimetry and strain‐stress tests, respectively. Moreover, the photo‐reversibility of CD‐based PUs is followed by UV absorption. In general, photo‐dimerization induces better mechanical properties of the final PUs. Materials obtained with short PCL‐diol ( = 530 g mol–1) and the highest amount of CD present higher reversibility processes. Therefore, these polymers are promising for application as coating systems.
Supramolecular nanofibers have a great potential to be used as gelating agents, polymer additives, and fibrous material for filtration purposes. To meet the requirements for practical and industrial applications on a large scale, e.g., production of filter media, it is desirable to develop supramolecular systems processable from environmentally friendly water‐based solvent mixtures. Moreover, assessing processing parameters to control the micro‐ and nanofiber diameter is of vital importance. Therefore, an alkoxy‐substituted 1,3,5‐benzenetrisamide, N,N′,N″‐tris(1‐(methoxymethyl)propyl)benzene‐1,3,5‐tricarboxamide is designed that can be self‐assembled into supramolecular nanofibers upon cooling from a water/isopropanol solvent mixture. It is demonstrated that parameters such as stirring velocity and the temperature range during processing allow for a precise adjustment of the cooling profile which in turn enables the control of the supramolecular nanofiber diameters.
Development of artificial soft materials that have good mechanical performances and autonomous healing ability is a longstanding pursuit but remains challenging. This work reports a kind of highly flexible, tough, and self‐healable poly(acrylic acid)/Fe(III) (PAA/Fe(III)) hydrogels. The hydrogels are dually cross‐linked by triblock copolymer micelles and ionic interaction between Fe(III) and carboxyl groups. Due to the coexistence of these two cross‐linking points, the resulting PAA/Fe(III) hydrogels are tough and can be flexibly stretched, bent, knotted, and twisted. The hydrogels can withstand a deformation of 600% and an ultimate stress as high as 250 kPa. Moreover, the dynamic ionic interaction also endows the hydrogels self‐healing properties. By varying the ratio of Fe(III)/AA, a compromised healing efficiency of 73% and an ultimate stress of 200 kPa are obtained.
Poly(ethylene glycol) diacrylate (PEG‐DA) hydrogels have been widely utilized to investigate cell–material interactions and as scaffolds for tissue engineering. Traditionally, PEG‐DA hydrogels are prepared via the UV‐cure of aqueous precursor solutions, but afford a limited range of pore size and interconnectivity that is essential for cellular proliferation and neotissue formation. To overcome these limitations, macroporous PEG‐DA hydrogels are prepared in this study using a combination of solvent‐induced phase separation (SIPS) and a fused salt template. PEG‐DA concentration in the organized fabrication solvent (20, 30, and 40 wt%) and average salt particle size (≈180, ≈270, and ≈460 μm) are varied and the resulting hydrated hydrogel morphology, swelling, mechanical properties, and degradation are characterized. These templated SIPS PEG‐DA hydrogels broaden PEG‐DA hydrogel properties and, in some cases, afford a series of compositions whose properties are decoupled.
A series of drawn melt‐crystallized linear polyethylenes (LPEs) with different molecular weight distributions (MWD = M w/M n) ranging from 2 to 25 are investigated with respect to the visible‐light transparency. The results indicate that the MWD of the LPEs significantly influences the visible‐light transparency of drawn melt‐crystallized LPEs. At a high MWD, drawn melt‐crystallized LPEs films are transparent and glass‐like, this in contrast to the LPEs with a low MWD. A mechanism behind the observed results is proposed based on differential scanning calorimetry (DSC) analysis, small‐angle X‐ray scattering, wide‐angle X‐ray scattering, and small‐angle light scattering experiments. A correlation between the molecular characteristics, especially the MWD, and the visible‐light transparency of the drawn melt‐crystallized LPEs is proposed.
A series of hybrid hydrogels based on poly(vinyl alcohol) (PVA)/agar/poly(ethylene glycol) (PEG) prepared by a solution casting method using e‐beam irradiation are investigated to determine the effect of agar and PEG content (1, 2, and 4 wt%) on their physicomechanical and rheological properties. The gel content of the hydrogels decreases with increasing agar and PEG contents. The equilibrium swelling of PVA hydrogel decreases on blending with agar while adding PEG to PVA/agar increases the swelling by about 400%. No obvious change in the dehydration behavior of the hybrid hydrogels is observed on changing agar and PEG contents. The solid‐like rheological behavior of the hydrogels is not significantly affected by agar content, while it approaches a liquid‐like behavior at high PEG loading. The tensile strength of the hybrid hydrogels is improved by increasing agar content, while its elongation‐at‐break is decreased. On the other hand, the opposite results are found regarding the influence of PEG and its content on the mechanical properties of the hybrid hydrogels.
For major advances in microfabricated drug delivery systems (DDS), fabrication methods with high throughput using biocompatible polymers are required. Once these DDS are fabricated, loading of drug poses a significant challenge. Here, hot punching is presented as an innovative method for drug loading in microfabricated DDS. The microfabricated DDS are microcontainers fabricated in photoresist SU‐8 and biopolymer poly‐l ‐lactic‐acid (PLLA). Furosemide (F) drug is embedded in poly‐ε‐caprolactone (PCL) polymer matrix. This F‐PCL drug polymer matrix is loaded in SU‐8 and PLLA microcontainers using hot punching with >99% yield. Thus, it is illustrated that hot punching allows high‐throughput, parallel loading of 3D polymer microcontainers with drug‐polymer matrices in a single process step.
In this work, the authors report an effective one‐pot method to prepare poly(ε‐caprolactone) (PCL)‐incorporated bovine serum albumin (BSA)/calcium alginate/hydroxyapatite (HAp) nanocomposite (NC) scaffolds by templating oil‐in‐water high internal phase emulsion (HIPE), which includes alginate, BSA, and HAp in water phase and PCL in oil phase. The water phase of HIPEs is solidified to form hydrogels containing emulsion droplets via gelation of alginate induced by Ca2+ ions released from HAp. And the prepared hydrogels are freeze‐dried to obtain PCL‐incorporated porous scaffolds. The obtained scaffolds possess interconnected pore structures. Increasing PCL concentration clearly enhances the compressive property and BSA stability, decreases the swelling ratio of scaffolds, which assists in improving the scaffold stability. The anti‐inflammatory drug ibuprofen can be highly efficiently loaded into scaffolds and released in a sustained rate. Furthermore, mouse bone mesenchymal stem cells can successfully proliferate on the scaffolds, proving the biocompatibility of scaffolds. All results show that the PCL‐incorporated NC scaffolds possess promising potentials in tissue engineering application.
Hydrogels, as soft and wet materials, have attracted great attention in the field of functional biomaterials. Most recently, the designed hydrogels, according to the energy dissipation principle, overcome the low mechanical strength, poor toughness, and limited recoverability of common hydrogels and show excellent mechanical properties. However, most of these novel designed hydrogels are lacking of instantaneous recovery and antifatigue properties. In this study, a mesoscopic inhomogeneous hydrogel consisting of carboxymethyl cellulose and polyacrylic acid is synthesized through a facile, one‐pot, visible‐light‐triggered polymerization. The prepared hydrogel can be stretched over 700% with fracture strength as high as 850 kPa, and shows a high elastic modulus (180 kPa). The microgel aggregated structure endows an efficient energy dissipation mechanism to the hydrogel. After the internal network structure stabilizing, the hydrogel exhibits a recovery time within 10 ms and over 92% resilience during impact and cyclic tensile tests, respectively. The hydrogel with such excellent mechanical properties can extend its application in biomaterial fields.
How to reasonably fabricate polymer network for high performance hydrogels is a critical issue but remains a challenge. This work reports an approach to high performance hydrogels by molecularly engineering fully flexible crosslinking (ffC) network. A model network cross‐linked by fully flexible crosslinking points of triblock copolymer micelles and ionic interactions is fabricated. Due to the unique structure, the resulting ffC hydrogels are mechanically robust, tough, and self‐recoverable. For as‐prepared ffC hydrogels, a tensile stress more than 3.5 MPa can be achieved and the energy dissipation can reach up to 6.61 MJ m−3 at the tensile strain of 125%. Moreover, ffC hydrogels fabricated under constant strain can achieve an energy dissipation ability up to 11.63 MJ m−3 at the tensile strain of 100% and a tensile stress of 17.57 MPa. Based on these results, a dynamic molecular mechanism in the ffC hydrogel network under tensile deformation is proposed. The high performances of the ffC hydrogels can be possibly attributed to the sequential breakage and energy dissipation of the flexible crosslinking points and the easily accessible polymer chain orientation during tensile deformation.
The ability to fabricate high‐quality colloidal photonic crystal (CPC) films in large areas is critical in many applications, ranging from flexible displays, security devices to optical enhancement. Herein, a large‐scaled CPC film with crack‐free structure and uniform optical performance is prepared via a hydrogen‐bond‐assisted method. The crack‐free CPC film is ascribed to the intermolecular hydrogen bonds between carboxyl ( COOH) moieties of poly(styrene‐methyl methacrylate acrylic acid) microspheres and isocyanate ( NCO ) moieties of polyurethane. Furthermore, the as‐prepared CPC film is applied as a Bragg reflection mirror for fluorescence enhancement. It is demonstrated that a fourfold enhancement of fluorescence signal is achieved when the stopband of CPCs overlaps with the emission wavelength of quantum dots. This simple method of preparing large‐area and crack‐free CPC film is promising for developing efficient optical devices.
Polymer‐based electrospun fibers have been intensively studied as antimicrobial membranes, drug carriers, and energetic materials. Inorganic fillers or small molecules have been routinely added into polymer matrices in order to enhance product functions. However, the electrospinning process is kinetically controlled and solvent rapidly evaporates due to the large surface‐to‐volume ratio of spinning liquid jet. When electrospinning a multicomponent system, complex phase behavior may occur and give rise to interesting internal structures of resulting products. Such kinetically driven phenomena deserve more attention for optimizing product performance. Here, electrospun poly(ε‐caprolactone)(PCL)/aminopropyl‐heptaisobutyl‐polyhedral oligomeric silsesquioxane (AMPOSS) fibers with AMPOSS content up to 30 wt% are studied as a model system to understand the impact of kinetically controlled phase separation on the fibers' internal structure, properties, and thermal stability. With sufficient AMPOSS loading, the hybrid fibers are found to have an AMPOSS‐shell/PCL‐core structure. The thermal stability of the as‐spun PCL/AMPOSS fibers is therefore greatly enhanced.
Bioprinting is a breakthrough technology that integrates living cells, biomaterials, and a robotic dispensing system to create complex structures that mimic original tissues and organs. One of the main components of bioprinting is bioink and hydrogel is essential in bioink formulation. In bioprinting, hydrogel should have good biocompatibility, provide good resolution, and have sufficient mechanical strength to support printed structures. Recently, thermoresponsive hydrogels have gained more and more attention due to their unique characteristic of tunable sol‐gel (liquid to solid phase) transition when temperature is changed, and many biomedical applications from drug delivery devices to tissue scaffolds have demonstrated the potentials of bioprinted thermosresponsive constructs. In this review, we discuss bioprintable thermoresponsive hydrogels with a particular focus on their gelation mechanisms, fabrication strategies using bioprinter and applications. The future prospects of the bioprinting‐based use of thermoresponsive hydrogels for next generation tissue engineering have also been discussed.
The direct injection of a drug into a joint can relieve osteoarthritic pain for a short period of time. The problem is that the drug will not stay at the allocated location. Therefore, a proof‐of‐concept in situ is designed forming hydrogel containing liposomes that are covalently linked to the hydrogel network. When the liposomes are filled with a cargo, the formed hydrogel is thus loaded with this cargo, too. Due to the link between the hydrogel and the liposomes, a compression or other mechanical force applied to the hydrogel will rupture the liposomes and release a small percentage of the cargo. Overall, a long‐term intra‐articular drug release is feasible.
A multiple shape memory and self‐healing poly(acrylic acid)‐graphene oxide‐Fe3+ (PAA‐GO‐Fe3+) hydrogel with supertough strength is synthesized containing dual physically cross‐linked PAA network by GO and Fe3+. The first GO cross‐linked hydrogel can be reversibly reinforced by immersing in FeCl3/HCl and pure water and softened by immersing in HCl. The tensile strength is 2.5 MPa with the break strain of 700%. Multiple shape memory capability is found depending on this unique feature, the hydrogel can be fixed in four temporary shapes by adjusting the immersing time in FeCl3/HCl and pure water, and recovered in sequence by immersing in HCl. This hydrogel also exhibits perfect self‐healing behavior, the cut as‐prepared hydrogel is almost completely healed by immersing in FeCl3/HCl. Besides, the hydrogel shows enhanced electrical conductivity with the presence of GO and Fe3+. This supertough hydrogel provides a new way to design soft actuators.
Green synthesis is one of the hot topics in the chemistry of hybrid organic–inorganic materials. A alcohol‐free sol–gel process has been developed to prepare optically transparent hybrid films from an epoxy bearing alkoxide, [2‐(3,4‐epoxy‐cyclohexyl)‐ethyl]‐trimethoxysilane (ECTMS). The synthesis is simple and effective because only two components, ECTMS and an aqueous solution of NaOH, are employed. Infrared spectroscopy has been used to monitor the reactivity of the precursor sol as a function of the aging time. Organic–inorganic hybrid films have been then prepared with the different sols via spin‐coating. The presence of the cyclohexyl ring slows down dramatically both the epoxide opening and the capability of the resulting diols in forming a tricyclic dioxane derivative. The highly basic conditions employed in the synthesis favor the formation of the cyclohexyl rings and cage‐ and ladder‐like silica structures. The hybrid films have shown a high transmittance in the visible range and a thermal stability up to 200 °C.
A self‐cleaning membrane that periodically rids itself of attached cells to maintain glucose diffusion could extend the lifetime of implanted glucose biosensors. Herein, we evaluate the functionality of thermoresponsive double network (DN) hydrogel membranes based on poly(N‐isopropylacrylamide) (PNIPAAm) and an electrostatic co‐monomer, 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS). DN hydrogels are comprised of a tightly crosslinked, ionized first network [P(NIPAAm‐co‐AMPS)] containing variable levels of AMPS (100:0–25:75 wt% ratio of NIPAAm:AMPS) and a loosely crosslinked, interpenetrating second network [PNIPAAm]. To meet the specific requirements of a subcutaneously implanted glucose biosensor, the volume phase transition temperature is tuned and essential properties, such as glucose diffusion kinetics, thermosensitivity, and cytocompatibility are evaluated. In addition, the self‐cleaning functionality is demonstrated through thermally driven cell detachment from the membranes in vitro.
A thin layer (around 2 nm in thickness) composed of a random copolymer of zwitterionic carboxymethyl betaine (CMB) and p‐trimethoxysilylstyrene (STMS) (9:1) is constructed on a glass substrate or a silicon wafer. The copolymer layer is highly resistant against nonspecific adsorption of bovine serum albumin (BSA). However, on UV irradiation at 193 nm, the layer becomes hydrophobic and BSA is significantly adsorbed on the substrate. Upon UV irradiation through a photomask, a patterning of the fluorophore‐labeled protein with a resolution of about 1 µm can be clearly observed. On the other hand, the copolymer layer of CMB and 3‐methacryloxypropyltrimethoxysilane (MPTMS) (9:1) without an aromatic group exhibit less distinct pattern. Further, the poly(CMB‐r‐STMS) layer decomposes more quickly compared with the poly(CMB‐r‐MPTMS) layer at low irradiation dose. The zwitterionic polymer layer with an aromatic anchor group will be used at the modification of substrates applicable to sensing devices.
Curdlan (β‐1,3 glucan) (7 wt%) with polyvinyl alcohol (PVA) (10 wt%) is blended at 1:2 weight ratio and electrospun to get nanofibers and is crosslinked with glutaraldehyde vapor to make it insoluble in water. It has a fiber diameter of less than 100 nm and is hydrophilic (contact angle = 35°). It is biodegradable (10% in 14 d) and also has a good swelling behavior (≈170%). More than 100% of L6 cells are viable on this scaffold after 3 d. The scanning electron microscope images also reveal that cells are able to attach and spread in the nanofibrous scaffolds. In vitro scratch assay indicates that the wound closure rate of curdlan/PVA scaffold is better than PVA scaffold probably due to the immunomodulatory properties of the biopolymer. Thus our results indicate that curdlan/PVA scaffold can be an ideal material for wound healing applications.
Carbon nanofiber/polycaprolactone (CNF/PCL) composite fibers are fabricated using a microfluidic approach. The fibers are made with different content levels of CNFs and flow rate ratios between the core and sheath fluids. The electrical conductivity and tensile properties of these fibers are then investigated. It is found that at a CNF concentration of 3 wt%, the electrical conductivity of the composite fiber significantly increases to 1.11 S m−1. The yield strength, Young's modulus, and ultimate strength of the 3 wt% CNF increase relative to the pure PCL by factors of 1.72, 2.88, and 1.23, respectively. Additionally, the results show that a microfluidic approach can be considered as an effective method to align CNFs along the fibers in the longitudinal direction.
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