A Comprehensive Review of Stimuli-Responsive Smart Polymer Materials-Recent Advances and Future Perspectives.

Today, smart materials are commonly used in various fields of science and technology, such as medicine, electronics, soft robotics, the chemical industry, the automotive field, and many others. Smart polymeric materials hold good promise for the future due to their endless possibilities. This group of advanced materials can be sensitive to changes or the presence of various chemical, physical, and biological stimuli, e.g., light, temperature, pH, magnetic/electric field, pressure, microorganisms, bacteria, viruses, toxic substances, and many others. This review concerns the newest achievements in the area of smart polymeric materials. The recent advances in the designing of stimuli-responsive polymers are described in this paper.

Adhesion Evolution: Designing Smart Polymeric Adhesive Systems with On-Demand Reversible Switchability.

Smart polymeric switchable adhesives represent a rapidly emerging class of advanced materials, exhibiting the ability to undergo on-demand transitioning between "On" and "Off" adhesion states. By selectively tuning external stimuli triggers (including temperature, light, electricity, magnetism, and chemical agents), we can engineer these materials to undergo reversible changes in their bonding capabilities. The strategic design selection of stimuli is a pivotal factor in the design of switchable adhesive systems. This review outlines recent advancements in the field of smart switchable polymeric adhesives over the past decade with a focus on the selection of stimulus triggers. These systems are further categorized into one of four adhesion switching mechanisms upon initiation by a specific stimuli-trigger: (i) interfacial adhesion, (ii) stiffness, (iii) contact area, or (iv) suction-based switching. Evaluation of adhesion switching performance across systems is primarily made based on three key metrics: (i) maximum adhesion strength, (ii) switch ratio, and (iii) switch time. Different stimuli and mechanisms offer distinct advantages and limitations, influencing the performance characteristics and applicability of these materials across domains such as detachable biomedical devices, robotic grippers, and climbing robots. This review thus offers a perspective on the present advancements and challenges in this emerging field, along with insights into future directions.

High stretchable and self-adhesive multifunctional hydrogel for wearable and flexible sensors.

Ionic conductive hydrogel has recently garnered significant research attention due to its potential applications in the field of wearable and flexible electronics. Nonetheless, the integration of multifunctional and synergistic advantages, including reliable electronic properties, high swelling capacity, exceptional mechanical characteristics, and self-adhesive properties, presents an ongoing challenge. In this study, we have developed an ionic conductive hydrogel through the co-polymerization of 4-Acryloylmorpholine (ACMO) and sodium acrylate using UV curing technology. The hydrogel exhibits excellent mechanical properties, high conductivity, superior swelling capacity, and remarkable self-adhesive attributes. The hydrogel serves as a highly sensitive strain sensor, enabling precise monitoring of both substantial and subtle human motions. Furthermore, the hydrogel demonstrates the capability to adhere to human skin, functioning as a human-machine interface for the detection of physiological signals, including electromyogram (EMG) signals, with low interfacial impedance. This work is anticipated to yield a new class of stretchable and conductive materials with diverse potential applications, ranging from flexible sensors and wearable bio-electronics to contributions in the field of artificial intelligence.

Recent Advances in Multi-Photon 3D Laser Printing: Active Materials and Applications.

Since the pioneering work of Kawata and colleagues in 1997, multi-photon 3D laser printing, also known as direct laser writing, has made significant advancements in a wide range of fields. Moreover, the development and commercialization of photocurable inks for this technique have expanded rapidly. One of the current trends is the transition from static to active printable materials, often referred to as 4D microprinting, which enables a new degree of control in the printed systems. This review focuses on four primary application areas: microrobotics, optics and photonics, microfluidics, and life sciences, highlighting recent progress and the crucial role of active materials, including liquid crystalline elastomers, hydrogels, shape memory polymers, and composites, among others. It also addresses ongoing challenges and provides insights into the future prospects in the different fields.

Physiochemical and mechanical characterisation of orthodontic 3D printed aligner material made of shape memory polymers (4D aligner material).

OBJECTIVES: To conduct a physiochemical and mechanical material analysis on 3D printed shape-memory aligners in comparison to thermoformed aligners. MATERIALS AND METHODS: Four materials were examined, including three thermoformed materials: CA Pro (CP), Zendura A (ZA), Zendura FLX (ZF), and one 3D printed material: Tera Harz (TC-85). Rectangular strips measuring 50 × 10 × 0.5 mm were produced from each material. Five tests were conducted, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), shape recovery tests, three-points bending (3 PB), and Vickers surface microhardness (VH). RESULTS: DSC recorded glass transition temperatures (Tg) at 79.9 °C for CP, 92.2 °C for ZA, 107.1 °C for ZF, and 42.3 °C for TC-85. In DMA analysis at 20-45 °C, a prominent decrease in storage modulus was observed, exclusively for TC-85, as the temperature increased. Notably, within the temperature range of 30-45 °C, TC-85 exhibited substantial shape recovery after 10 min, reaching up to 86.1 %, while thermoformed materials showed minimal recovery (1.5-2.9 %). In 3 PB test (at 30, 37, 45 °C), ZA demonstrated the highest force at 2 mm bending, while TC-85 exhibited the lowest. Regarding VH at room temperature, there was a significant decrease for both ZA and ZF after thermoforming. ZA had the highest hardness, followed by ZF and TC-85, with CP showing the lowest values. CONCLUSIONS: TC-85 demonstrates exceptional shape memory at oral temperature, improving adaptation, reducing force decay, and enabling, together with its higher flexibility, extensive tooth movement per step. Additionally, it maintains microhardness similar to thermoformed sheets, ensuring the durability and effectiveness of dental aligners. CLINICAL RELEVANCE: The 3D printed aligner material with shape memory characteristics (4D aligner) has revolutionized the orthodontic aligner field. It showed mechanical properties more suitable for orthodontic treatment than thermoforming materials. Additionally, it offers enhanced control over aligner design and thickness, while optimizing the overall workflow. It also minimizes material wastage, and reduces production expenses.

Self-Healing Polymeric Materials and Composites for Additive Manufacturing.

Self-healing polymers have received widespread attention due to their ability to repair damage autonomously and increase material stability, reliability, and economy. However, the processability of self-healing materials has yet to be studied, limiting the application of rich self-healing mechanisms. Additive manufacturing effectively improves the shortcomings of conventional processing while increasing production speed, accuracy, and complexity, offering great promise for self-healing polymer applications. This article summarizes the current self-healing mechanisms of self-healing polymers and their corresponding additive manufacturing methods, and provides an outlook on future developments in the field.

Lipid polymer hybrid nanoparticles: a custom-tailored next-generation approach for cancer therapeutics.

Lipid-based polymeric nanoparticles are the highly popular carrier systems for cancer drug therapy. But presently, detailed investigations have revealed their flaws as drug delivery carriers. Lipid polymer hybrid nanoparticles (LPHNPs) are advanced core-shell nanoconstructs with a polymeric core region enclosed by a lipidic layer, presumed to be derived from both liposomes and polymeric nanounits. This unique concept is of utmost importance as a combinable drug delivery platform in oncology due to its dual structured character. To add advantage and restrict one's limitation by other, LPHNPs have been designed so to gain number of advantages such as stability, high loading of cargo, increased biocompatibility, rate-limiting controlled release, and elevated drug half-lives as well as therapeutic effectiveness while minimizing their drawbacks. The outer shell, in particular, can be functionalized in a variety of ways with stimuli-responsive moieties and ligands to provide intelligent holding and for active targeting of antineoplastic medicines, transport of genes, and theragnostic. This review comprehensively provides insight into recent substantial advancements in developing strategies for treating various cancer using LPHNPs. The bioactivity assessment factors have also been highlighted with a discussion of LPHNPs future clinical prospects.

Smart Polymers for Soft Materials: From Solution Processing to Organic Solids.

Polymeric materials are ubiquitous in our everyday life, where they find a broad range of uses-spanning across common household items to advanced materials for modern technologies. In the context of the latter, so called "smart polymers" have received a lot of attention. These systems are soluble in water below their lower critical solution temperature Tℓ and often exhibit counterintuitive solvation behavior in mixed solvents. A polymer is known as smart-responsive when a slight change in external stimuli can significantly change its structure, functionm and stability. The interplay of different interactions, especially hydrogen bonds, can also be used for the design of lightweight high-performance organic solids with tunable properties. Here, a general scheme for establishing a structure-property relationship is a challenge using the conventional simulation techniques and also in standard experiments. From the theoretical side, a broad range of all-atom, multiscale, generic, and analytical techniques have been developed linking monomer level interaction details with macroscopic material properties. In this review, we briefly summarize the recent developments in the field of smart polymers, together with complementary experiments. For this purpose, we will specifically discuss the following: (1) the solution processing of responsive polymers and (2) their use in organic solids, with a goal to provide a microscopic understanding that may be used as a guiding tool for future experiments and/or simulations regarding designing advanced functional materials.

Stimuli-responsive biomaterials: smart avenue toward 4D bioprinting.

3D bioprinting is an advanced technology combining cells and bioactive molecules within a single bioscaffold; however, this scaffold cannot change, modify or grow in response to a dynamic implemented environment. Lately, a new era of smart polymers and hydrogels has emerged, which can add another dimension, e.g., time to 3D bioprinting, to address some of the current approaches' limitations. This concept is indicated as 4D bioprinting. This approach may assist in fabricating tissue-like structures with a configuration and function that mimic the natural tissue. These scaffolds can change and reform as the tissue are transformed with the potential of specific drug or biomolecules released for various biomedical applications, such as biosensing, wound healing, soft robotics, drug delivery, and tissue engineering, though 4D bioprinting is still in its early stages and more works are required to advance it. In this review article, the critical challenge in the field of 4D bioprinting and transformations from 3D bioprinting to 4D phases is reviewed. Also, the mechanistic aspects from the chemistry and material science point of view are discussed too.

Advances in Material Modification with Smart Functional Polymers for Combating Biofilms in Biomedical Applications.

Biofilms as living microorganism communities are found anywhere, and for the healthcare sector, these constitute a threat and allied mechanism for health-associated or nosocomial infections. This review states the basis of biofilms and their formation. It focuses on their relevance for the biomedical sector, generalities, and the major advances in modified or new synthesized materials to prevent or control biofilm formation in biomedicine. Biofilm is conceptualized as an aggregate of cells highly communicated in an extracellular matrix, which the formation obeys to molecular and genetic basis. The biofilm offers protection to microorganisms from unfavorable environmental conditions. The most frequent genera of microorganisms forming biofilms and reported in infections are Staphylococcus spp., Escherichia spp., and Candida spp. in implants, heart valves, catheters, medical devices, and prostheses. During the last decade, biofilms have been most commonly related to health-associated infections and deaths in Europe, the United States, and Mexico. Smart, functional polymers are materials capable of responding to diverse stimuli. These represent a strategy to fight against biofilms through the modification or synthesis of new materials. Polypropylene and poly-N-isopropyl acrylamide were used enough in the literature analysis performed. Even smart polymers serve as delivery systems for other substances, such as antibiotics, for biofilm control.

Effects of Steam Sterilization on the Properties of Stimuli-Responsive Polymer-Based Hydrogels.

Hydrogels based on stimuli-responsive polymers can change their characteristics in response to small variations in environmental conditions, such as temperature, pH, and ionic strength, among others. In the case of some routes of administration, such as ophthalmic and parenteral, the formulations must meet specific requirements, namely sterility. Therefore, it is essential to study the effect of the sterilization method on the integrity of smart gel systems. Thus, this work aimed to study the effect of steam sterilization (121 °C, 15 min) on the properties of hydrogels based on the following stimuli-responsive polymers: Carbopol® 940, Pluronic® F-127, and sodium alginate. The properties of the prepared hydrogels-pH, texture, rheological behavior, and sol-gel phase transition-were evaluated to compare and identify the differences between sterilized and non-sterilized hydrogels. The influence of steam sterilization on physicochemical stability was also investigated by Fourier-transform infrared spectroscopy and differential scanning calorimetry. The results of this study showed that the Carbopol® 940 hydrogel was the one that suffered fewer changes in the studied properties after sterilization. By contrast, sterilization was found to cause slight changes in the Pluronic® F-127 hydrogel regarding gelation temperature/time, as well as a considerable decrease in the viscosity of the sodium alginate hydrogel. There were no considerable differences in the chemical and physical characteristics of the hydrogels after steam sterilization. It is possible to conclude that steam sterilization is suitable for Carbopol® 940 hydrogels. Contrarily, this technique does not seem adequate for the sterilization of alginate or Pluronic® F-127 hydrogels, as it could considerably alter their properties.

Impact of the Chemical Structure of Photoreactive Urethane (Meth)Acrylates with Various (Meth)Acrylate Groups and Built-In Diels-Alder Reaction Adducts on the UV-Curing Process and Self-Healing Properties.

A series of UV-curable urethane (meth)acrylates were obtained by copolymerization of the Diels-Alder adduct (HODA), isophorone diisocyanate, PEG1000, and various hydroxy (meth)acrylates. The aim of the present work was to determine the influence of the chemical structure of the introduced (meth)acrylic groups, i.e., hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, on the UV-curing process and self-healing properties of cured coatings. The chemical structure of prepolymers was characterized by FTIR and NMR spectroscopy, whereas the UV-curing process was monitored in real time using FTIR and photo-DSC. In turn, the self-healing properties were characterized in relation to the thermally reversible mechanism, which was tested using the following methods: an FTIR spectroscope equipped with a heating attachment; DSC and TG apparatus; and an optical microscope equipped with a stage with programmable heating. The result of comprehensive research on the self-healing of photocurable coatings in the context of the presence of various photoreactive groups and the course of the curing process allows one to control the self-healing process by reducing the effective healing temperature. The self-healing properties, taken together with the fast UV curing of the coatings and excellent properties of cured coatings, make the material attractive for a variety of applications, in particular in cases where coatings are not repaired, e.g., for economic reasons or when it is not possible, such as in flexible electronic screens, car paint film, and aircraft interior finishes.

Advances in 4D printing: from stimulation to simulation.

The advancement of four-dimensional (4D) printing has been fueled by the rise in demand for additive manufacturing and the expansion in shape-memory materials. The printing of smart substances that respond to external stimuli is known as 4D printing. 4D printing allows highly controlled shapes to simulate the physiological milieu by adding time dimensions. The 4D printing is suitable with current progress in smart compounds, printers, and its mechanism of action. The 4D printing paradigm, a revolutionary enhancement of 3D printing, was anticipated by various engineering disciplines. Tissue engineering, medicinal, consumer items, aerospace, and organ engineering use 4D printing technology. The current review mainly focuses on the basics of 4D printing and the methods used therein. It also discusses the time-dependent behavior of stimulus-sensitive compounds, which are widely used in 4D printing. In addition, this review highlights material aspects, specifically related to shape-memory polymers, stimuli-responsive materials (classified as physical, chemical, and biological), and modified materials, the backbone of 4D printing technology. Finally, potential applications of 4D printing in the biomedical sector are also discussed with challenges and future perspectives.

Rational Understanding of Loading and Release of Doxorubicin by UV-Light- and pH-Responsive Poly(NIPAM-co-SPMA) Micelle-like Aggregates.

A deep understanding of the interactions between micelle-like aggregates and antineoplastic drugs is paramount to control their adequate delivery. Herein, Poly(NIPAM-co-SPMA) copolymer nanocarriers were synthesized according to our previous published methodology, and the loading and release of poorly and highly water-soluble doxorubicin forms (Dox and Dox-HCl, respectively) were evaluated upon UV light irradiation and pH-variation stimuli. Capillary electrophoresis (CE) coupled to a fluorescence detector (LIF) allowed us to specifically characterize these systems and deeply study the loading and release processes. For this purpose, varying concentrations of doxorubicin were tested, and the loading/release rates were indirectly quantified thanks to the "free" doxorubicin concentration in solution. This study highlighted that Dox loading (9.4 µg/mg) was more effective than Dox-HCl loading (5.5 µg/mg). In contrast, 68 and 74% of Dox-HCl were respectively released after 2 min upon pH variation (from 7.4 to 6.0) and combined UV + pH 6.0 stimuli, while only 27% of Dox was invariably released upon application of the same stimuli. These results are coherent with the characteristics of both DoxHCl and Dox: Electrostatic interactions between Dox-HCl and the micelle-membrane structure (NIPAM) seemed predominant, while hydrophobic interactions were expected between Dox and the SP moieties at the inner part of the micelle-like aggregate, leading to different behaviors in both loading and release of the two doxorubicin forms. For doxorubicin loading concentrations higher than 3 µM, the electrophoretic profiles presented an additional peak. Thanks to CE characterizations, this peak was attributed to the formation of a complex formed between the nonaggregated copolymer and the doxorubicin molecules. This report therefore undergoes deep characterization of the dynamic formation of different micelle/drug complexes involved in the global drug-delivery behavior and therefore contributes to the development of more effective stimuli-responsive nanocarriers.

Polyelectrolytes for Enzyme Immobilization and the Regulation of Their Properties.

In this review, we considered aspects related to the application of polyelectrolytes, primarily synthetic polyanions and polycations, to immobilize enzymes and regulate their properties. We mainly focused on the description of works in which polyelectrolytes were used to create complex and unusual systems (self-regulated enzyme-polyelectrolyte complexes, artificial chaperones, polyelectrolyte brushes, layer-by-layer immobilization and others). These works represent the field of "smart polymers", whilst the trivial use of charged polymers as carriers for adsorption or covalent immobilization of proteins is beyond the scope of this short review. In addition, we have included a section on the molecular modeling of interactions between proteins and polyelectrolytes, as modeling the binding of proteins with a strictly defined, and already known, spatial structure, to disordered polymeric molecules has its own unique characteristics.

Modification of Tubings for Peristaltic Pumping of Biopharmaceutics.

Protein particle formation during peristaltic pumping of biopharmaceuticals is due to protein film formation on the inner tubing surface followed by rupture of the film by the roller movement. Protein adsorption can be prevented by addition of surfactants as well as by increasing the hydrophilicity of the inner surface. Attempts based on covalent surface coating were mechanically not stable against the stress of roller movement. We successfully incorporated surface segregating smart polymers based on a polydimethylsiloxane (PDMS) backbone and polyethylene glycol (PEG) side blocks in the tubing wall matrix. For this we applied an easy, reproducible and cost-effective process based on soaking of tubing in toluene containing the PDMS-PEG copolymer. With this tubing modification we could drastically reduce protein particle formation during peristaltic pumping of a monoclonal antibody and human growth hormone (HGH) formulation in silicone and thermoplastic elastomer-based tubing. The modification did not impact the tubing integrity during pumping while hydrophilicity was increased and protein adsorption was prevented. Free PDMS-PEG copolymer might have an additional stabilizing effect, but less than 50 ppm of the PDMS-PEG copolymer leached from the modified tubing during 1 h of pumping in the experimental setup. In summary, we present a new method for the modification of tubings which reduces protein adsorption and particle formation during any operation involving peristaltic pumping, e.g. transfer, filling, or tangential flow filtration.

Biosensor-Integrated Drug Delivery Systems as New Materials for Biomedical Applications.

Biosensor-integrated drug delivery systems are innovative devices in the health area, enabling continuous monitoring and drug administration. The use of smart polymer, bioMEMS, and electrochemical sensors have been extensively studied for these systems, especially for chronic diseases such as diabetes mellitus, cancer and cardiovascular diseases as well as advances in regenerative medicine. Basically, the technology involves sensors designed for the continuous analysis of biological molecules followed by drug release in response to specific signals. The advantages include high sensitivity and fast drug release. In this work, the main advances of biosensor-integrated drug delivery systems as new biomedical materials to improve the patients' quality of life with chronic diseases are discussed.

Biomaterials for Tissue Engineering Applications and Current Updates in the Field: A Comprehensive Review.

Tissue engineering has emerged as an interesting field nowadays; it focuses on accelerating the auto-healing mechanism of tissues rather than organ transplantation. It involves implanting an In Vitro cultured initiative tissue or a scaffold loaded with tissue regenerating ingredients at the damaged area. Both techniques are based on the use of biodegradable, biocompatible polymers as scaffolding materials which are either derived from natural (e.g. alginates, celluloses, and zein) or synthetic sources (e.g. PLGA, PCL, and PLA). This review discusses in detail the recent applications of different biomaterials in tissue engineering highlighting the targeted tissues besides the in vitro and in vivo key findings. As well, smart biomaterials (e.g. chitosan) are fascinating candidates in the field as they are capable of elucidating a chemical or physical transformation as response to external stimuli (e.g. temperature, pH, magnetic or electric fields). Recent trends in tissue engineering are summarized in this review highlighting the use of stem cells, 3D printing techniques, and the most recent 4D printing approach which relies on the use of smart biomaterials to produce a dynamic scaffold resembling the natural tissue. Furthermore, the application of advanced tissue engineering techniques provides hope for the researchers to recognize COVID-19/host interaction, also, it presents a promising solution to rejuvenate the destroyed lung tissues.

Recent Developments in Shape Memory Elastomers for Biotechnology Applications.

Shape memory elastomers have revolutionised the world since their introduction in the 20th century. The ability to tailor chemical structures to produce a family of materials in wide-ranging forms with versatile properties has propelled them to be ubiquitous. Recent challenges in the end-of-life management of polymeric materials should prompt us to ask, 'what innovations in polymeric materials can make a strong case for their use as efficient materials?' The development of smart elastomers that can acquire, convey, or process a stimulus (such as temperature, pressure, electromagnetic field, moisture, and chemical signals) and reply by creating a useful effect, specifically a reversible change in shape, is one such innovation. Here, we present a brief overview of shape memory elastomers (SMEs) and thereafter a review of recent advances in their development. We discuss the complex processing of structure-property relations and how they differ for a range of stimuli-responsive SMEs, self-healing SMEs, thermoplastic SMEs, and antibacterial and antifouling SMEs. Following innovations in SEMs, the SMEs are forecast to have significant potential in biotechnology based on their tailorable physical properties that are suited to a range of different external stimuli.

Multiple Responsiveness of Polymer Actuators.

To improve photosensitivity of polymer materials, an effective protocol is to increase the content of photosensitive moieties. However, most of photosensitive units are toxic. The high content is not acceptable for real-world applications. Therefore, achieving photosensitive polymers with low content of photosensitive moieties but maintaining their photosensitivity remains a challenge. Herein, a protocol is reported to address this challenge by combining photosensitive monomers with hygroscopic monomers, where the synergistic action of two types of functional moieties can improve the photosensitivity of polymer network. Upon exposure to light irradiation, the polymer can be driven by not only the structural isomerization of photosensitive units, but also the photothermal effects. This synergistic effect results in the polymer-based soft actuators capable of showing rapid response to light even at the extremely-low content of photosensitive moieties of 2.6 mol.%. Importantly, the combination of hygroscopic and photosensitive moieties provides polymer with multiple responsiveness including acidochromism, humidity responsiveness, photohardening, shape memory, photochromism, and in situ swelling, making it useful in sensing systems, information transmission, and artificial muscles.