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Donor-acceptor Stenhouse adducts (DASAs) are a photo-switch class that undergoes triene cyclisation in response to visible light. Herein, electrochemical oxidation is demonstrated as an effective alternative stimulus for the triene cyclisation commonly associated with photo-switching.

Herein, we report a stimuli-responsive hydrogel with inhibitory activity against Escherichia coli prepared by chemical crosslinking of carboxymethyl chitosan (CMCs) and hydroxyethyl cellulose (HEC). The hydrogels were prepared by esterification of chitosan (Cs) with monochloroacetic acid to produce CMCs which were then chemically crosslinked to HEC using citric acid as the crosslinking agent. To impart a stimuli responsiveness property to the hydrogels, polydiacetylene-zinc oxide (PDA-ZnO) nanosheets were synthesized in situ during the crosslinking reaction followed by photopolymerization of the resultant composite. To achieve this, ZnO was anchored on carboxylic groups in 10,12-pentacosadiynoic acid (PCDA) layers to restrict the movement of the alkyl portion of PCDA during crosslinking CMCs and HEC hydrogels. This was followed by irradiating the composite with UV radiation to photopolymerize the PCDA to PDA within the hydrogel matrix so as to impart thermal and pH responsiveness to the hydrogel. From the results obtained, the prepared hydrogel had a pH-dependent swelling capacity as it absorbed more water in acidic media as compared to basic media. The incorporation of PDA-ZnO resulted in a thermochromic composite responsive to pH evidenced by a visible colour transition from pale purple to pale pink. Upon swelling, PDA-ZnO-CMCs-HEC hydrogels had significant inhibitory activity against E. coli attributed to the slow release of the ZnO nanoparticles as compared to CMCs-HEC hydrogels. In conclusion, the developed hydrogel was found to have stimuli-responsive properties and inhibitory activity against E. coli attributed to zinc nanoparticles.

Despite their conventional and widespread use, oral and intravenous routes of drug administration face several limitations. In particular, orally administered drugs undergo enzymatic degradation in the gastrointestinal tract and first-pass metabolism in the liver, which tend to decrease their bioavailability. Intravenous infusions of medications are invasive, painful and stressful for patients and carry the risk of infections, tissue damage and other adverse reactions. In order to account for these disadvantages, alternative routes of drug delivery, such as transdermal, nasal, oromucosal, ocular and others, have been considered. Moreover, drug formulations have been modified in order to improve their storage stability, solubility, absorption and safety. Recently, stimuli-responsive polymers have been shown to achieve controlled release and enhance the bioavailability of multiple drugs. In this review, we discuss the most up-to-date use of stimuli-responsive materials in order to optimize the delivery of medications that are unstable to pH or undergo primary metabolism via transdermal, nasal, oromucosal and ocular routes. Release kinetics, diffusion parameters and permeation rate of the drug via the mucosa or skin are discussed as well.

Gas therapy has received widespread attention from the medical community as an emerging and promising therapeutic approach to cancer treatment. Among all gas molecules, nitric oxide (NO) was the first one to be applied in the biomedical field for its intriguing properties and unique anti-tumor mechanisms which have become a research hotspot in recent years. Despite the great progress of NO in cancer therapy, the non-specific distribution of NO in vivo and its side effects on normal tissue at high concentrations have impaired its clinical application. Therefore, it is important to develop facile NO-based nanomedicines to achieve the on-demand release of NO in tumor tissue while avoiding the leakage of NO in normal tissue, which could enhance therapeutic efficacy and reduce side effects at the same time. In recent years, numerous studies have reported the design and development of NO-based nanomedicines which were triggered by exogenous stimulus (light, ultrasound, X-ray) or tumor endogenous signals (glutathione, weak acid, glucose). In this review, we summarized the design principles and release behaviors of NO-based nanomedicines upon various stimuli and their applications in synergistic cancer therapy. We also discuss the anti-tumor mechanisms of NO-based nanomedicines in vivo for enhanced cancer therapy. Moreover, we discuss the existing challenges and further perspectives in this field in the aim of furthering its development.

Immunotherapy has been investigated for decades, and it has provided promising results in preclinical studies. The most important issue that hinders researchers from advancing to clinical studies is the delivery system for immunotherapy agents, such as antigens, adjuvants and agonists, and the activation of these agents at the tumour site. Polymers are among the most versatile materials for a variety of treatments and diagnostics, and some polymers are reactive to either endogenous or exogenous stimuli. Utilizing this advantage, researchers have been developing novel and effective polymeric nanomaterials that can deliver immunotherapeutic moieties. In this review, we summarized recent works on stimuli-responsive polymeric nanomaterials that deliver antigens, adjuvants and agonists to tumours for immunotherapy purposes.

Smart materials represent an elegant class of (macro)-molecules endowed with the ability to react to chemical/physical changes in the environment. Herein, we prepared new photo responsive azobenzenes possessing halogen bond donor groups. The X-ray structures of two molecules highlight supramolecular organizations governed by unusual noncovalent bonds. In azo dye I-azo-NO2, the nitro group is engaged in orthogonal H···O···I halogen and hydrogen bonding, linking the units in parallel undulating chains. As concern parent I-azo-NH-MMA, a non-centrosymmetric pattern is formed due to a very rare I···π interaction involving the alkene group supplemented by hydrogen bonds. The Cambridge Structural Database contains only four structures with the same I···CH2=C contact. For all compounds, a 19F NMR spectroscopic analysis confirms the formation of halogen bonds in solution through a recognition process with chloride anion, and the reversible photo-responsiveness is demonstrated upon exposing a solution to UV light irradiation. Finally, intermediate I-azo-NO2 also shows a pronounced color change due to pH variation. These azobenzenes are thereby attractive building blocks to design multi-stimuli responsive materials for highly functional devices.

Two temperature and pH responsive submicron hydrogels based on poly(N- methylenebisacrylamide), chitosan and &beta, cyclodextrines (PNCS/CD hydrogel) with varying poly(N-isopropylacrylamide) to chitosan ratios were synthesized according to a simplified procedure, reflecting improved stimuli responsive properties and excellent bio-barrier properties, granted by incorporated chitosan. Hydrogels were applied to cotton-cellulose fabric as active coatings. Subsequently, antimicrobially active savory essential oil (EO) was embedded into the hydrogels in order to develop temperature- and pH-responsive cotton-cellulose fabric with double antimicrobial activity, i.e., bio-barrier formation of chitosan along with the proactive release of savory EO at predetermined conditions. The influence of the hydrogels chemical composition on stimuli responsive and antibacterial properties were assessed. Both PNCS/CD hydrogels showed stimuli responsiveness along with controlled release of savory EO. The chemical composition of the hydrogels strongly influenced the size of the hydrogel particles, their temperature and pH responsiveness, and the bio-barrier forming activity. The increased concentration of chitosan resulted in superior overall stimuli responsiveness and excellent synergy between the antimicrobial activities of the hydrogel and released savory EO.

The innovative research in genome editing domains such as CRISPR-Cas technology has enabled genetic engineers to manipulate the genomes of living organisms effectively in order to develop the next generation of therapeutic tools. This technique has started the new era of “genome surgery”. Despite these advances, the barriers of CRISPR-Cas9 techniques in clinical applications include efficient delivery of CRISPR/Cas9 and risk of off-target effects. Various types of viral and non-viral vectors are designed to deliver the CRISPR/Cas9 machinery into the desired cell. These methods still suffer difficulties such as immune response, lack of specificity, and efficiency. The extracellular and intracellular environments of cells and tissues differ in pH, redox species, enzyme activity, and light sensitivity. Recently, smart nanoparticles have been synthesized for CRISPR/Cas9 delivery to cells based on endogenous (pH, enzyme, redox specie, ATP) and exogenous (magnetic, ultrasound, temperature, light) stimulus signals. These methodologies can leverage genome editing through biological signals found within disease cells with less off-target effects. Here, we review the recent advances in stimulus-based smart nanoparticles to deliver the CRISPR/Cas9 machinery into the desired cell. This review article will provide extensive information to cautiously utilize smart nanoparticles for basic biomedical applications and therapeutic genome editing.

Biocompatible nanosystems based on polymeric materials are promising drug delivery nanocarrier candidates for antitumor therapy. However, the efficacy is unsatisfying due to nonspecific accumulation and drug release of the nanoparticles in normal tissue. Recently, the nanosystems that can be triggered by tumor-specific stimuli have drawn great interest for drug delivery applications due to their controllable drug release properties. In this review, various polymers and external stimuli that can be employed to develop stimuli-responsive polymeric nanosystems are discussed, and finally, we delineate the challenges in designing this kind of Nanomedicine to improve the therapeutic efficacy.

Polyelectrolyte gels are an important class of polymer gels and a versatile platform with charged polymer networks with ionisable groups. They have drawn significant recent attention as a class of smart material and have demonstrated potential for a variety of applications. This review begins with the fundamentals of polyelectrolyte gels, which encompass various classifications (i.e., origin, charge, shape) and crucial aspects (ionic conductivity and stimuli responsiveness). It further centralises recent developments of polyelectrolyte gels, emphasising their synthesis, structure–property relationships and responsive properties. Sequentially, this review demonstrates how polyelectrolyte gels’ flourishing properties create attractiveness to a range of applications including tissue engineering, drug delivery, actuators and bioelectronics. Finally, the review outlines the indisputable appeal, further improvements and emerging trends in polyelectrolyte gels.

Poly(aspartamide) derivatives, one kind of amino acid-based polymers with excellent biocompatibility and biodegradability, meet the key requirements for application in various areas of biomedicine. Poly(aspartamide) derivatives with stimuli-responsiveness can usually respond to external stimuli to change their chemical or physical properties. Using external stimuli such as temperature and pH as switches, these smart poly(aspartamide) derivatives can be used for convenient drug loading and controlled release. Here, we review the synthesis strategies for preparing these stimuli-responsive poly(aspartamide) derivatives and the latest developments in their applications as drug carriers.

Millions of years’ evolution has imparted life on earth with excellent environment adaptability. Of particular interest to scientists are some plants capable of macroscopically and reversibly altering their morphological and mechanical properties in response to external stimuli from the surrounding environment. These intriguing natural phenomena and underlying actuation mechanisms have provided important design guidance and principles for man-made soft robotic systems. Constructing bio-inspired soft robotic systems with effective actuation requires the efficient supply of mechanical energy generated from external inputs, such as temperature, light, and electricity. By combining bio-inspired designs with stimuli-responsive materials, various intelligent soft robotic systems that demonstrate promising and exciting results have been developed. As one of the building materials for soft robotics, hydrogels are gaining increasing attention owing to their advantageous properties, such as ultra-tunable modulus, high compliance, varying stimuli-responsiveness, good biocompatibility, and high transparency. In this review article, we summarize the recent progress on plant-inspired soft robotics assembled by stimuli-responsive hydrogels with a particular focus on their actuation mechanisms, fabrication, and application. Meanwhile, some critical challenges and problems associated with current hydrogel-based soft robotics are briefly introduced, and possible solutions are proposed. We expect that this review would provide elementary tutorial guidelines to audiences who are interested in the study on nature-inspired soft robotics, especially hydrogel-based intelligent soft robotic systems.

The temperature and mechanism of phase transition of poly(N-isopropylacrylamide-co-acrylic acid) [P(NiPAAm-co-AAc)], which is one of the multi-stimuli responsive polymers, were investigated at various pHs using infrared (IR) spectroscopy, two-dimensional (2D) gradient mapping, and two-dimensional correlation spectroscopy (2D-COS). The determined phase transition temperature of P(NiPAAm-co-AAc) at pH 4, 3, and 2 based on 2D gradient mapping and principal component analysis (PCA) showed that it decreases with decreasing pH, because COOH group in AAc changes with variation of pH. The results of 2D-COS analysis indicated that the phase transition mechanism of P(NiPAAm-co-AAc) hydrogel at pH4 is different from that at pH2 due to the effect of COOH group of AAc.

The epoch of nanotechnology has authorized novel investigation strategies in the area of drug delivery. Liposomes are attractive biomimetic nanocarriers characterized by their biocompatibility, high loading capacity, and their ability to reduce encapsulated drug toxicity. Nevertheless, various limitations including physical instability, lack of site specificity, and low targeting abilities have impeded the use of solo liposomes. Metal nanocarriers are emerging moieties that can enhance the therapeutic activity of many drugs with improved release and targeted potential, yet numerous barriers, such as colloidal instability, cellular toxicity, and poor cellular uptake, restrain their applicability in vivo. The empire of nanohybrid systems has shelled to overcome these curbs and to combine the criteria of liposomes and metal nanocarriers for successful theranostic delivery. Metallic moieties can be embedded or functionalized on the liposomal systems. The current review sheds light on different liposomal-metal nanohybrid systems that were designed as cellular bearers for therapeutic agents, delivering them to their targeted terminus to combat one of the most widely recognized diseases, cancer.

In these times of Industrial 4.0 and Health 4.0, people currently want to enhance the ability of science and technology, to focus on patient aspects. However, with intelligent, green energy and biomedicine these days, traditional three-dimensional (3D) printing technology has been unable to meet our needs, so 4D printing has now arisen. In this research, a shape-memory composite material with 3D printing technology was used for 4D printing technology. The authors used fused deposition modeling (FDM) to print a polylactic acid (PLA) strip onto the surface of paper to create a shape-memory composite material, and a stimulus (heat) was used to deform and recover the shape of this material. The deformation angle and recovery angle of the material were studied with various processing parameters (heating temperature, heating time, pitch, and printing speed). This research discusses optimal processing related to shape-memory situations of stimulus-responsive composite materials. The optimal deformation angle (maximum) of the stimulus-responsive composite material was found with a thermal stimulus for an optimal heating temperature of 190 °C, a heating time of 20 s, a pitch of 1.5 mm, and a printing speed of 80 mm/s. The optimal recovery angle (minimum) of this material was found with a thermal stimulus for an optimal heating temperature of 170 °C, a heating time of 90 s, a pitch of 2.0 mm, and a printing speed of 80 mm/s. The most important factor affecting both the deformation and recovery angle of the stimulus-responsive composite material was the heating temperature. Refereed/Peer-reviewed

Recently, tunable photonic crystals (PhCs) have received great research interest, thanks to the wide range of applications in which they can be employed, such as light emission and sensing, among others. In addition, the versatility and ease of fabrication of PhCs allow for the integration of a large range of responsive elements that, in turn, can permit active tuning of PhC optical properties upon application of external stimuli, e.g., physical, chemical or even biological triggers. In this work, we summarize the most employed theoretical tools used for the design of optical properties of responsive PhCs and the most used fabrication techniques. Furthermore, we collect the most relevant results related to this field, with particular emphasis on electrochromic devices.

Hybrid stimuli-responsive soft robots have been extensively developed by incorporating multi-functional materials, such as carbon-based nanoparticles, nanowires, low-dimensional materials, and liquid crystals. In addition to the general functions of conventional soft robots, hybrid stimuli-responsive soft robots have displayed significantly advanced multi-mechanical, electrical, or/and optical properties accompanied with smart shape transformation in response to external stimuli, such as heat, light, and even biomaterials. This review surveys the current enhanced scientific methods to synthesize the integration of multi-functional materials within stimuli-responsive soft robots. Furthermore, this review focuses on the applications of hybrid stimuli-responsive soft robots in the forms of actuators and sensors that display multi-responsive and highly sensitive properties. Finally, it highlights the current challenges of stimuli-responsive soft robots and suggests perspectives on future directions for achieving intelligent hybrid stimuli-responsive soft robots applicable in real environments.

Currently, research in nanoparticles as a drug delivery system has broadened to include their use as a delivery system for bioactive substances and a diagnostic or theranostic system. Nanogels, nanoparticles containing a high amount of water, have gained attention due to their advantages of colloidal stability, core-shell structure, and adjustable structural components. These advantages provide the potential to design and fabricate multifunctional nanosystems for various biomedical applications. Modified or functionalized polymers and some metals are components that markedly enhance the features of the nanogels, such as tunable amphiphilicity, biocompatibility, stimuli-responsiveness, or sensing moieties, leading to specificity, stability, and tracking abilities. Here, we review the diverse designs of core-shell structure nanogels along with studies on the fabrication and demonstration of the responsiveness of nanogels to different stimuli, temperature, pH, reductive environment, or radiation. Furthermore, additional biomedical applications are presented to illustrate the versatility of the nanogels.

Peptide-based drug delivery systems have many advantages when compared to synthetic systems in that they have better biocompatibility, biochemical and biophysical properties, lack of toxicity, controlled molecular weight via solid phase synthesis and purification. Lysosomes, solid lipid nanoparticles, dendrimers, polymeric micelles can be applied by intravenous administration, however they are of artificial nature and thus may induce side effects and possess lack of ability to penetrate the blood-brain barrier. An analysis of nontoxic drug delivery systems and an establishment of prospective trends in the development of drug delivery systems was needed. This review paper summarizes data, mainly from the past 5 years, devoted to the use of peptide-based carriers for delivery of various toxic drugs, mostly anticancer or drugs with limiting bioavailability. Peptide-based drug delivery platforms are utilized as peptide–drug conjugates, injectable biodegradable particles and depots for delivering small molecule pharmaceutical substances (500 Da) and therapeutic proteins. Controlled drug delivery systems that can effectively deliver anticancer and peptide-based drugs leading to accelerated recovery without significant side effects are discussed. Moreover, cell penetrating peptides and their molecular mechanisms as targeting peptides, as well as stimuli responsive (enzyme-responsive and pH-responsive) peptides and peptide-based self-assembly scaffolds are also reviewed.

Simple Summary DNA based and stimuli-responsive smart nano-carrier system can efficiently deliver encapsulated cargos in response to various driving thresholds. The conditional release of encapsulated carriers via modifications in the dynamic structure of DNA in response to tumor microenvironment has led to the specific delivery of active agents to the tumors. Therefore, specific drug delivery enhances the therapeutic efficacy and decreases the side effects on the neighboring healthy cells. Despite the great potential for pharmacological applications of the DNA-assisted and pH-sensitive smart nano-carriers, some challenges should be addressed before clinical transition. Since the therapeutic efficacies of DNA based smart nano-carriers have only been investigated in a proof-of-concept manner, the detailed in vivo parameters of the nano-carriers must be investigated and elucidated, including colloidal stability, circulating half-life, immunogenicity, dose-dependent cytotoxicity, pharmacokinetics, and clearance mechanisms. Abstract The rapid development of multidrug co-delivery and nano-medicines has made spontaneous progress in tumor treatment and diagnosis. DNA is a unique biological molecule that can be tailored and molded into various nanostructures. The addition of ligands or stimuli-responsive elements enables DNA nanostructures to mediate highly targeted drug delivery to the cancer cells. Smart DNA nanostructures, owing to their various shapes, sizes, geometry, sequences, and characteristics, have various modes of cellular internalization and final disposition. On the other hand, functionalized DNA nanocarriers have specific receptor-mediated uptake, and most of these ligand anchored nanostructures able to escape lysosomal degradation. DNA-based and stimuli responsive nano-carrier systems are the latest advancement in cancer targeting. The data exploration from various studies demonstrated that the DNA nanostructure and stimuli responsive drug delivery systems are perfect tools to overcome the problems existing in the cancer treatment including toxicity and compromised drug efficacy. In this light, the review summarized the insights about various types of DNA nanostructures and stimuli responsive nanocarrier systems applications for diagnosis and treatment of cancer.

Stimuli-responsive materials offer a large variety of possibilities in fabrication of solid- state devices. Phase change materials (PCMs) undergo rapid and drastic changes of their optical properties upon switching from one crystallographic phase to another one. This peculiarity makes PCMs ideal candidates for a number of applications including sensors, active displays, photonic volatile and non-volatile memories for information storage and computer science and optoelectronic devices. This review analyzes different examples of PCMs, in particular germanium–antimonium tellurides and vanadium dioxide (VO2) and their applications in the above-mentioned fields, with a detailed discussion on potential, limitations and challenges.

Properties and applications of synthetic thiol- and disulfide-based materials, principally polymers, are reviewed. Emphasis is placed on soft and self-assembling materials in which interconversion of the thiol and disulfide groups initiates stimulus-responses and/or self-healing for biomedical and non-biomedical applications.

Simple Summary Cancer remains as the world second leading cause of death. The severe side effects associated to high doses of chemotherapy and the development of drug resistance are major drawbacks for a successful cancer treatment. Therefore, new formulations that promote localized therapy at tumor sites are needed to improve the therapeutic outcomes and patient welfare. The use of hydrogels is a very promising alternative, since they can be composed by smart materials able to respond to external factors, changing their properties accordingly and promoting a localized drug delivery. As a result, a more specific, efficient, and less toxic local cancer treatment can be accomplished. In this context, the most important characteristics of hydrogels recent studies regarding the application of pH-, light-, ionic strength-, and magnetic-responsive hydrogels in cancer treatment are here presented. Abstract Cancer remains as the second leading cause of death, worldwide. Despite the enormous important advances observed in the last decades, advanced stages of the disease remain incurable. The severe side effects associated to systemic high doses of chemotherapy and the development of drug resistance impairs a safe and efficiency anticancer therapy. Therefore, new formulations are continuously under research and development to improve anticancer drugs therapeutic index through localized delivery at tumor sites. Among a wide range of possibilities, hydrogels have recently gained special attention due to their potential to allow in situ sustained and controlled anticancer drug release. In particular, stimuli-responsive hydrogels which are able to change their physical state from liquid to gel accordingly to external factors such as temperature, pH, light, ionic strength, and magnetic field, among others. Some of these formulations presented promising results for the localized control and treatment of cancer. The present work aims to discuss the main properties and application of stimuli-responsive hydrogels in cancer treatment and summarize the most important advances observed in the last decades focusing on the use of pH-, light-, ionic strength-, and magnetic-responsive hydrogels.

The efficient and selective delivery of therapeutic drugs to the target site remains the main obstacle in the development of new drugs and therapeutic interventions. Up until today, nanomicelles have shown their prospective as nanocarriers for drug delivery owing to their small size, good biocompatibility, and capacity to effectively entrap lipophilic drugs in their core. Nanomicelles are formed via self-assembly in aqueous media of amphiphilic molecules into well-organized supramolecular structures. Molecular weights and structure of the core and corona forming blocks are important properties that will determine the size of nanomicelles and their shape. Selective delivery is achieved via novel design of various stimuli-responsive nanomicelles that release drugs based on endogenous or exogenous stimulations such as pH, temperature, ultrasound, light, redox potential, and others. This review summarizes the emerging micellar nanocarriers developed with various designs, their outstanding properties, and underlying principles that grant targeted and continuous drug delivery. Finally, future perspectives, and challenges for nanomicelles are discussed based on the current achievements and remaining issues.

A synthetic route for redox-sensitive and non-sensitive core multi-shell (CMS) carriers with sizes below 20 nm and narrow molecular weight distributions was established. Cyclic voltammetric measurements were conducted characterizing the redox potentials of reduction-sensitive CMS while showcasing its reducibility through glutathione and tris(2-carboxyethyl)-phosphine as a proof of concept. Measurements of reduction-initiated release of the model dye Nile red by time-dependent fluorescence spectroscopy showed a pronounced release for the redox-sensitive CMS nanocarrier (up to 90% within 24 h) while the non-sensitive nanocarriers showed no release in PBS. Penetration experiments using ex vivo human skin showed that the redox-sensitive CMS nanocarrier could deliver higher percentages of the loaded macrocyclic dye meso-tetra (m-hydroxyphenyl) porphyrin (mTHPP) to the skin as compared to the non-sensitive CMS nanocarrier. Encapsulation experiments showed that these CMS nanocarriers can encapsulate dyes or drugs with different molecular weights and hydrophobicity. A drug content of 1 to 6 wt% was achieved for the anti-inflammatory drugs dexamethasone and rapamycin as well as fluorescent dyes such as Nile red and porphyrins. These results show that redox-initiated drug release is a promising strategy to improve the topical drug delivery of macrolide drugs.

The role of specific interactions in the self-assembly process of low molecular weight gelators (LMWGs) was studied by altering the nonbonding interactions responsible for gel formation via structural modification of the gelator/nongelator. This was achieved by modifying pyridyl moieties of bis(pyridyl) urea-based hydrogelator (4&ndash, BPU) and the isomer (3&ndash, BPU) to pyridyl N&ndash, oxide compounds (L1 and L2, respectively). The modification of the functional groups resulted in the tuning of the gelation properties of the parent gelator, which induced/enhanced the gelation properties. The modified compounds displayed better mechanical and thermal stabilities and the introduction of the N&ndash, oxide moieties had a prominent effect on the morphologies of the gel network, which was evident from the scanning electron microscopy (SEM) images. The effect of various interactions due to the introduction of N&ndash, oxide moieties in the gel network formation was analyzed by comparing the solid-state interactions of the compounds using single crystal X-ray diffraction and computational studies, which were correlated with the enhanced gelation properties. This study shows the importance of specific nonbonding interactions and the spatial arrangement of the functional groups in the supramolecular gel network formation.

Integration of materials acts as a bridge between the electronic and biological worlds, which has revolutionized the development of bioelectronic devices. This review highlights the rapidly emerging field of switchable interface and its bioelectronics applications. This review article highlights the role and importance of two-dimensional (2D) materials, especially graphene, in the field of bioelectronics. Because of the excellent electrical, optical, and mechanical properties graphene have promising application in the field of bioelectronics. The easy integration, biocompatibility, mechanical flexibility, and conformity add impact in its use for the fabrication of bioelectronic devices. In addition, the switchable behavior of this material adds an impact on the study of natural biochemical processes. In general, the behavior of the interfacial materials can be tuned with modest changes in the bioelectronics interface systems. It is also believed that switchable behavior of materials responds to a major change at the nanoscale level by regulating the behavior of the stimuli-responsive interface architecture.

In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)20-b-poly(N-isopropylacrylamide)11-b-poly(oligo ethylene glycol methyl ether acrylate)18 (PDMAEA20-b-PNIPAM11-b-POEGA18) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and 1H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q1PDMAEA20-b-PNIPAM11-b-POEGA18 as well as the Q6PDMAEA20-b-PNIPAM11-b-POEGA18 quaternized triblock terpolymers (Q1 and Q6 prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH3I) and 1-iodohexane (C6H13I) as the quaternizing agents and the SPDMAEA20-b-PNIPAM11-b-POEGA18 sulfobetainized triblock terpolymer using 1,3 propanesultone (C3H6O3S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery.

One strategy that has gained much attention in the last decades is the understanding and further mimicking of structures and behaviours found in nature, as inspiration to develop materials with additional functionalities. This review presents recent advances in stimuli-responsive gels with emphasis on functional hydrogels and microgels. The first part of the review highlights the high impact of stimuli-responsive hydrogels in materials science. From macro to micro scale, the review also collects the most recent studies on the preparation of hybrid polymeric microgels composed of a nanoparticle (able to respond to external stimuli), encapsulated or grown into a stimuli-responsive matrix (microgel). This combination gave rise to interesting multi-responsive functional microgels and paved a new path for the preparation of multi-stimuli “smart” systems. Finally, special attention is focused on a new generation of functional stimuli-responsive polymer hydrogels able to self-shape (shape-memory) and/or self-repair. This last functionality could be considered as the closing loop for smart polymeric gels., This work is funded by National Funds through FCT—Portuguese Foundation for Science and Technology, Reference UID/CTM/50025/2013 and FEDER funds through the COMPETE 2020 Program under the project number POCI-01-0145-FEDER-007688. C. Echeverria acknowledges the Juan de la Cierva contract (IJCI-2015-26432) from MINECO—Spanish Ministry of Economy, Industry and Competitiveness.