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Four-dimensional printing refers to a process through which a 3D printed object transforms from one structure into another through the influence of an external energy input. Self-folding structures have been extensively studied to advance 3D printing technology into 4D using stimuli-responsive polymers. Designing and applying self-folding structures requires an understanding of the material properties so that the structural designs can be tailored to the targeted applications. Poly(N-iso-propylacrylamide) (PNIPAM) was used as the thermo-responsive material in this study to 3D print hydrogel samples that can bend or fold with temperature changes. A double-layer printed structure, with PNIPAM as the self-folding layer and polyethylene glycol (PEG) as the supporting layer, provided the mechanical robustness and overall flexibility to accommodate geometric changes. The mechanical properties of the multi-material 3D printing were tested to confirm the contribution of the PEG support to the double-layer system. The desired folding of the structures, as a response to temperature changes, was obtained by adding kirigami-inspired cuts to the design. An excellent shape-shifting capability was obtained by tuning the design. The experimental observations were supported by COMSOL Multiphysics® software simulations, predicting the control over the folding of the double-layer systems. [ABSTRACT FROM AUTHOR]

In cancer therapy, it is essential to selectively release cytotoxic agents into the tumor to prevent the adverse effects associated with anticancer drugs. Thus, in this study, a stimuli-sensitive polymer–drug conjugate was synthesized for selective drug release. Doxorubicin (DOX) and docetaxel (DTX) were conjugated onto novel poly(jasmine lactone) based copolymer via a thioketal (TK) linker. In addition, a photosensitizer (chlorin e6) was attached to the polymer, which served as a reactive oxygen species generator to cleave the TK linker. The conjugate is readily self-assembled into micelles less than 100 nm in size. Micelles demonstrate a notable increase in their ability to cause cell death when exposed to near-infrared (NIR) light on MDA-MB-231 breast cancer cells. The increase in cytotoxicity is higher than that observed with the combination of free DOX and DTX. The accumulation of DOX in the nucleus after release from the micelles (laser irradiation) was also confirmed by confocal microscopy. In the absence of light, micelles did not show any toxicity while the free drugs were found toxic irrespective of the light exposure. The obtained results suggest the targeted drug delivery potential of micelles regulated by the external stimuli, i.e., NIR light. [ABSTRACT FROM AUTHOR]

Monoolein cubic phase incorporating poly(dimethylaminoethyl methacrylate-co-phenyl vinyl sulfide) (P(DMAEMA-co-PVS)) and indocyanine green (ICG, a photosensitizer) was prepared as a multiple-responsive carrier. P(DMAEMA-co-PVS), prepared by a free radical polymerization, was air/water interface-active and it exhibited lower critical solution temperature (LCST). The polymer increased in its LCST by H2O2 treatment, possibly because of the hydrolytic detachment of DMAEMA pendant, evidenced by 1H NMR and FT-IR spectroscopy. Water channels surrounded by lipid matrix, characteristic of cubic phase, was observed on TEM photos and the inclusion of the additives (e.g., P(DMAEMA-co-PVS) had little effect on the structure. The cubic phases increased their thermal stability upon the inclusion of the polymer chains and they maintained their integrity once the temperature was kept below 60 °C, supported by the polarized optical microscopy and the differential scanning calorimetry. The release of a cargo (i.e., fluorescent dextran) was suppressed at body temperature (37 °C) at the H2O2 concentration of normal tissue (e.g., 0.000002%), possibly due to an entangled network structure formed by the thermally induced inter/intramolecular hydrophobic interaction of the polymer chains. The release was markedly promoted at the H2O2 concentration of tumor tissue (e.g., 0.0034%), possibly because the thermally induced hydrophobic interaction can be weakened by the hydrolytic degradation. In addition, the release was significantly enhanced by NIR irradiation. The cubic phase would be used as a drug carrier which releases its payload at a target site in a selected manner in answering to H2O2 and NIR irradiation. [ABSTRACT FROM AUTHOR]

Hydrogels comprise of a group of crosslinked hydrophilic polymeric materials which are capable of absorbing and holding large quantities of water in their three-dimensional network structure without undergoing dissolution. More importantly, the ability of 'smart' hydrogels to respond to certain environmental changes e.g. pH, heat, light, magnetic field, biomolecules have set them apart as a unique class of materials. A combination of several such useful and unique properties have resulted in a tremendous progress toward development of advanced hydrogel-based materials, as is evident from an explosive amount of research publications available in this area over the last few decades. Owing particularly to their biocompatibility and biodegradability, hydrogels have become a material of prime importance in context to a wide range of applications starting from simple contact lenses to more complex ones e.g. in tissue repair, drug delivery, sensors, 3D bioprinting, soft robotics and agriculture. This review includes i) an overview of hydrogels and its classifications based on source, structure, crosslinking mechanism and stimuli responsiveness, ii) detailed discussion on some of the most advanced research works being carried out in the field over the last few years in context to few smart applications that have become the need of the hour, particularly in the domain of biomedical applications. [ABSTRACT FROM AUTHOR]

This work demonstrates our effort to develop stimuli responsive cellulose films for the detection of dimethyl amines, a biogenic amine, released during food decomposition. Herein, we demonstrate that thin layer deposition of polydiacetylene‐zinc oxide nanosheets (PDA‐ZnO) on cellulose (CE) paper yields a stimuli responsive strip exhibiting strong thermochromism and solvatochromism against dimethyl amine. The incorporation of Zn nanoclusters within the composite plays an essential role in achieving reversible thermochromism while strong intermolecular interactions promote adsorption of PDA‐ZnO on cellulose paper. X‐ray diffraction and infrared spectroscopy reveal that the Zn2+ ions intercalate with PDA bilayer and strongly interact with the carboxylate headgroup of PDA. Furthermore, the reversible thermochromism persist when the nanosheets are deposited on cellulose (CE) paper when assembling PDA‐ZnO−CE paper. In addition, PDA‐ZnO−CE displayed selective solvatochromism allowing the utilization of the paper in the detection of dimethyl amine as it displayed a distinct and remarkable purple to orange colour transition. In particular, the response of the PDA‐ZnO−CE paper in several other organic solvents was poor as no transitions were observed hence its selectivity towards dimethylamine. In conclusion, the incorporation of PDA‐ZnO on cellulose paper is a step forward towards designing of a stimuli responsive packaging material that can detect biogenic amines released during food decomposition thereby preventing food poisoning. [ABSTRACT FROM AUTHOR]

Nanotechnology-enabled pesticide delivery systems have been widely studied and show great prospects in modern agriculture. Nanodelivery systems not only achieve the controlled release of agrochemicals but also possess many unique characteristics. This study presents the development of a pH-responsive pesticide nanoformulation utilizing hollow mesoporous silica nanoparticles (HMSNs) as a nanocarrier. The nanocarrier was loaded with the photosensitive pesticide prochloraz (Pro) and then combined with ZnO quantum dots (ZnO QDs) through electrostatic interactions. ZnO QDs serve as both the pH-responsive gatekeeper and the enhancer of the pesticide. The results demonstrate that the prepared nanopesticide exhibits high loading efficiency (24.96%) for Pro. Compared with Pro technical, the degradation rate of Pro loaded in HMSNs@Pro@ZnO QDs was reduced by 26.4% after 24 h ultraviolet (UV) exposure, indicating clearly improved photostability. In a weak acidic environment (pH 5.0), the accumulated release of the nanopesticide after 48 h was 2.67-fold higher than that in a neutral environment. This indicates the excellent pH-responsive characteristic of the nanopesticide. The tracking experiments revealed that HMSNs can be absorbed by rice leaves and subsequently transported to other tissues, indicating their potential for effective systemic distribution and targeted delivery. Furthermore, the bioactivity assays confirmed the fungicidal efficacy of the nanopesticide against rice blast disease. Therefore, the constructed nanopesticide holds great prospect in nanoenabled agriculture, offering a novel strategy to enhance pesticide utilization. [ABSTRACT FROM AUTHOR]

Development of efficient and low cost electrocatalysts has been an important area of research in the field of materials chemistry. In this regard metal‐organic gels (MOGs) are one of the promising materials and they are being utilized for various materials applications including energy conversion and storage. Electrochemical applications of the MOGs are still in its infancy and further studies are required for exploration of structure‐property correlation that is crucial for targeted and efficient materials design. Herein we report multi stimuli responsive MOGs containing a tris‐tetrazole‐tri‐amido based organic ligand. The self‐assembly of the threefold symmetric ligand with Co(II)/Ni(II) acetates results in the MOGs with distinct morphological and structural characteristics, regardless of containing the same organic ligand. These MOGs were synthesized by direct mixing of the precursors under ambient conditions. The xerogels of these MOGs (Co‐MOG′ and Ni‐MOG′) exhibit excellent OER performance as the Co‐MOG′ and Ni‐MOG′ shows the overpotential of 312 mV and 418 mV at 10 mA/cm2 in an alkaline electrolyte. Electrocatalytic performance of the xerogels were correlated to their structural features like distinct morphology and porosity of the material that facilitates the mass transfer and maximum exposure to the electrochemical active sites. Importantly, this work demonstrates the functional application of MOGs as electrocatalysts for OER and the effect of metal ion, porosity and morphology on their overall performance. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive or smart materials have recently shown a significant impact on the frontier of material science and engineering. The exponential development of synthetic host molecules (SHMs) over the last decades and their corresponding host–guest chemistry, have empowered researchers with new opportunities to design and construct tailored or guest‐specific smart materials. In this Minireview, we present the recent advancements in synthetic host based smart materials, ranging from the fabrication strategies to the state‐of‐art applications including adsorption, separation, luminescence, self‐healing and actuation. The role that the host–guest chemistry plays in these systems is highlighted throughout to give a better prospective of the available possibilities for emerging materials of future economies. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive or smart materials have recently shown a significant impact on the frontier of material science and engineering. The exponential development of synthetic host molecules (SHMs) over the last decades and their corresponding host–guest chemistry, have empowered researchers with new opportunities to design and construct tailored or guest‐specific smart materials. In this Minireview, we present the recent advancements in synthetic host based smart materials, ranging from the fabrication strategies to the state‐of‐art applications including adsorption, separation, luminescence, self‐healing and actuation. The role that the host–guest chemistry plays in these systems is highlighted throughout to give a better prospective of the available possibilities for emerging materials of future economies. [ABSTRACT FROM AUTHOR]

The last decade has seen a meteoric rise in studies investigating polymeric aggregates as nanocarriers. When it comes to morphology, size, functionality, and immunostability, polymeric nanocarriers (PNCs) are unparalleled. With characteristics such as large surface area to volume ratio, amphiphilic nano‐environment, non‐toxic components, chemically modifiable composition, external surface alteration potential, uniform particle size, and stimuli‐dependent self‐assembly, PNCs have emerged as strong candidates for therapeutic applications. The article reviews the latest research on different challenges and strategies for targeted drug delivery and shall serve as guide to the researchers in designing site‐specific nanocarriers for application in future. The review systematically discusses the fundamental structural variation of the nanocarriers with emphasis on the influence of chemical alterations and the resulting effects on functionality; addresses the difficulties encountered with modes of administration; target selectivity and stimulus response. [ABSTRACT FROM AUTHOR]

Deoxyribonucleic acid (DNA) hydrogels are a unique class of programmable, biocompatible materials able to respond to complex stimuli, making them valuable in drug delivery, analyte detection, cell growth, and shape‐memory materials. However, unmodified DNA hydrogels in the literature are very soft, rarely reaching a storage modulus of 103 Pa, and they lack functionality, limiting their applications. Here, a DNA/small‐molecule motif to create stiff hydrogels from unmodified DNA, reaching 105 Pa in storage modulus is used. The motif consists of an interaction between polyadenine and cyanuric acid—which has 3‐thymine like faces—into multimicrometer supramolecular fibers. The mechanical properties of these hydrogels are readily tuned, they are self‐healing and thixotropic. They integrate a high density of small, nontoxic molecules, and are functionalized simply by varying the molecule sidechain. They respond to three independent stimuli, including a small molecule stimulus. These stimuli are used to integrate and release DNA wireframe and DNA origami nanostructures within the hydrogel. The hydrogel is applied as an injectable delivery vector, releasing an antisense oligonucleotide in cells, and increasing its gene silencing efficacy. This work provides tunable, stimuli‐responsive, exceptionally stiff all‐DNA hydrogels from simple sequences, extending these materials' capabilities. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive polymer networks like microgels and hydrogels possess a variety of properties that need to be analyzed for their rational design and successful application in the targeted field of interest. Nanoscale characterization of gels can be achieved by highly selective and sensitive techniques including high‐resolution NMR spectroscopy, relaxometry, and diffusometry. This review is focusing on recent results using 1H and 13C 1D and 2D NMR techniques, which give chemically site‐selective information about the polymer network revealing the interplay between structure and dynamics of polymer networks at the nanoscale level. By that, NMR can allow to obtain information about i) internal structure, ii) stimuli‐induced phase transition, iii) mesh size, and iv) aggregation of microgels and hydrogels. The rational design of responsive microgels and hydrogels with application in drug delivery, cell carrier systems, catalysis, actuators, and as antibacterial agent can be made, if crucial polymer network properties can be correlated with cross‐linking density, type of cross‐link interactions, electrical charges, hydrophobic nano‐structuring, and dispersion concentration. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] Cesium lead halide perovskite quantum dots (QDs) have attracted immense attention for luminescent materials due to their narrow emission bands and color-tunable emission. However, indispensable surface ligands originating from ligand-assisted synthesis strategies severely deteriorate the stability and luminescence properties of QDs since these ligands have a highly dynamic binding. Herein, we used a green fluorescence BODIPY molecule containing thiol (named SH-BDP) to regulate the CsPbBr 3 QDs surface by ligand regulation. Density functional theory calculations proved that the SH-BDP molecule could bind to the exposed Pb of CsPbBr 3 QDs stronger than traditional ligands to form stable SH-BDP-QDs. Moreover, the SH-BDP fixed on the CsPbBr 3 QDs surface can improve water and light resistance. It also served as a knob to tune their luminescence properties and the reversible thermal-stimuli response. Finally, the multi-response property of SH-BDP-QDs was realized under polar solvent or heat along with UV light. In addition, we used the SH-BDP-QDs to create various anti-counterfeiting labels; several luminous modes were achieved under different external stimuli, which improved the quality of the optical anti-counterfeiting labels and ensured information security. This work indicates the immense potential of surface ligand manipulation in improving the stability and multi-stimuli-responsive optical encoding of perovskite quantum dots. [ABSTRACT FROM AUTHOR]

Addressing the challenge of poor wound healing in chronic wounds remains complex, as the underlying physiological mechanisms are still not fully understood. Traditional wound dressings often fail to meet the specific needs of the chronic wound healing process. Recently, considerable interest has shifted toward employing biomacromolecule-based smart wound dressings to facilitate wound healing. These stimuli-responsive dressings have undergone substantial development to manage local drug delivery, demonstrating promising therapeutic effects in treating chronic wound defects. They have displayed improved drug release profiles both in vitro and in vivo. Recently, there have been advancements in the development of innovative dual and multi-stimuli responsive dressings that react to combinations of signals including pH-temperature, pH-enzyme, pH-ROS, pH-glucose, pH-NIR, and multiple stimuli. This paper offers an in-depth review of recent progress in responsive wound dressings based on biomacromolecules, with a specific focus on their design, drug release capabilities, and therapeutic advantages. [ABSTRACT FROM AUTHOR]

Bilirubin (BR) is among the most potent endogenous antioxidants that originates from the heme catabolic pathway. Despite being considered as a dangerous and cytotoxic waste product at high concentrations, BR has potent antioxidant effects leading to the reduction of oxidative stress and inflammation, which play an important role in the development and progression of cancer. The purpose of this study is to introduce PEGylated BR nanoparticles (NPs), themselves or in combination with other anti-cancer agents. BR is effective when loaded into various nanoparticles and used in cancer therapy. Interestingly, BRNPs can be manipulated to create stimuli-responsive carriers providing a sustained and controlled, as well as on-demand, release of drug in response to internal or external factors such as reactive oxygen species, glutathione, light, enzymes, and acidic pH. This review suggests that BRNPs have the potential as tumor microenvironment-responsive delivery systems for effective targeting of various types of cancers. [Display omitted] [ABSTRACT FROM AUTHOR]

Addressing the challenge of poor wound healing in chronic wounds remains complex, as the underlying physiological mechanisms are still not fully understood. Traditional wound dressings often fail to meet the specific needs of the chronic wound healing process. Recently, considerable interest has shifted toward employing biomacromolecule-based smart wound dressings to facilitate wound healing. These stimuli-responsive dressings have undergone substantial development to manage local drug delivery, demonstrating promising therapeutic effects in treating chronic wound defects. They have displayed improved drug release profiles both in vitro and in vivo. Recently, there have been advancements in the development of innovative dual and multi-stimuli responsive dressings that react to combinations of signals including pH-temperature, pH-enzyme, pH-ROS, pH-glucose, pH-NIR, and multiple stimuli. This paper offers an in-depth review of recent progress in responsive wound dressings based on biomacromolecules, with a specific focus on their design, drug release capabilities, and therapeutic advantages. [ABSTRACT FROM AUTHOR]

Spinal cord injury (SCI) is a debilitating condition that can result in significant functional impairment and loss of quality of life. There is a growing interest in developing new therapies for SCI, and hydrogel-based multimodal therapeutic strategies have emerged as a promising approach. They offer several advantages for SCI repair, including biocompatibility, tunable mechanical properties, low immunogenicity, and the ability to deliver therapeutic agents. This article provides an overview of the recent advances in hydrogel-based therapy strategies for SCI repair, particularly within the past three years. We summarize the SCI hydrogels with varied characteristics such as phase-change hydrogels, self-healing hydrogel, oriented fibers hydrogel, and self-assembled microspheres hydrogel, as well as different functional hydrogels such as conductive hydrogels, stimuli-responsive hydrogels, adhesive hydrogel, antioxidant hydrogel, sustained-release hydrogel, etc. The composition, preparation, and therapeutic effect of these hydrogels are briefly discussed and comprehensively evaluated. In the end, the future development of hydrogels in SCI repair is prospected to inspire more researchers to invest in this promising field. Various types of hydrogels, including phase-change hydrogels, self-healing hydrogel, oriented fibers hydrogel, and self-assembled microspheres hydrogel, as well as different functional hydrogels such as conductive hydrogels, stimuli-responsive hydrogels, are employed as biological scaffolds, combined with stem cells, exosomes, and neurotrophic factors, in the treatment of SCI. [Display omitted] [ABSTRACT FROM AUTHOR]

Lung cancer is one of the most common cancers, affecting more than 2.1 million people across the globe every year. A very high occurrence and mortality rate of lung cancer have prompted active research in this area with both conventional and novel forms of therapies including the use of nanomaterials based drug delivery agents. Specifically, the unique physico-chemical and biological properties of porous nanomaterials have gained significant momentum as drug delivery agents for delivering a combination of drugs or merging diagnosis with targeted therapy for cancer treatment. This review focuses on the emergence of nano-porous materials for drug delivery in lung cancer. The review analyses the currently used nanoporous materials, including inorganic, organic and hybrid porous materials for delivering drugs for various types of therapies, including chemo, radio and phototherapy. It also analyses the selected research on stimuli-responsive nanoporous materials for drug delivery in lung cancer before summarizing the various findings and projecting the future of emerging trends. This review provides a strong foundation for the current status of the research on nanoporous materials, their limitations and the potential for improving their design to overcome the unique challenges of delivering drugs for the treatment of lung cancer. [ABSTRACT FROM AUTHOR]

Electromerism is a very well‐known phenomenon in transition metal chemistry. In main group chemistry, this concept has only started getting attention recently. We report stimuli responsive low‐valent silicon compounds exhibiting electromerism. A mixed‐valent silaiminyl‐silylene 1, [LSi−Si(NDipp)L] (L=PhC(NtBu)2), was synthesized in a single step from amidinate‐chlorosilylene. Compound 1 has two interconnected Si atoms in formally +I and +III oxidation states. Upon treatment with Lewis acidic CuIX (X=mesityl, Cl, Br, I), electron redistribution occurs resulting in the formation of [{LSi(NDipp)Si(L)}−CuX], in which both silicon atoms are in the +II formal oxidation state. Removal of the copper center from [{LSi(NDipp)Si(L)}−CuX] by using a Lewis basic carbene led to reformation of the precursor [LSi−Si(NDipp)L]. Thus, the process is fully reversible. This showcases the first example of Lewis acid/base‐induced reversible electromerism in silicon chemistry. [ABSTRACT FROM AUTHOR]

Electromerism is a very well‐known phenomenon in transition metal chemistry. In main group chemistry, this concept has only started getting attention recently. We report stimuli responsive low‐valent silicon compounds exhibiting electromerism. A mixed‐valent silaiminyl‐silylene 1, [LSi−Si(NDipp)L] (L=PhC(NtBu)2), was synthesized in a single step from amidinate‐chlorosilylene. Compound 1 has two interconnected Si atoms in formally +I and +III oxidation states. Upon treatment with Lewis acidic CuIX (X=mesityl, Cl, Br, I), electron redistribution occurs resulting in the formation of [{LSi(NDipp)Si(L)}−CuX], in which both silicon atoms are in the +II formal oxidation state. Removal of the copper center from [{LSi(NDipp)Si(L)}−CuX] by using a Lewis basic carbene led to reformation of the precursor [LSi−Si(NDipp)L]. Thus, the process is fully reversible. This showcases the first example of Lewis acid/base‐induced reversible electromerism in silicon chemistry. [ABSTRACT FROM AUTHOR]

Cancer seriously threatens human health. Surgery, radiotherapy and chemotherapy are the three pillars of traditional cancer treatment, with targeted therapy and immunotherapy emerging over recent decades. Standard drug regimens are mostly executed via intravenous injection (IV), especially for chemotherapy agents. However, these treatments pose severe risks, including off-target toxic side effects, low drug accumulation and penetration at the tumor site, repeated administration, etc., leading to inadequate treatment and failure to meet patients' needs. Arising from these challenges, a local regional anticancer strategy has been proposed to enhance therapeutic efficacy and concomitantly reduce systemic toxicity. With the advances in biomaterials and our understanding of the tumor microenvironment, in situ stimulus-responsive hydrogels, also called smart hydrogels, have been extensively investigated for local anticancer therapy due to their injectability, compatibility and responsiveness to various stimuli (pH, enzyme, heat, light, magnetic fields, electric fields etc.). Herein, we focus on the latest progress regarding various stimuli that cause phase transition and drug release from smart hydrogels in local regional anticancer therapy. Additionally, the challenges and future trends of the reviewed in situ smart hydrogels for local drug delivery are summarized and proposed. [ABSTRACT FROM AUTHOR]

Systemic treatments for rheumatoid arthritis are associated with many side effects. This study aimed to minimize the side effects associated with the systemic administration of leflunomide (LEF) by formulating LEF-loaded emulsomes (EMLs) for intra-articular administration. Additionally, EMLs were loaded with supramagnetic nanoparticles (SPIONs) to enhance joint localization, where a magnet was placed on the joint area after intra-articular administration. Full in vitro characterization, including colloidal characteristics, entrapment efficiency, and in vitro release were conducted besides the in vivo evaluation in rats with adjuvant-induced arthritis. In vivo study included joint diameter measurement, X-ray radiographic analysis, RT-PCR analysis, Western blotting, ELISA for inflammatory markers, and histopathological examination of dissected joints. The particle size and entrapment efficiency of the selected LEF SPION EMLs were 198.2 nm and 83.7%, respectively. The EMLs exhibited sustained release for 24 h. Moreover, in vivo evaluation revealed LEF SPION EMLs to be superior to the LEF suspension, likely due to the increase in LEF solubility by nanoencapsulation that improved the pharmacological effects and the use of SPION that ensured the localization of EMLs in the intra-articular cavity upon administration. [ABSTRACT FROM AUTHOR]

Intelligent nanomedicines integrated with stimuli-responsive components enable on-demand customizable treatment options which would improve therapeutic outcome and reduce systemic toxicity. In this work, we explore the synergistic therapeutic potential of photodynamic therapy and immunometabolic modulation to achieve tumour regression and to trigger an adaptive immunity to prevent tumour recurrence. The therapeutic potential of the fabricated Bioengineered Immunomodulatory Organelle targeted Nanozymes (BIONs) was tested on 3D printed mini-brains which could effectively recapitulate the biologically relevant interactions between glioblastoma cells and macrophages. In the presence of glioblastoma organotypic brain slices, activated BIONs upregulated the cell surface expression of CD86, a costimulatory molecule and CD83, maturation marker, on monocyte derived dendritic cells, suggesting its ability to elicit a strong immune response. Furthermore, the antigen pulsed dendritic cells by chemotaxis and transendothelial migration readily relocate into the draining lymph node where they present the antigenic cargo to enable the proliferation of T lymphocytes. The stealth and tunable catalytic activity of BIONs prevent ROS mediated diseases such as acute kidney injury by providing environment dependent protection without compromising on its promising anti-cancer activity. [Display omitted] [ABSTRACT FROM AUTHOR]

In this work, using supramolecular polyurethanes theories, two polycaprolactone-based polyurethanes with 2-ureido-4-[1H]-pyrimidinone (UPy) motifs capable of forming quadruple hydrogen bonds were synthetized and characterized, focusing our attention on their capability to show thermally activated shape-memory response. In particular, 1H NMR analyses confirmed the chemical structure of the supramolecular polyurethanes, while DSC showed their totally amorphous morphology. DMTA in tensile mode was used to study their thermally activated shape-memory properties. In our case, the UPy units are the switching domains while the network formed by the segregated hard segments is the permanent domain obtained materials with excellent shape-memory response at both 100 and 85 °C. These materials are promising for multi-responsive materials where bio-based and potentially recyclable polymers with excellent shape-memory properties are needed. [ABSTRACT FROM AUTHOR]

Traditional open surgery complications are typically due to trauma caused by accessing the procedural site rather than the procedure itself. Minimally invasive surgery allows for fewer complications as microdevices operate through small incisions or natural orifices. However, current minimally invasive tools typically have restricted maneuverability, accessibility, and positional control of microdevices. Thermomagnetic-responsive microgrippers are microscopic multi-fingered devices that respond to temperature changes due to the presence of thermal-responsive polymers. Polymeric devices, made of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAM-AAc) and polypropylene fumarate (PPF), self-fold due to swelling and contracting of the hydrogel layer. In comparison, soft metallic devices feature a pre-stressed metal bilayer and polymer hinges that soften with increased temperature. Both types of microdevices can self-actuate when exposed to the elevated temperature of a cancerous tumor region, allowing for direct targeting for biopsies. Microgrippers can also be doped to become magnetically responsive, allowing for direction without tethers and the retrieval of microdevices containing excised tissue. The smaller size of stimuli-responsive microgrippers allows for their movement through hard-to-reach areas within the body and the successful extraction of intact cells, RNA and DNA. This review discusses the mechanisms of thermal- and magnetic-responsive microdevices and recent advances in microgripper technology to improve minimally invasive surgical techniques. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) play a crucial role in the design of novel materials. The ionic nature of ILs provides numerous advantages in drug delivery, acting as a green solvent or active ingredient to enhance the solubility, permeability, and binding efficiency of drugs. They could also function as a structuring agent in the development of nano/micro particles for drug delivery, including micelles, vesicles, gels, emulsion, and more. This review summarize the ILs and IL-based gel structures with their advanced drug delivery applications. The first part of review focuses on the role of ILs in drug formulation and the applications of ILs in drug delivery. The second part of review offers a comprehensive overview of recent drug delivery applications of IL-based gel. It aims to offer new perspectives and attract more attention to open up new avenues in the biomedical applications of ILs and IL-based gels. [Display omitted] • Discussion on the classification and properties of ionic liquids, along with their key roles in drug formulation. • Identification of the properties and applications of ionic liquids and ionogels in various delivery methods. • Exploration of the classification, preparation, processing methods, and biomedical characteristics of ionogel. • Highlighting the challenges associated with ionic liquids and ionogels in drug delivery. [ABSTRACT FROM AUTHOR]

α-cyanostilbene derivatives, known as AIE molecules, have the potential to serve as optical recorders and vapor sensor by altering the molecular aggregation and / or stacking models. Despite the significant scientific and technological importance of the correlation between molecular stacking modes and modulated optical properties, relevant research remains scarce. Herein, two thermodynamically stable crystalline phase (BCr and GCr) were found for a biphenyl-based cyanostilbenic compound, DSB-SQ , condensed from its solution. Uniquely, the BCr demonstrated reversible mechanochromism and irreversible thermalchromism, whereas GCr remained unaffected by exposure to light, heat, grinding, etc. The discoloration process was correlated with the variation of local dipole coupling modes during the phase transition, leading to a significant change in π-π overlap and delocalization of excited states. Finally, the BCr was doped with polyvinyl alcohol (PVA) to prepare a composite membrane with dynamic information storage and encryption function. [Display omitted] [ABSTRACT FROM AUTHOR]

Design and fabrication of freestanding chiro‐photonic crystal film with the ability to change color over the whole visible light spectrum is appealing for anticounterfeiting technology and smart labels. Utilizing a newly synthesized light‐responsive molecular motor functionalized with cholesterol (chol‐MM) on the rotor, novel light‐controlled photonic crystal is prepared by doping the novel chol‐MM into liquid crystals (LCs). Thanks to the liquid crystalline cholesterol substituent, the chol‐MM can be triggered by visible light (420 nm). At the same time, the miscibility of chol‐MM in LC matrix is significantly enhanced. Integrating the chol‐MM with thermochromic hydrogen‐bonded LC matrix, thermal and light dual‐responsive cholesteric LC (CLC) material is prepared, in which the nanoscale helical pitch is tunable by photo‐induced molecular motions of chol‐MM. More importantly, utilizing UV‐initiated polymerization of the visible light‐modulated CLC material, structural colored photonic crystal films with arbitrary colorful patterns are fabricated. Such freestanding helical nanostructured labels have potential in the application of encrypted communication and anticounterfeiting. [ABSTRACT FROM AUTHOR]

Protein therapeutics have become increasingly popular for the treatment of a variety of diseases owing to their specificity to targets of interest. However, challenges associated with them have limited their use for a range of ailments, including the limited options available for local controlled delivery. To address this challenge, degradable hydrogel microparticles, or microgels, loaded with model biocargoes were created with tunable release profiles or triggered burst release using chemistries responsive to endogenous or exogeneous stimuli, respectively. Specifically, microfluidic flow-focusing was utilized to form homogenous microgels with different spontaneous click chemistries that afforded degradation either in response to redox environments for sustained cargo release or light for on-demand cargo release. The resulting microgels were an appropriate size to remain localized within tissues upon injection and were easily passed through a needle relevant for injection, providing means for localized delivery. Release of a model biopolymer was observed over the course of several weeks for redox-responsive formulations or triggered for immediate release from the light-responsive formulation. Overall, we demonstrate the ability of microgels to be formulated with different materials chemistries to achieve various therapeutic release modalities, providing new tools for creation of more complex protein release profiles to improve therapeutic regimens. [ABSTRACT FROM AUTHOR]

Recently, we presented a strategy for packaging peptides as side‐chains in high‐density brush polymers. For this globular protein‐like polymer (PLP) formulation, therapeutic peptides were shown to resist proteolytic degradation, enter cells efficiently and maintain biological function. In this paper, we establish the role charge plays in dictating the cellular uptake of these peptide formulations, finding that peptides with a net positive charge will enter cells when polymerized, while those formed from anionic or neutral peptides remain outside of cells. Given these findings, we explored whether cellular uptake could be selectively induced by a stimulus. In our design, a cationic peptide is appended to a sequence of charge‐neutralizing anionic amino acids through stimuli‐responsive cleavable linkers. As a proof‐of‐concept study, we tested this strategy with two different classes of stimuli, exogenous UV light and an enzyme (a matrix metalloproteinase) associated with the inflammatory response. The key finding is that these materials enter cells only when acted upon by the stimulus. This approach makes it possible to achieve delivery of the polymers, therapeutic peptides or an appended cargo into cells in response to an appropriate stimulus. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] • DMSN with highly loaded hydrophobic drug was used as the drug delivery vehicle. • DMSN featured with small particle size, high pore volume and large pore size. • A vacuum rotary evaporation-mediated casting method was applied for drug loading. • A GSH-responsive PMAsh shell and Tf were functionalized for tumor-targeting therapy. The efficacy of hydrophobic chemotherapy drugs in cancer treatment is often hampered by their poor solubility in the physiological environment, which causes their low delivery efficiency in the body. This manuscript develops an intelligent nanocarrier (~100 nm) drug delivery system that can highly load a water-insoluble drug, and possesses desirable tumor-targeting properties for cancer therapy. In this system, highly porous silica nanoparticles (pore volume ~ 1.4 cm3 g−1) with a dendritic pore structure (denoted as DMSN) are applied as a matrix for drug loading. A facile, vacuum rotary evaporation-mediated casting method is applied to quantitatively load a high content of a hydrophobic drug (i.e., paclitaxel) in the DMSN matrix. A thiol-modified poly(methacrylic acid) (denoted as PMAsh) shell is then assembled and crosslinked via disulfide bonds on the particle surface to improve the dispersibility of the particles in an aqueous environment. After functionalization of the PMAsh shell with the targeting ligand transferrin (Tf), the nanocarriers exhibit accumulation ability on tumor cells, both in vitro and in vivo. Combining the fascinating properties of high drug-loading, excellent colloidal stability, low cytotoxicity, targeting ability and glutathione-responsive PMAsh shell deconstruction properties, the nanocarriers described here hold great promise for the efficient delivery of hydrophobic drugs and tumor treatment. [ABSTRACT FROM AUTHOR]

Chemotherapy using single drug is not successful now a days due to the emergence of multidrug-resistant cancer cells. In the present work, Methotrexate (MTX) and Mitomycin C (MMC) loaded hydrogel sensitive to both reduction and pH are prepared and well characterized using various instrumentation techniques like FTIR, XRD, SEM and TEM. The drug loading and encapsulation efficiencies (DEE and DLE) of MTX are found to be 90.5 and 54.3% respectively and for MMC the value is 95.1 and 62.7% respectively. Invitro cytotoxicity and Apoptosis studies confirm the increased anticancer activity and selectivity of the novel carrier. [ABSTRACT FROM AUTHOR]

Acid stimulus responsive stealthy nanoparticles were prepared by utilizing three types of copolymers, i.e. acid cleavable polycaprolactone-polyethyleneimine-polyethylene glycol (PCL-PEI-PEG), acid charge reversal polycaprolactone-polyethyleneimine (PCL-PEI), and ligand containing polycaprolactone-polyethyleneimine-folate (PCL-PEI-Fol). FTIR, NMR, and UV-visible spectroscopy confirmed the formation of these copolymers. Acid cleavable property of PCL-PEI-PEG copolymer was examined by FTIR. The formation of nanoparticles was determined by DLS and SEM. Aggregation, structural destabilization, and charge reversibility of nanoparticles at low pH were evaluated by DLS, SEM, and Zeta analyzer, respectively. MTT assay was used to evaluate anticancer effect of nanoparticles. Overall, nanoparticles exhibited improved cytotoxic activity against MCF-7 cancer cells. [ABSTRACT FROM AUTHOR]

Developing safe and efficient delivery systems for therapeutic biomacromolecules is a long‐standing challenge. Herein, we report a newly developed combinatorial library of cholesteryl‐based disulfide bond‐containing biodegradable cationic lipidoid nanoparticles. We have identified a subset of this library which is effective for protein and mRNA delivery in vitro and in vivo. These lipidoids showed comparable transfection efficacies but much lower cytotoxicities compared to the Lpf2k in vitro. In vivo studies in adult mice demonstrated the successful delivery of genome engineering protein and mRNA molecules in the skeletal muscle (via intramuscular injection), lung and spleen (via intravenous injection), and brain (via lateral ventricle infusion). [ABSTRACT FROM AUTHOR]

Developing safe and efficient delivery systems for therapeutic biomacromolecules is a long‐standing challenge. Herein, we report a newly developed combinatorial library of cholesteryl‐based disulfide bond‐containing biodegradable cationic lipidoid nanoparticles. We have identified a subset of this library which is effective for protein and mRNA delivery in vitro and in vivo. These lipidoids showed comparable transfection efficacies but much lower cytotoxicities compared to the Lpf2k in vitro. In vivo studies in adult mice demonstrated the successful delivery of genome engineering protein and mRNA molecules in the skeletal muscle (via intramuscular injection), lung and spleen (via intravenous injection), and brain (via lateral ventricle infusion). [ABSTRACT FROM AUTHOR]

Novel thermal- and pH-responsive hollow nanocapsules (HNCaps) were fabricated through the grafting of a thiol-end capped PNIPAAm-b-PAA by thiol-ene "click" reaction onto PMMA HNCaps. The lowest critical solution temperature (LCST) of the fabricated HNCaps was obtained as 38–40°C. The fabricated nanosystem was loaded with doxorubicin hydrochloride (Dox), and its drug loading and encapsulation efficiencies were obtained as 62 and 53%, respectively. The in vitro stimuli-responsive drug release behavior of the fabricated nanomedicine was investigated extensively. The anticancer activity of the drug-loaded HNCaps was evaluated using MTT assay against MCF7 cells. The results exhibited excellent potential of nanosystem as a drug delivery system (DDS) for cancer chemotherapy. Novel thermal- and pH-responsive poly(methyl metacrylate)-grafted-[poly(N-isopropylacrylamide-block-acrylic acid)] hollow nanocapsules were fabricated as "smart" anticancer drug delivery system (DDS). [ABSTRACT FROM AUTHOR]

Conventional tumor-targeted drug delivery systems (DDSs) face challenges, such as unsatisfied systemic circulation, low targeting efficiency, poor tumoral penetration, and uncontrolled drug release. Recently, tumor cellular molecules-triggered DDSs have aroused great interests in addressing such dilemmas. With the introduction of several additional functionalities, the properties of these smart DDSs including size, surface charge and ligand exposure can response to different tumor microenvironments for a more efficient tumor targeting, and eventually achieve desired drug release for an optimized therapeutic efficiency. This review highlights the recent research progresses on smart tumor environment responsive drug delivery systems for targeted drug delivery. Dynamic targeting strategies and functional moieties sensitive to a variety of tumor cellular stimuli, including pH, glutathione, adenosine-triphosphate, reactive oxygen species, enzyme and inflammatory factors are summarized. Special emphasis of this review is placed on their responsive mechanisms, drug loading models, drawbacks and merits. Several typical multi-stimuli responsive DDSs are listed. And the main challenges and potential future development are discussed. [ABSTRACT FROM AUTHOR]

Bioinspired actuators with stimuli-responsive and deformable properties are being pursued in fields such as artificial tissues, medical devices and diagnostics, and intelligent biosensors. These applications require that actuator systems have biocompatibility, controlled deformability, biodegradability, mechanical durability, and stable reversibility. Herein, we report a bionic actuator system consisting of stimuli-responsive genetically engineered silk-elastin-like protein (SELP) hydrogels and wood-derived cellulose nanofibers (CNFs), which respond to temperature and ionic strength underwater by eco-friendly methods. Programmed site-selective actuation can be predicted and folded into three-dimensional (3D) origami-like shapes. The reversible deformation performance of the SELP/CNF actuators was quantified, and complex spatial transformations of multilayer actuators were demonstrated, including a biomimetic flower design with selective petal movements. Such actuators consisting entirely of biocompatible and biodegradable materials will offer an option toward constructing stimuli-responsive systems for in vivo biomedicine soft robotics and bionic research. [ABSTRACT FROM AUTHOR]

Lung cancer is one of the major causes of cancer-related deaths worldwide. Stimuli-responsive polymers and nanoparticles, which respond to exogenous or endogenous stimuli in the tumor microenvironment, have been widely investigated for spatiotemporal chemotherapeutic drug release applications for cancer chemotherapy. We developed glutathione (GSH)-responsive polyurethane nanoparticles (GPUs) using a GSH-cleavable disulfide bond containing polyurethane that responds to elevated levels of GSH within lung cancer cells. The polyurethane nanoparticles were fabricated using a single emulsion and mixed organic solvent method. Cisplatin-loaded GSH-sensitive nanoparticles (CGPU) displayed a GSH-dose dependent release of cisplatin. In addition, a significant reduction in in vitro survival fraction of A549 lung cancer cells was observed compared to free cisplatin of equivalent concentration (survival fraction of ~0.5 and ~0.7, respectively). The in vivo biodistribution studies showed localization of fluorescently labeled GPUs (~7% of total injected dose per gram tissue) in the lung tumor regions after mouse-tail IV injections in xenograft A549 lung tumor models. The animals exposed to CGPUs also exhibited the inhibition of lung tumor growth compared to animals administered with saline (tumor growth rate of 1.5 vs. 13 in saline) and free cisplatin (tumor growth rate of 5.9) in mouse xenograft A549 lung tumor models within 14 days. These nanoparticles have potential to be used for on-demand drug release for an enhanced chemotherapy to effectively treat lung cancer. Unlabelled Image • Glutathione is abundantly available in lung cancer microenvironment. • Biodegradable polyurethane nanoparticles were fabricated via a single emulsion with a mixed organic solvent. • GSH-sensitive degradable polyurethane nanoparticles (GPUs) released encapsulated cisplatin in response to elevated glutathione levels. • Cisplatin loaded GPUs significantly reduced tumor growth in a subcutaneous A549 lung tumor mouse model compared to the free cisplatin. [ABSTRACT FROM AUTHOR]

Self‐assembly of 3D structures presents an attractive and scalable route to realize reconfigurable and functionally capable mesoscale devices without human intervention. A common approach for achieving this is to utilize stimuli‐responsive folding of hinged structures, which requires the integration of different materials and/or geometric arrangements along the hinges. It is demonstrated that the inclusion of Kirigami cuts in planar, hingeless bilayer thin sheets can be used to produce complex 3D shapes in an on‐demand manner. Nonlinear finite element models are developed to elucidate the mechanics of shape morphing in bilayer thin sheets and verify the predictions through swelling experiments of planar, millimeter‐scaled PDMS (polydimethylsiloxane) bilayers in organic solvents. Building upon the mechanistic understandings, The transformation of Kirigami‐cut simple bilayers into 3D shapes such as letters from the Roman alphabet (to make "ADVANCED FUNCTIONAL MATERIALS") and open/closed polyhedral architectures is experimentally demonstrated. A possible application of the bilayers as tether‐less optical metamaterials with dynamically tunable light transmission and reflection behaviors is also shown. As the proposed mechanistic design principles could be applied to a variety of materials, this research broadly contributes toward the development of smart, tetherless, and reconfigurable multifunctional systems. [ABSTRACT FROM AUTHOR]

This review presents an overview of the versatile shape memory polyurethane/graphene nanocomposites. Shape memory polyurethanes can recover their original shape from an intermediate shape when triggered by an external stimulus, such as heat, electrical voltage, light, pH change, or water absorption. Shape memory polymers have a successful history in commercial use. The applications for shape memory polymers are highly varied across numerous industries ranging from aircraft structure to biomedical implants. Three different groups of stimuli-responsive shape memory polyurethane/graphene nanocomposites, thermoresponsive, resistive heating actuated, and photon absorption actuated, will be discussed in this review. The applications of shape memory polyurethane/graphene nanocomposite as actuators are also discussed. This article will be pioneering in widespread impression on the state-of-the-art knowledge in shape memory polyurethane/graphene nanocomposites. It does not intend to be an extensive summary, but instead is a guide for scientists looking to apply these uniquely functional materials for advance high-performance applications. Future research may reveal shape memory applications for polyurethane/graphene nanocomposites in electronics, aerospace, and biomedical industries. [ABSTRACT FROM AUTHOR]

The narrowly dispersed functional silica/poly(di(metacryloylooxy-1-ethoxy) methane-co-acryl amide) (SiO2/P(DMOEM-co-AAm)) core-shell microspheres were synthesized by distillation precipitation polymerization of DMOEM as a degradable crosslinker and AAm as a functional monomer with the presence of 3-(methacryloxy)propyltrimethoxysilane (MPS) modified silica microspheres as seeds. Indole-3-acetic acid (IAA) can be efficiently loaded into the microspheres with a loading capacity of 37.5% via hydrogen-bonding interaction between the carboxylic acid group of IAA and the amide groups on the surface of SiO2/P(DMOEM-co-AAm). The loaded IAA can be triggered released by pH due to the presence of pH-responsive crosslinker (DMOEM). [ABSTRACT FROM AUTHOR]

Self‐assembly of asymmetric block copolymers (BCPs) around active pore edges has emerged as an important strategy to produce smart membranes with tunable pathways for solute transport. However, thus far, it is still challenging to manipulate pore shape and functionality for directional transformation under external stimuli. Here, a versatile strategy by mesoscale simulations to design stimuli‐responsive pores with various edge decorations in hybrid membranes is reported. Dopant BCPs are used as decorators to stabilize pore edges and extend their function in reconfiguring pores in response to repeated membrane stretching/shrinking caused by external stimuli. The decoration morphologies are predictable since the assemblies of dopant BCPs around pore edges are closely related to their self‐assemblies in solution. The coassembly between different BCPs in the hybrid membrane for the control of pore morphology is featured, and the parameter settings, including block incompatibility and molecular architecture for the construction of a specific pore, are determined. Results show that harnessed dopant BCPs in the hybrid membrane can enhance pore formation and induce directional pore shape and functionality transformation. Diversified pore decorations exhibit potential that can be further explored in selective solute transport and the design of stimuli‐responsive smart nanodevices. [ABSTRACT FROM AUTHOR]

Development of macromolecules provides applicable platforms for the delivery of therapeutics. In this general overview, we focus on the design principles of synthetic polymers, with disulfide bonds located in either the polymer backbone or side chains. We also discuss the role of disulfide bonds, as well as the remaining questions to better understand their applications in therapeutic delivery systems. [ABSTRACT FROM AUTHOR]

[Display omitted] The advent of 3D printing technology in the 1980s enabled the fabrication of patient-specific products with precise shape, size, and complexity. A variety of 3D printing techniques, such as direct ink writing by extrusion, particle fusion printing, light-induced printing, volumetric bioprinting, and inkjet printing, have been explored recently for the purpose of developing desired 3D printed objects. Among these techniques, direct ink writing has been used extensively due to its affordability, ease of use, potential for scaling up, and faster speed. This approach saves time and resources while allowing for the flexible use of various materials. The lack of a variety of varied printing inks, however, continues to be an impediment to its widespread commercial use. Owing to their quick gelling behaviour, extrudability, and shape fidelity, injectable hydrogels have become interesting alternatives for printing inks. Hydrogel inks can be developed by either natural or synthetic polymers, or a combination of the both, to achieve the desired rheological and mechanical properties utilizing various strategies of crosslinking and incorporation of nanoparticles like nanoclay, bioactive glass, graphene oxide and silica nanoparticles. Further, various stimuli responsive hydrogel inks responding to various external stimuli (such as temperature, pH, magnetic field) can be developed to prepare engineered biostructures that can be used in healthcare sector. This review provides a spotlight on recent advancement in developing hydrogel inks and their different physicochemical aspects for developing desired engineered biostructures. Finally, we discuss the opportunities of 4D printing, current difficulties and future prospects for hydrogel inks-based 3D printing to emphasize the significant scope for future innovations. [ABSTRACT FROM AUTHOR]

The many postpolymerization modification opportunities of biocompatible poly(2‐alkyl/aryl‐2‐oxazoline)s (PAOx), such as thiol–ene/thiol–yne, azide–alkyne cycloadditions, amidation, and transesterification, are one of the most appealing features of this polymer class for its popularity in biomedicine. Inspired by recent reports on guanidine‐catalyzed transesterification and amidation reactions of methyl ester substrates, we explored the use of guanidines as a reactant for the modification of methyl ester functional PAOx, to obtain the respective acyl guanidines. The obtained acyl guanidines functional polymers display reactivity toward α‐haloketones, yielding imidazole functional PAOx. The obtained polymer structures are protonated in a broad pH range, and the acyl guanidine moiety is demonstrated to be a cleavable linker under basic conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2616–2624 [ABSTRACT FROM AUTHOR]

Abstract: Nanotechnology, a relatively novel technique, has much potential in smart drug delivery. Development of novel nanosized particulate drug delivery systems (DDS) may help in disease prevention, diagnosis, and treatment of many of the important diseases. Nanogels have particle sizes in the 0-100 nm range, and the three-dimensional network is maintained by varying the solvent quality. This review article describes concisely the current trends and concepts involved in the design and development of nanogel DDS. This review also explores the various approaches of drug loading, release mechanisms, characterization, and biomedical applications. Optimized nanogel systems can be developed on the basis of the site of action and pattern of drug release desired for improved therapeutic benefits. This can be achieved by using the appropriate method of preparation (physical or chemical) and drug loading mechanism by modifying the geometry and surface of the nanogels. The properties of nanogels are dependent on the constituent materials/components (synthetic or natural) and on external stimuli (pH, temperature, ionic strength or incorporation of hydrophilic residues) in the case of stimuli-sensitive nanogels. Due to the high stability, biodegradability, biocompatibility, large surface area, and minimal resources required for manufacture of nanogels, their applications (such as in oral, pulmonary, nasal, ocular, and topical routes) have gained special attention in the development of pharmaceutical drug carriers.Graphical abstract: [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Nanocarriers based on β-Cyclodextrin modified with Maleic anhydride and NIPAM for dual, pH and temperature responsive drug release are reported. • Multiple functionalities conjugated to magnetic nanoparticle platform in two step one pot synthesis with urethane /urea linkages. • Simultaneous loading and release of Doxorubicin and Curcumin. • Endocytosis monitored by fluorescence. • Targeted cancer cell death in vitro manifested by significant tumor regression in vivo. Abstract Multifunctional nanoconjugates possessing an assortment of key functionalities such as magnetism, florescence, cell-targeting, pH and thermo-responsive features were developed for dual drug delivery. The novelty lies in careful conjugation of each of the functionality with magnetic Fe 3 O 4 nanoparticles by virtue of urethane linkages instead of silica in a simple one pot synthesis. Further β-cyclodextrin (CD) was utilized to carry hydrophobic as well as hydrophilic drug. Superlative release of DOX could be obtained under acidic pH conditions and elevated temperature, which coincides with the tumor microenvironment. Mathematical modelling studies revealed that the drug release kinetics followed diffusion mechanism for both hydrophobic drug and hydrophilic drug. A number of fluorophores onto a single nanoparticle produced a strong fluorescence signal to optically track the nanoconjugates. Enhanced internalization due to folate specificity could be observed by fluorescence imaging. Further their accumulation driven by magnet near tumor site led to magnetic hyperthermia. in vitro studies confirmed the nontoxicity and hemocompatibility of the nanoconjugates. Remarkable cell death was observed with drug-loaded nanoconjugates at very low concentrations in cancer cells. The internalization and cellular uptake of poor bioavailable anticancer agent curcumin were found to be remarkably enhanced on dosing the drug loaded nanoconjugates as compared to free curcumin. Site specific drug delivery due to folate conjugation and subsequent significant suppression in tumor growth was demonstrated by in vivo studies. [ABSTRACT FROM AUTHOR]