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The incorporation of nanofillers into polymeric matrix has been proven to be an effective route to reinforce their mechanical properties, and the usage of binary fillers that combines the advantages of the two fillers could lead to further property enhancement. In this work, binary nanofillers consist of multi-walled carbon nanotubes (MWCNTs)-bridged fumed silica (FSiO2) were synthesized for the first time by Pt coupling reaction of methyldiethoxysilane (MDES) modified MWCNTs and triethoxyvinylsilane (TEVS) functionized SiO2, in which MDES modified MWCNTs was synthesized by reacting OH-functionized MWCNTs with MDES, while TEVS-FSiO2 was obtained by reacting fume silica with TEVS. The binary MWCNTs-bridged-FSiO2 was introduced into liquid silicone rubber (LSR) for mechanical reinforcement. It is shown that the interfacial interaction between binary fillers and LSR matrix is significantly enhanced due to the chemical bridging as well as the excess TEVS molecules on SiO2, and the Young's modulus, tensile strength and tear strength of the LSR could be increased by 64%, 29% and 52%, respectively, with incorporation of only 0.25 phr of MWCNTs for the binary fillers. The observed mechanical enhancement could be attributed to good interfacial interaction between the fillers and LSR due to the existence of SiO2 (with excess matrix compatible molecules) on the surface of MWCNTs, which facilitate the filler dispersion in LSR matrix and the promote stress transfer from matrix to MWCNTs, as well as the advantages of extremely high aspect ratio and excellent mechanical strength of MWCNTs.

Dilute acid polymerizes degassed, aqueous acrylamide with concomitant gelation, without the need for added free radical initiator or cross-linking agent. This reaction is accelerated by sonication or UV irradiation, but inhibited by adventitious oxygen or the addition of a free radical inhibitor, suggesting an acid-accelerated free radical process. The resulting hydrogels are thixotropic in nature and partially disrupted by the addition of chaotropic agents, indicating the importance of hydrogen bonding to the 3D network. This discovery was made while trying to prepare pectin-polyacrylamide hydrogels. We observed that pectin initiated the gelation of acrylamide, but only if the aqueous pectin samples had a pH lower than ca. 5.

Upconversion of light has attracted intensive studies for biomedical research, because it enables deeper tissue analysis owing to the longer wavelength of incident light, compared with conventional downconversion fluorescent materials. Triplet-triplet annihilation (TTA), as a typical mechanism of upconversion, does not necessitate high power excitation and exhibits a higher quantum yield than rare earth upconversion owing to more sensitizer options with higher absorption coefficients. A desirable wavelength range of excitation and emission can be realized by careful selection of the combination of sensitizer and activator. Therefore, TTA-UC is worth exploring further for biorelated applications, such as bioimaging and biodetection. Recent developments are reviewed in this article.

A porous tough hydrogel (alginate–polyacrylamide) is successfully synthesized using a photo-gelling polymer as a templating agent. Unlike current porous hydrogels, we present a useful pore-enhancing strategy without sacrificing the mechanical properties of the parent matrix. These porous tough hydrogels, as 3D cell culture scaffolds, can mimic the extracellular matrix and allow maximum nutrient exchange.

Recent advances in host-guest chemistry have significantly influenced the construction of supramolecular soft biomaterials. The highly selective and non-covalent interactions provide vast possibilities of manipulating supramolecular self-assemblies at the molecular level, allowing a rational design to control the sizes and morphologies of the resultant objects as carrier vehicles in a delivery system. In this Focus Review, the most recent developments of supramolecular self-assemblies through host-guest inclusion, including nanoparticles, micelles, vesicles, hydrogels, and various stimuli-responsive morphology transition materials are presented. These sophisticated materials with diverse functions, oriented towards therapeutic agent delivery, are further summarized into several active domains in the areas of drug delivery, gene delivery, co-delivery and site-specific targeting deliveries. Finally, the possible strategies for future design of multifunctional delivery carriers by combining host-guest chemistry with biological interface science are proposed.

In situ gel delivery systems are preferred over conventional systems due to sustained and prolonged release action of therapeutic payload onto the targeted site. Thermogel, a form of in situ gel-forming polymeric formulation, undergoes sol-gel transition after administration into the body. At room temperature, the system is an aqueous polymer solution that easily entraps therapeutic payload by mixing. Upon injection, the higher physiological temperature causes gelation in situ because of the presence of thermosensitive polymers. The gel degrades gradually over time, allowing sustained release of therapeutics localized to the site of interest. This minimizes systemic toxicity and improved efficacy of drug release to the targeted site. Thermogel properties can be easily altered for specific applications via substitution and modification of components in diblock and triblock copolymer systems. The feasibility of fine-tuning allows modifications to biodegradability, biocompatibility, biological functionalization, mechanical properties, and drug release profile. This review summarized recent development in thermogel research with a focus on synthesis and self-assembly mechanisms, gel biodegradability, and applications for drug delivery, cell encapsulation and tissue engineering. This review also assessed inadequacy of material properties as a stand-alone factor on therapeutic action efficacy in human trials, with a focus on OncoGel, an experimental thermogel that demonstrated excellent individual or synergistic drug delivery system in preclinical trials but lacked therapeutic impact in human trials. Detailed analysis from all aspects must be considered during technology development for a successful thermogel platform in drug delivery and tissue engineering.

Optogenetics is a promising neuronal modulation strategy in neuroscience, which enables real-time neuromodulation in free-moving animals with high spatiotemporal control. However, it still suffers from several disadvantages, including low penetration of excitation light and the invasiveness of the insertion of the light delivery system. The incorporation of nanomaterials with different properties into optogenetics may bring new opportunities to solve the problems encountered in optogenetics, from the delivery/expression of the optogene to the stimulation/inhibition and follow-up sensing of neural activity. The challenges of nanomaterial-mediated optogenetics are also discussed. This review elaborates on the feasibility of incorporating nanomaterials into optogenetics and analyzes the benefits of nanomaterial-mediated optogenetics.

In this study, we report the synthesis and characterisation of a thermogelling poly(carbonate urethane) system comprising poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG) and poly(polytetrahydrofuran carbonate) (PTHF carbonate). The incorporation of PTHF carbonate allowed for the control of the lower critical solution temperature (LCST) and decreased critical gelation concentration (CGC) of the thermogels significantly. In addition, the as-prepared thermogels displayed low toxicity against HepG2, L02 and HEK293T cells. Drug release studies were carried out using doxorubicin (Dox). Studies conducted using nude mice models with hepatocellular carcinoma revealed that the Dox-loaded poly(PEG/PPG/PTHF carbonate urethane) thermogels showed excellent in vivo anti-tumour performance and effectively inhibited tumour growth in the tested model.

Pluronic F127 exhibits thermogelling behaviour at 20–30 °C via a micelle packing mechanism. Disruption of the micelle packing increases the sol-gel temperature, but results in the decrease of modulus. Herein, we reported a method to modify F127 with polyhedral oligosilsesquioxane (POSS) to impart a higher gelling temperature without yielding the property and strength of the thermogel. The thermal degradation temperature was enhanced to 15 °C after POSS incorporation and the gelling temperature shifted 10 °C higher, without sacrificing the modulus of the gel. Rheological studies supported the claim that the gel property was reinforced after POSS incorporation. F127-POSS copolymer matrix stored more energy from POSS reinforcement, which saw larger Lissajous curve areas before the collapse of the microstructure for the same amount of stress applied. These results indicated that modification with POSS would raise the sol-gel transition temperature without sacrificing the modulus of the gel.

International audience; The synthesis of multi-arm poly([R]-3-hydroxybutyrate) (PHB)-based triblock copolymers (poly([R]-3-hydroxybutyrate)-b-poly(N-isopropylacrylamide)-b-[[poly(methyl ether methacrylate)-g-poly(ethylene glycol)]-co-[poly(methacrylate)-g-poly(propylene glycol)]], PHB-b-PNIPAAM-b-(PPEGMEMA-co-PPPGMA), and their subsequent self-assembly into thermo-responsive hydrogels is described. Atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAAM) followed by poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) and poly(propylene glycol) methacrylate (PPGMA) was achieved from bromoesterified multi-arm PHB macroinitiators. The composition of the resulting copolymers was investigated by 1H and 13C J-MOD NMR spectroscopy as well as size-exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The copolymers featuring different architectures and distinct hydrophilic/hydrophobic contents were found to self-assemble into thermo-responsive gels in aqueous solution. Rheological studies indicated that the linear one-arm PHB-based copolymer tend to form a micellar solution, whereas the two- and four-arm PHB-based copolymers afforded gels with enhanced mechanical properties and solid-like behavior. These investigations are the first to correlate the gelation properties to the arm number of a PHB-based copolymer. All copolymers revealed a double thermo-responsive behavior due to the NIPAAM and PPGMA blocks, thus allowing first the copolymer self-assembly at room temperature, and then the delivery of a drug at body temperature (37 °C). The non-significant toxic response of the gels, as assessed by the cell viability of the CCD-112CoN human fibroblast cell line with different concentrations of the triblock copolymers ranging from 0.03 to 1 mg mL−1, suggest that these PHB-based thermo-responsive gels are promising candidate biomaterials for drug-delivery applications.

A new drug concentration meter is developed. In vivo drug release can be monitored precisely via a self-indicating drug delivery system consisting of a new aggregation-induced emission thermoresponsive hydrogel. By taking the advantage of a self-indicating system, one can easily detect the depletion of drugs, and reinject to maintain a dosage in the optimal therapeutic window. ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore) Accepted version

The delivery of genetic materials into cells to elicit cellular responses has been extensively studied by biomaterials scientists globally. Many materials such as lipids, peptides, viruses, synthetically modified cationic polymers and certain inorganic nanomaterials could be used to complex the negatively charged plasmids and deliver the formed package into cells. The recent literature on the delivery of genetic materials utilising inorganic nanoparticles is carefully examined in this review. We have picked out the most relevant references and concisely summarised the findings with illustrated examples. We further propose alternative approaches and suggest future pathways towards the practical use of multifunctional nanocarriers.

The synthesis and gene transfection efficiency of a series of amphiphilic copolymers, poly(2-(dimethylamino)ethyl methacrylate)-poly (methacrylate isobutyl polyhedral oligomeric silsesquioxane) (PDMAEMA-POSS) copolymers are reported. The hydrophobic POSS interior allows a cell-sensitizing drug such as paclitaxel to be incorporated, whereas the cationic and hydrophilic PDMAEMA corona allows the complexation of anionic DNA to form a nano-sized polyplex. These drug-encapsulated copolymers display excellent gene transfection efficiency compared with polyethylenimine or PDMAEMA homopolymers.