Photoresponsive and UCST-Type thermoresponsive block Copolymer-Based composite micelles for Dual-Stimuli-Triggered selective and programmable release

Quinoa, the antient crop used by the Andean and Inca civilizations, contains a diverse blend of bioactive phytochemicals that have found roles in the mitigation or treatment for a multitude of diseases such as hyperuricemia, hyperlipidemia, multiple types of cancer, celiac disease, diabetes mellitus, anemia, fatty liver disease, osteoporosis, celiac disease, diabetes mellitus, microbial infections, dysbiosis, hyperthyroidism, and ulcerative colitis. Being rich in macro- and micro- nutrients, it is used in a variety of culinary dishes including cereals, Indian kheer, Egyptian kishk, soups, cereals, and many bakery items including bread, cupcakes, and cookies. It is also an effective alternative for patients that cannot digest gluten or individuals on vegetarian diet. Quinoa can be cultivated in harsh environments due to its tolerance to abiotic stresses such as high heat temperature, high salt content in soil, low water conditions, and presence of heavy metals in soil. Novel approaches for using quinoa include treating water contaminated with heavy metals like chromium, cadmium, nickel, arsenic, lead, and wastewater treatment. It has been used to prepare biodegradable films for food packaging, ready-to-eat protein hydrolysates, functional foods and drug delivery systems like composite micelles, microspheres, and nanoparticles. Quinoa can prevent the rancidity of lipids and microbial contamination in packaged food. In future, study on the genetic variants of quinoa, further expansion into its natural constituents, and research or clinical trials for treatment of many diseases can be done.

The rapid formation of methane hydrates in subsea pipelines threatens flow safety, while conventional inhibitors face environmental and efficiency limitations. This study investigates a poly(N-vinylcaprolactam)-glycine (PVCap-glycine) composite system for synergistic methane hydrate inhibition. Experimental results demonstrate superior performance: the composite system extends induction time to 672 min (135% and 37% longer than the single PVCap and glycine, respectively), reduces gas consumption by 72.6%, and lowers peak gas consumption rates by 25-45.5% compared to the blank system. Mechanistically, glycine disrupts water's hydrogen-bond network through carboxyl groups, delaying quasi-clathrate nucleation, while PVCap's hydrophobic chains adsorb on crystal nuclei, forming mass-transfer barriers. Their hydrophobic association generates composite micelles, increasing interfacial resistance by approximately 40% and elevating nucleation energy barriers. Notably, substituting glycine for partial PVCap reduces environmental burdens while achieving 135% longer induction time and 45.2% lower gas consumption than the single PVCap, overcoming the performance limitations of individual inhibitors at their optimal concentrations. The synergy originates from glycine's molecular-scale water perturbation and PVCap's interfacial regulation, coupled with wax-induced physicochemical barriers, enabling dual thermodynamic-kinetic inhibition. This synergistic strategy enables high-performance, low-environmental-impact inhibitors for deep-sea pipeline safety.

Myricetin (Myr), a flavonoid compound exhibiting antioxidant, anti-inflammatory, antibacterial, antiviral and anti-obesity properties, suffers from limited bioavailability due to inherent hydrophobicity, thermosensitivity and photosensitivity. To overcome these limitations, we engineered edible dock protein (EDP)-edible dock polysaccharide (EDPS) composite micelles to enhance Myr's encapsulation efficiency and stability. The highest encapsulation efficiency of Myr was 92.5% when the concentration of EDPS was 7.5 g kg-1. The zeta potential, particle size and polydispersity index of the Myr-EDP-EDPS composite micelles were - 21.3 mV, 512.6 nm and 0.35 under this condition, respectively. Meanwhile the hydrophilicity and surface tension of the composite micelles were increased with the enhancement of EDPS concentration. Both Fourier transform infrared and X-ray diffraction spectroscopy indicated that EDPS was successfully coated on the surface of the Myr-EDP micelles. The encapsulation by EDPS further enhanced stability of Myr, resulting in 98.42% retention after 3 months at 4 °C and a 2.7-fold increase in ultraviolet stability. In addition, the main driving forces were hydrogen bonding and van der Waals forces during the formation of the Myr-EDP-EDPS composite micelles. In vitro experiments exhibited that the EDPS-coated Myr-EDP composite micelles enhance gastric stability of Myr by 1.38-fold and enable its effective release in the small intestine. The EDP-EDPS composite micelle system effectively enhances the encapsulation and stability of Myr. This nanotechnology represents a highly promising strategy for developing functional food ingredients featuring optimized stability. © 2025 Society of Chemical Industry.

Mitigating ACQ and enhancing solubility: A dual strategy for real-time aquatic product freshness detection.

The precise control of reaction kinetics and the synchronous regulation of the micelle assembly in the soft-templating method for synthesizing ordered mesoporous carbon presents a significant challenge. In this study, a versatile ethanol-mediated self-assembly strategy is introduced to synthesize ordered mesoporous carbons (OMCs) with diverse morphologies and well-defined mesostructures using liquefied wood (LW). Ethanol functions as both a proton-trapping agent and a linker between carbon precursors and templates, enabling fine-tuned regulation of the self-assembly kinetics while providing additional hydrogen bonding interactions. Furthermore, the micelle structure can be precisely manipulated from cylindrical to spherical through ethanol-induced selective swelling of hydrophilic blocks, resulting in a reduction in packing parameter (p) from 1/3 < (p) <1/2 to (p) ≤ 1/3. Notably, the spherical composite micelles self-assemble into single crystals with highly ordered body-centered mesostructures. The fabricated ordered mesoporous carbon single crystal (OMCSC) electrochemical sensing polymers exhibit absolute enantiomeric discrimination for L- and D-tryptophan. This EtOH-mediated self-assembly approach not only elucidates the role of ethanol in the self-assembly process but also offers a promising pathway for fabricating versatile OMCs from renewable biomass resources.

Background: Liver cancer, especially hepatocellular carcinoma, a prevalent malignant tumor of the digestive system, poses significant therapeutic challenges. While traditional chemotherapy can inhibit tumor progression, its clinical application is limited by insufficient efficacy. Hydrophobic therapeutic agents further encounter challenges including low tumor specificity, poor bioavailability, and severe systemic toxicity. This study aimed to develop a liver-targeted, glutathione (GSH)-responsive micellar system to synergistically enhance drug delivery and antitumor efficacy. Methods: A GSH-responsive disulfide bond was chemically synthesized to conjugate glycyrrhetinic acid (GA) with curcumin (Cur) at a molar ratio of 1:1, forming a prodrug Cur-GA (CGA). This prodrug was co-assembled with glycyrrhizic acid (GL) at a 300% w/w loading ratio into micelles. The system was characterized for physicochemical properties, in vitro drug release in PBS (7.4) without GSH and in PBS (5.0) with 0, 5, or 10 mM GSH, cellular uptake in HepG2 cells, and in vivo efficacy in H22 hepatoma-bearing BALB/c mice. Results: The optimized micelles exhibited a hydrodynamic diameter of 157.67 ± 2.14 nm (PDI: 0.20 ± 0.02) and spherical morphology under TEM. The concentration of CUR in micelles can reach 1.04 mg/mL. In vitro release profiles confirmed GSH-dependent drug release, with 67.5% vs. <40% cumulative Cur release observed at 24 h with/without 10 mM GSH. Flow cytometry and high-content imaging revealed 1.8-fold higher cellular uptake of CGA-GL micelles compared to free drug (p < 0.001). In vivo, CGA-GL micelles achieving 3.6-fold higher tumor accumulation than non-targeted controls (p < 0.001), leading to 58.7% tumor volume reduction (p < 0.001). Conclusions: The GA/GL-based micellar system synergistically enhanced efficacy through active targeting and stimuli-responsive release, providing a promising approach to overcome current limitations in hydrophobic drug delivery for hepatocellular carcinoma therapy.

Synergistic antimicrobial efficacy of glabrol and colistin through micelle-based co-delivery against multidrug-resistant bacterial pathogens.

Photodynamic therapy efficiency is constrained by tumor hypoxia and insufficient photosensitizer accumulation. To address these limitations, an oxygen-supplying nanoplatform was developed through function-oriented polymer design. Briefly, an amphiphilic copolymer (PFOC-PEI) was firstly synthesized through chemical conjugation of perfluorooctanoic acid with branched polyethyleneimine, forming micelles capable of encapsulating chlorin e6, while alleviating hypoxia via fluorocarbon-mediated oxygen delivery. To enhance tumor-selective delivery for biocompatibility, a pH-responsive polyanion (PEI-DMMA) derived from 2,3-dimethylmaleic anhydride modification was integrated, yielding composite micelles (Ce6-PFOC-PEI/PEI-DMMA) with tumor stimulus responsiveness charge reversal and oxygen carrying capabilities. The nanocarrier maintained negative surface charge under physiological conditions to prolong blood circulation, while switching to positive charge at tumor sites through microenvironmental-triggered cleavage of acid-labile amide bonds, thereby enhancing tumor accumulation. In vitro studies demonstrated 1.5-fold higher cellular uptake of Ce6-PFOC-PEI/PEI-DMMA under acidic conditions compared to non-hydrolytic controls (Ce6-PFOC-PEI/PEI-SA), correlating with enhanced ROS generation in C6 glioma cells. The improved phototoxicity was evidenced by lower IC50 values against C6 cells. In vivo evaluation revealed 87% tumor growth inhibition in C6 tumor-bearing nude mice of Ce6-PFOC-PEI/PEI-DMMA, which is superior to those of Ce6-PFOC-PEI/PEI-SA (69%) and Ce6-PFOC-PEI (73%). This oxygen self-supplying platform integrates fluorocarbon-mediated oxygenation with pH-responsive charge reversal, demonstrating enhanced PDT efficacy while maintaining favorable biosafety.

Abstract Over the past decade, there has been growing research interest in deriving advanced carbonaceous materials with unique architectures, including diverse morphologies and compositions, from polymer‐based precursors with tailored nano/micro‐structures. The organic–organic assembly between organic molecules and block copolymers (BCPs) has emerged as a promising strategy for advancing the preformed polymers with multiple levels of complexity. This review provides a comprehensive overview of the synthesis and potential applications of unique carbonaceous nano/micro‐structures derived from commonly used organic precursors, including phenol/formaldehyde, dopamine, and biomass. It begins with a brief summary of the polymerization mechanism for each type of precursors. Following this, it details the delicate design and preparation strategies for unique polymer architectures, including the formation mechanisms of the first‐level assembly involving BCPs and organic precursors, which form composite micelles as building units, and the principles for manipulation the higher‐level assembly process of the composite micelles, illustrated with some representative examples. The review then highlights the advanced applications of these materials in heterogeneous catalysts, secondary batteries, separation, and intelligent drug delivery systems. Finally, the synthetic challenges and potential development directions of unique carbonaceous nano/micro‐structures are outlined, underscoring a pathway for developing advanced materials.

pH and redox dually responsive micelles loaded with anti-cancer drug and OA-Bi2S3 nanodots for chemo-photothermal synergistic treatment of cancers

Mesoporous materials endowed with a hollow structure offer ample opportunities due to their integrated functionalities; however, current approaches mainly rely on the recruitment of solid rigid templates, and feasible strategies with better simplicity and tunability remain infertile. Here, we report a novel emulsion-driven coassembly method for constructing a highly tailored hollow architecture in mesoporous carbon, which can be completely processed on oil-water liquid interfaces instead of a solid rigid template. Such a facile and flexible methodology relies on the subtle employment of a 1,3,5-trimethylbenzene (TMB) additive, which acts as both an emulsion template and a swelling agent, leading to a compatible integration of oil droplets and composite micelles. The solution-based assembly process also shows high controllability, endowing the hollow carbon mesostructure with a uniform morphology of hundreds of nanometers and tunable cavities from 0 to 130 nm in diameter and porosities (mesopore sizes 2.5-7.7 nm; surface area 179-355 m2 g-1). Because of the unique features in permeability, diffusion, and surface access, the hollow mesoporous carbon nanospheres exhibit excellent high rate and cycling performances for sodium-ion storage. Our study reveals a cooperative assembly on the liquid interface, which could provide an alternative toolbox for constructing delicate mesostructures and complex hierarchies toward advanced technologies.

Construction and characterization of a novel Myr-OSADS-CIn micelle for enhanced stability and bioavailability of myricetin

In recent years, a great deal of work has been devoted to the development of thermoresponsive polymers that can be made into new types of smart materials. In this paper, a branched polymer, HTPB-g-(PNIPAM/PEG), with polyolefin chain segments as the backbone and having polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNIPAM) as side chains was synthesized by ATRP and click reactions using N3-HTPB-Br as the macroinitiator. This initiator was designed and synthesized using hydroxyl-terminated polybutadiene (HTPB) as the substrate. The temperature-responsive behavior of the branched polymer was investigated. The lower critical solution temperature (LCST) of the branched polymer was determined by ultraviolet and visible spectrophotometry (UV-vis) and was found to be 35.2 °C. The relationship between the diameter size of micelles and temperature was determined by dynamic light scattering (DLS). It was found that the diameter size changed at 36 °C, which was nearly consistent with the result obtained by UV-vis. The results of the study indicate that HTPB-g-(PNIPAM/PEG) is a temperature-responsive polymer. At room temperature, the polymer can self-assemble into composite micelles, with the main chain as the core and the branched chain as the shell. When the temperature was increased beyond LCST, the polyolefin main chain along with the PNIPAM branched chain assembled to form the nucleus, and the PEG branched chain constituted the shell.

Abstract The hydrothermal/soft templating method is an effective way to synthesize ordered mesoporous carbon (OMC), yet the mechanism of this strategy is not well illustrated. Herein, a hydrothermal temperature‐controlled approach is developed to precisely synthesize OMCs with well‐defined morphologies from liquefied wood (LW). As the hydrothermal temperature increases from 130 to 210°C, the hydrophilicity of the hydrophilic blocks decreases accompanied by the increase of the relative volume of the hydrophobic block, resulting in the packing parameter p of micelles changing from p ≤ 1/3 to 1/3 &lt; p &lt; 1/2, which transforms the micelle's structure from spherical to cylindrical. Additionally, accelerated nucleation occurred with the increased hydrothermal temperature. When the rate of nucleation is matched to the self‐assembly of the composite micelles, the composite micelles grow into worm‐like morphology and an ordered p6m mesostructure. This hydrothermal temperature‐controlled strategy provides a straightforward and effective approach for synthesizing OMCs with various morphologies from LW, addressing the previously insufficiently elucidated micelle formation mechanism in the hydrothermal/soft templating method.

Dynamic coassembly of nanodiamonds and block copolymers in organic solvents

Astaxanthin (AST) is approved by the US Food and Drug Administration (FDA) as a safe dietary supplement for humans. As a potent lipid-soluble keto-carotenoid, it is widely used in food, cosmetics, and the pharmaceutical industry. However, its low solubility limits its powerful biological activity and its application in these fields. This study aims to develop a delivery system to address the low solubility and bioavailability of AST and to enhance its antioxidant capacity. Astaxanthin-loaded composite micelles were successfully prepared via coaxial electrospray technology. Astaxanthin existed in the amorphous state in the electro-sprayed formulation with an approximate particle size of 186.28 nm and with a polydispersity index of 0.243. In this delivery system, Soluplus and copovidone (PVPVA 64) were the main polymeric matrix for AST, which then released the drug upon contact with aqueous media, resulting in an overall increase in drug solubility and a release rate of 94.08%. Meanwhile, lecithin, and Polyethylene glycol-grafted Chitosan (PEG-g-CS)could support the absorption of AST in the gastrointestinal tract, assisting transmembrane transport. The relative bioavailability reached about 308.33% and the reactive oxygen species (ROS) scavenging efficiency of the formulation was 44.10%, which was 1.57 times higher than that of free astaxanthin (28.10%) when both were at the same concentration level based on astaxanthin. Coaxial electrospray could be applied to prepare a composite micelles system for the delivery of poorly water-soluble active ingredients in functional food, cosmetics, and medicine. © 2023 Society of Chemical Industry.

Fluorescent nanodiamonds (FNDs) are versatile nanomaterials with promising properties. However, efficient functionalization of FNDs for biomedical applications remains challenging. In this study, we demonstrate mesoporous polydopamine (mPDA) encapsulation of FNDs. The mPDA shell is generated by sequential formation of micelles via self-assembly of Pluronic F127 (F127) with 1,3,5-trimethyl benzene (TMB) and composite micelles via oxidation and self-polymerization of dopamine hydrochloride (DA). The surface of the mPDA shell can be readily functionalized with thiol-terminated methoxy polyethylene glycol (mPEG-SH), hyperbranched polyglycerol (HPG), and d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS). The PEGylated FND@mPDA particles are efficiently taken up by, and employed as a fluorescent imaging probe for, HeLa cells. HPG-functionalized FND@mPDA is conjugated with an amino-terminated oligonucleotide to detect microRNA via hybridization. Finally, the increased surface area of the mPDA shell permits efficient loading of doxorubicin hydrochloride. Further modification with TPGS increases drug delivery efficiency, resulting in high toxicity to cancer cells.

Abstract The architectures of carbon materials prepared via soft‐templating method greatly depend on the assembly pattern of micelles. Herein, a kinetics‐controlled strategy is developed to fabricate ordered mesoporous carbon (OMC) single crystals from liquefied wood by using melamine to regulate the polymerization rate of carbon precursors, which further affects the assembly process. Due to the slow hydroxymethylation reaction of melamine with formaldehyde in acid, the addition of melamine can decelerate the reaction kinetics to produce no seed nuclei at the initial stage, which favors the composite micelles to orderly aggregate and further grow in a layer‐by‐layer pattern to form OMC single crystals after carbonization. The OMC single crystals with high specific surface areas (733 m2 g−1), uniform mesopore size (3.2 nm), and ordered Im3m mesostructure are ideal supports to couple with Ag nanoparticles to act as efficient catalysts, which exhibits remarkable catalytic performance for the reduction of 4‐nitrophenol.

The accumulation and sustained release of drugs in the colonic inflammatory region are the favorable strategy for treating ulcerative colitis (UC). In this study, we developed a synergistic anti-inflammatory drug (quercetin/EGCG)-loaded micelle using hydrolytic quinoa protein (HQP) and cationic lotus root starch (CLRS) by a layer-by-layer assembly method. The encapsulation efficiency of quercetin and EGCG in the Que-HQP-EGCG-CLRS micelles reached 91.5 and 89.4%, respectively. This composite micelle exhibited a core-shell structure, where Que-HQP-EGCG was the core and CLRS was the coating shell. Moreover, the in vitro experiments indicated that these micelles can make Que/EGCG pass through gastric environments stably and delay their release in the intestine. Animal experiments further confirmed that the Que-HQP-EGCG-CLRS micelles can efficiently accumulate in the colonic inflammatory region and enable sustained release of drugs (more than 24 h), thus notably alleviating the symptoms of UC. These results suggested that Que-HQP-EGCG-CLRS micelles have good gastric stability, colonic inflammatory-accumulated effect, and sustained drug release ability, which are a promising co-delivery system for UC treatment.