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Stimuli-responsive molecular systems support within permanently porous materials offer the opportunity to host dynamic functions in multifunctional smart materials. However, the construction of highly porous frameworks featuring external-stimuli responsiveness, for example by light excitation, is still in its infancy. Here a general strategy is presented to construct spiropyran-functionalized highly porous switchable aromatic frameworks by modular and high-precision anchoring of molecular hooks and an innovative in situ solid-state grafting approach. Three spiropyran-grafted frameworks bearing distinct functional groups exhibiting various stimuli-responsiveness are generated by two-step post-solid-state synthesis of a parent indole-based material. The quantitative transformation and preservation of high porosity are demonstrated by spectroscopic and gas adsorption techniques. For the first time, a highly efficient strategy is provided to construct multi-stimuli-responsive, yet structurally robust, spiropyran materials with high pore capacity which is proved essential for the reversible and quantitative isomerization in the bulk as demonstrated by solid-state NMR spectroscopy. The overall strategy allows to construct dynamic materials that undergoes reversible transformation of spiropyran to zwitterionic merocyanine, by chemical and physical stimulation, showing potential for pH active control, responsive gas uptake and release, contaminant removal, and water harvesting.

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Targeted and controllable drug release at lesion sites with the aid of visual navigation in real-time is of great significance for precise theranostics of cancers. Benefiting from the marvelous features (e.g., bright emission and phototheranostic effects in aggregates) of aggregation-induced emission (AIE) materials, constructing AIE-based multifunctional nanocarriers that act as all-arounders to integrate multimodalities for precise theranostics is highly desirable. Here, an intelligent nanoplatform (P-TN-Dox@CM) with homologous targeting, controllable drug release, and in vivo dual-modal imaging for precise chemo-photothermal synergistic therapy is proposed. AIE photothermic agent (TN) and anticancer drug (Dox) are encapsulated in thermo-/pH-responsive nanogels (PNA), and the tumor cell membranes are camouflaged onto the surface of nanogels. Active targeting can be realized through homologous effects derived from source tumor cell membranes, which advantageously elevates the specific drug delivery to tumor sites. After being engulfed into tumor cells, the nanogels exhibit a burst drug release at low pH. The near-infrared (NIR) photoinduced local hyperthermia can activate severe cytotoxicity and further accelerate drug release, thus generating enhanced synergistic chemo-photothermal therapy to thoroughly eradicate tumors. Moreover, P-TN-Dox@CM nanogels could achieve NIR-fluorescence/photothermal dual-modal imaging to monitor the dynamic distribution of therapeutics in real-time. This work highlights the great potential of smart P-TN-Dox@CM nanogels as a versatile nanoplatform to integrate multimodalities for precise chemo-photothermal synergistic therapy in combating cancers.

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Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid-liquid interface, have emerged as "smart emulsifiers" with attributes of high emulsification efficiency, long-term stability, and on-demand emulsification/demulsification capabilities. However, only pH-responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc+ ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. The Fc+ groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi-stimuli-responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

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Metallohydrogels and lanthanide (Ln) fluorescent materials have gained much attention recently. In this study, we designed and synthesized a facile gelator of a phenylalanine-based derivative containing an indazole group (namely IZF). It was found that IZF can self-assemble to form hydrogel at pH ≤ 7. Meanwhile, IZF and Tb3+/Eu3+ can co-assemble to generate IZF-Tb and IZF-Eu metallohydrogels with green and red fluorescence, respectively, at pH 8-11, with excellent multi-stimuli responsiveness. The bimetallic hydrogels of IZF-Tb/Eu exhibit different colors under UV light by adjusting the ratio of Tb3+ and Eu3+. Moreover, white light emission was achieved with IZF-Tb/Eu bimetallic gels through doping carbon dots (CDs) by tailoring the stoichiometric ratio of Ln-complex and CDs. Remarkably, IZF-Tb and IZF-Eu could be used as fluorescent inks with excellent stability. This study indicates that the amino acid derivative-based Ln-metallohydrogels are excellent candidates for constructing information storage and multiple anti-counterfeiting materials.

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Aqueous dispersions of nanogels that respond to switches in environmental pH and/or temperature by changes in their hydrodynamic radius (Rh ) and/or ζ-potential are prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization-induced thermal (70 °C) self-assembly (PITSA) of N-isopropylacrylamide (NIPAM) in the presence of a poly(methacrylic acid) (PMAA)-substituted macromolecular chain transfer agent and a cross-linker. Photochromic spiropyran (SP) moieties are coupled to the carboxylic acid groups of the nanogels. Upon UV irradiation, the neutral SP isomerizes to the zwitterionic merocyanine (ME) form. Upon UV light irradiation, microgels formed by assembly of SP nanogels undergo a collective motion toward the UV-light source.

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Despite the fact that nanocarriers as drug delivery systems overcome the limitation of chemotherapy, the leakage of encapsulated drugs during the delivery process to the target site can still cause toxic effects to healthy cells in other tissues and organs in the body. Controlling drug release at the target site, responding to stimuli that originated from internal changes within the body, as well as stimuli manipulated by external sources has recently received significant attention. Owning to the spherical shape and porous structure, dendrimer is utilized as a material for drug delivery. Moreover, the surface region of dendrimer has various moieties facilitating the surface functionalization to develop the desired material. Therefore, multi-stimuli-responsive dendrimers or 'smart' dendrimers that respond to more than two stimuli will be an inspired attempt to achieve the site-specific release and reduce as much as possible the side effects of the drug. The aim of this review was to delve much deeper into the recent progress of multi-stimuli-responsive dendrimers in the delivery of anticancer drugs in addition to the major potential challenges.

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Engineered protein polymers that display responsiveness to multiple stimuli are emerging as a promising class of soft material with unprecedented functionality. The remarkable advancement in genetic engineering and biosynthesis has created the opportunity for precise control over the amino acid sequence, size, structure and resulting functions of such biomimetic proteins. Herein, we describe the multi-stimuli-responsive characteristics of a resilin-mimetic protein, An16-resilin (An16), derived from the consensus sequence of resilin gene in the mosquito Anopheles gambiae. We demonstrate that An16 is an intrinsically disordered protein that displays unusual dual-phase thermal transition behavior along with responsiveness to pH, ion, light and humidity. Identifying the molecular mechanisms that allow An16 to sense and switch in response to varying environments furthers the ability to design intelligent biomacromolecules.

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