Localized self-assembly of macroscopically structured supramolecular hydrogels through reaction-diffusion.

Localized molecular self-assembly has been developed as an effective approach for the fabrication of spatially resolved supramolecular hydrogels, showing great potential for many high-tech applications. However, the fabrication of macroscopically structured supramolecular hydrogels through molecular self-assembly remains a challenge. Herein, we report on localized self-assembly of low molecular weight hydrogelators through a simple reaction-diffusion approach, giving rise to various macroscopically patterned supramolecular hydrogels. This is achieved on the basis of an acid-catalyzed hydrazone supramolecular hydrogelator system. The acid was pre-loaded in a polydimethylsiloxane (PDMS) substrate, generating a proton gradient in the vicinity of the PDMS surface after immersing the PDMS in the aqueous solution of the hydrogelator precursors. The acid dramatically accelerates the in situ formation and self-assembly of the hydrazone hydrogelators, leading to localized formation of supramolecular hydrogels. The growth rate of the supramolecular hydrogels can be easily tuned through controlling the concentrations of the hydrogelator precursors and HCl. Importantly, differently shaped supramolecular hydrogel objects can be obtained by simply changing the shapes of PDMS. This work suggests that reaction-diffusion-mediated localized hydrogelation can serve as an approach towards macroscopically structuralized supramolecular hydrogels, which may find potential applications ranging from tissue engineering to biosensors.

Robust Electrostatic-Templated Polymerization for Controllable Synthesis of Stable and Permeable Polyelectrolyte Vesicles.

Polymer vesicles are of profound interest for designing delivery vehicles and nanoreactors toward a variety of biomedical and catalytic applications, yet robust synthesis of stable and permeable vesicles remains challenging. Here, we propose an electrostatic-templated polymerization that enables fabrication of polyelectrolyte vesicles with simultaneously regulated stability and permeability. In our design, cationic monomers were copolymerized with cross-linkers in the presence of a polyanionic-neutral diblock copolymer as a template. By properly choosing the block length ratio of the template, we fabricated a type of polyion complex vesicle consisting of a cross-linked cationic membrane, electrostatically assembled with the template copolymer which can be removed by sequential dissociation and separation under concentrated salt. We finally obtained stable polyelectrolyte vesicles of regulated size, membrane permeability, and response properties by tuning the synthesis factors including ionic strength, cross-linker type, and fraction as well as different monomers and concentrations. As a proof-of-concept, lipase was loaded in the designed cationic vesicles, which exhibited enhanced enzyme stability and activity. Our study has developed a novel and robust strategy for controllable synthesis of a new class of stable and permeable polymer (polyelectrolyte) vesicles that feature great potential applications as functional delivery carriers and nanoreactors.

Facile Electret-Based Self-Powered Soft Sensor for Noncontact Positioning and Information Translation.

Noncontact sensors have demonstrated significant potential in human-machine interactions (HMIs) in terms of hygiene and less wear and tear. The development of soft, stable, and simply structured noncontact sensors is highly desired for their practical applications in HMIs. This work reports on electret-based self-powered noncontact sensors that are soft, transparent, stable, and easy to manufacture. The sensors contain a three-layer structure with a thickness of 0.34 mm that is fabricated by simply stacking a polymeric electret layer, an electrode layer, and a substrate layer together. The fabricated sensors show high charge-retention capability, keeping over 98% of the initial surface potential even after 90 h, and can accurately and repeatedly sense external approaching objects with impressive durability. The intensity of the detected signal shows a strong dependence on the distance between the object and the sensor, capable of sensing a distance as small as 2 mm. Furthermore, the sensors can report stable signals in response to external objects over 3000 cycles. By virtue of the signal dependence on distance, an intelligent noncontact positioning system is developed that can precisely detect the location of an approaching object. Finally, by integrating with eyeglasses, the transparent sensor successfully captures the movements of blinks for information translation. This work may contribute to the development of stable and easily manufactured noncontact soft sensors for HMI applications, for instance, assisting with communication for locked-in syndrome patients.

Dextran-based antibacterial hydrogel-derived fluorescent sensors for the visual monitoring of AgNPs.

The unpredictable release behavior of metal nanoparticles/metal ions from metal nanoparticle-loaded hydrogels, without a suitable in situ detection method, is resulting in serious cytotoxicity. To optimize the preparation and design of antibacterial hydrogels for in situ detection of metal nanoparticles, an in-situ detection platform based on the fluorescence signal change caused by the potential surface energy transfer of silver nanoparticles (AgNPs) and carbon dots (CD) through silver mirror reaction and Schiff base reaction was established. The antimicrobial test results show that the composite antimicrobial hydrogel, with lower dosages of AgNPs and CD, exhibited a higher inhibition rate of 99.1 % against E. coli and 99.8 % against S. aureus compared to the single antimicrobial component. This suggests a potential synergistic antimicrobial activity. Furthermore, the fluorescence detection platform was established with a difference of <3 µg between detected values and actual values over a period of 72 h. This demonstrates the excellent in situ detection capability of the hydrogel in antimicrobial-related applications.

Spatiotemporal control over self-assembly of supramolecular hydrogels through reaction-diffusion.

Supramolecular self-assembly is ubiquitous in living system and is usually controlled to proceed in time and space through sophisticated reaction-diffusion processes, underpinning various vital cellular functions. In this contribution, we demonstrate how spatiotemporal self-assembly of supramolecular hydrogels can be realized through a simple reaction-diffusion-mediated transient transduction of pH signal. In the reaction-diffusion system, a relatively faster diffusion of acid followed by delayed enzymatic production and diffusion of base from the opposite site enables a transient transduction of pH signal in the substrate. By coupling such reaction-diffusion system with pH-sensitive gelators, dynamic supramolecular hydrogels with tunable lifetimes are formed at defined locations. The hydrogel fibers show interesting dynamic growing behaviors under the regulation of transient pH signal, reminiscent of their biological counterpart. We further demonstrate a proof-of-concept application of the developed methodology for dynamic information encoding in a soft substrate. We envision that this work may provide a potent approach to enable transient transduction of various chemical signals for the construction of new colloidal materials with the capability to evolve their structures and functionalities in time and space.

Nitrogen-oxygen co-doped carbon@silica hollow spheres as encapsulated Pd nanoreactors for acetylene dialkoxycarbonylation.

The introduction of heteroatoms into hollow carbon spheres is imperative for enhancing catalytic activity. Consequently, we investigated the utilization of nitrogen-oxygen(N/O) co-doped hollow carbon (C)/silica (SiO2) nanospheres (NxC@mSiO2), which have a large internal volume and a nano-constrained environment that limits metal aggregation and loss, making them a potential candidate. In this study, we demonstrate the synthesis of nitrogen-oxygen (N/O) co-doped hollow carbon spheres using resorcinol and formaldehyde as carbon precursors, covered with silica, and encapsulated with palladium nanoparticles (NPs) in situ. The N/O co-doping process introduced defects on the surface of the internal C structure, which acted as active sites and facilitated substrate adsorption. Subsequent treatment with hydrogen peroxide (H2O2) introduced numerous carboxyl groups onto the C structure, increasing the catalytic environment as acid auxiliaries. The carboxyl group is present in the carbon structure, as determined calculations based on by density functional theory, reduces the adsorption energy of acetylene, thereby promoting its adsorption and enrichment. Furthermore, H2O2-treatment enhanced the oxygen defects in the carbon structure, improving the dispersion of Pd NPs and defect structure. The Pd/NxC@mSiO2-H2O2 catalysts demonstrated outstanding performance in the acetylene dialkoxycarbonylation reaction, showcasing high selectivity towards 1,4-dicarboxylate (>93 %) and remarkable acetylene conversion (>92 %). Notably, the catalyst exhibited exceptional selectivity and durability throughout the reaction.

Influence of Dopamine Methacrylamide on Swelling Behavior and Nanomechanical Properties of PNIPAM Microgels.

The combination of the catechol-containing comonomer dopamine methacrylamide (DMA) with stimuli-responsive poly(N-isopropylacrylamide) (PNIPAM) microgels bears a huge potential in research and for applications due to the versatile properties of catechols. This research gives the first detailed insights into the influence of DMA on the swelling of PNIPAM microgels and their nanomechanical properties. Dynamic light scattering measurements showed that DMA decreases the volume phase transition temperature and completion temperature due to its higher hydrophobicity when compared to NIPAM, while sharpening the transition. The cross-linking ability of DMA decreases the swelling ratios and mesh sizes of the microgels. Microgels adsorbed at the solid surface are characterized by atomic force microscopy─as the DMA content increases, microgels protrude more from the surface. Force spectroscopy measurements below and above the volume phase transition temperature display a stiffening of the microgels with the incorporation of DMA and upon heating across its entire cross section as evidenced by an increase in the E modulus. This confirms the cross-linking ability of DMA. The affine network factor ß, derived from the Flory-Rehner theory, is linearly correlated with the E moduli of both pure PNIPAM and P(NIPAM-co-DMA) microgels. However, large DMA amounts hinder the microgel shrinking while maintaining mechanical stiffness, possibly due to catechol interactions within the microgel network.

Simple and biodegradable mesoporous silica nanocarriers for enhancing antitumor therapy through photochemical synergism.

The biosafety and degradability of nanocarriers have always been an important factor restricting their entry into the clinic. In this work, a new nano-system was prepared by coating the photothermal effect of dopamine-doped mesoporous silica nanoparticles with carboxymethyl chitin through electrostatic interaction, and is further anchored with folic acid on the surface for targeted delivery of anti-cancer the drug doxorubicin (DOX). The nano-system (DOX@PDA/MSN-CMCS-FA) is simply modified CMCS after being loaded with DOX and has good dispersibility, and the drug loading is 10.6%. In vitro release studies have shown that the release rate of PDA/MSN-CMCS-FA is 40% in pH 5.5. Effective degradation is debris in 14 d acidic environments. Due to the anti-infrared photothermal effects of PDA doping and DOX chemotherapy, the semi-lethal concentration (IC50) of nanoparticles (NPS) was 14.95 µg/mL, which can inhibit tumor cell growth by photochemical synergistic treatment, and have certain degradation performance.

Continuous-Flow Nanoprecipitation Method to Synthesize Degradable Hollow Mesoporous Organosilica Nanoparticles for Insecticide Delivery.

Degradable mesoporous organosilica nanoparticles (MONPs) are attracting significant attention in the area of designing smart drug carriers mainly due to their excellent stability and multiple functions. However, the efficient, controllable, and large-scale production of MONPs still faces huge challenges. Herein, a novel and facile continuous-flow nanoprecipitation strategy was reported to synthesize hollow MONPs with highly uniform and tailored properties. The synthesized hollow MONPs possessed a large surface area (SBET > 1070.1 m2 g-1), narrow size distribution, large hollow cavity, and thin shell. Interestingly, the incorporation of organic moieties into silica cross-linked networks led to the timely degradation of nanocarriers with the desired responsiveness. Moreover, the applicability of the as-obtained hollow MONPs has been demonstrated in the loading and pH-responsive release of thiamethoxam (THI). The resultant THI-loaded MONPs possessed long-term storage stability at a low temperature and showed release behaviors in response to a basic environment. Benefiting from the shielding property of MONPs, THI-loaded MONPs manifested superior stability against the photolysis as compared to that of the THI technical. This work provides a new consideration for promoting the advancement of nanotechnology in agricultural fields.

Dynamic Growth of Macroscopically Structured Supramolecular Hydrogels through Orchestrated Reaction-Diffusion.

Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl2 and Na2 CO3 ) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities.

Smart Protein-Based Fluorescent Nanoparticles Prepared by a Continuous Nanoprecipitation Method for Pesticides' Precise Delivery and Tracing.

It is highly desirable to develop smart and green pesticide nanoformulations for improving pesticide targeting and reducing their inherent toxicity. Herein, we demonstrate a continuous nanoprecipitation method to construct a novel type of enzyme-responsive fluorescent nanopesticides (denoted as ABM@BSA-FITC/GA NPs) based on abamectin, fluorescein isothiocyanate isomer (FITC)-modified protein, and food-grade gum arabic. The as-prepared ABM@BSA-FITC/GA NPs exhibit good water dispersibility, excellent storage stability, and enhanced wettability compared to commercial formulations. The controlled release of pesticides can be achieved through protein degradation caused by trypsin. Most importantly, the deposition, distribution, and transport of the ABM@BSA-FITC/GA NPs are precisely tracked on target plants (cabbage and cucumber) by fluorescence. Furthermore, the ABM@BSA-FITC/GA NPs show the high control efficacy against Plutella xylostella L., which is comparable with commercial emulsifiable concentrate formulation. In consideration of its eco-friendly composition and absence of organic solvent, this pesticide nanoformulation has promising potential in sustainable plant protection.

High inhabitation activity of CMCS/Phytic acid/Zn2+ nanoparticles via flash nanoprecipitation (FNP) for bacterial and fungal infections.

Plant diseases prompted by fungi and bacteria are one of the most serious threats to global crop production and food security. The destruction of these infections posed a major challenge to plant protection by chemical control. Herein, we develop CMCS/PA/Zn2+ nanoparticles (NPs) using carboxymethyl chitosan (CMCS), phytic acid (PA) and metal ions (Zn2+) via flash nanoprecipitation (FNP) strategy. Metal complexes of PA with specified antibacterial and antifungal activities are expected to hold the potential and play a significant role in antimicrobial treatment. The size and size distribution of NPs was confirmed through Dynamic and Static Light Scatterer (DSLS). In acidic-infection microenvironment, the CMCS/PA/Zn2+ NPs can disintegrate and release Zn2+ in situ thus stimulated the corresponding antimicrobial activity. These CMCS/PA/Zn2+ NPs showed outstanding antibacterial efficacy (98 %) against S. aureus and E. coli bacteria in vitro, as well as an impressive antifungal efficacy of 98 % and 81 % against R. solani and B. cinerea at 50 µg/mL respectively. This study contributes a prospective idea to the development of organic-inorganic hybrid NPs as environmentally-friendly and safe agricultural antimicrobials.

Bifunctional Polymer Brush Reactor for In Situ Synthesis of Hollow Silica-Supported Gold Nanocatalysts.

Gold nanoparticles (AuNPs) on carriers have received wide attention as catalysts as a result of their excellent stability and catalytic performance. Herein, we report the design and synthesis of hollow silica-supported gold nanocatalysts (SNPs@AuNPs) composed of highly dispersed AuNPs with approximately 4.30 nm using an in situ colloidal polyelectrolyte template strategy. The monodisperse polystyrene nanospheres accompanied by poly[(2-methacryloyloxyethyl)trimethylammonium chloride] brushes were first synthesized. Subsequently, the facile polymer-brush-engaged strategy for the synthesis of hollow SNPs@AuNPs involves in situ reduction of AuNPs, hydrolytic condensation of silica, and a chemical etching process. In combination with dynamic light scattering, transmission electron microscopy, small-angle X-ray scattering, X-ray powder diffraction, and Fourier transform infrared spectroscopy, the as-obtained polymer brushes were proven as effective versatile nanoreactors for the synthesis of AuNPs and silica nanoparticles without any catalysts. Benefiting from the structural advantages, the resultant hollow SNPs@AuNPs manifested superior catalytic activity and reusability for the reduction of p-nitrophenol by sodium borohydride in aqueous solution. With a delicate design, we believe that this synthetic strategy can be extended to fabricate multifunctional nanomaterials with diverse compositions, which would be of great interest in catalysis, energy, and many other important domains.

Tea-derived carbon dots with two ratiometric fluorescence channels for the independent detection of Hg2+ and H2O.

Ratiometric fluorescence carbon dots (CDs) that serve as probes have attracted more attention on account of their unique optical properties, low toxicity, anti-interference, and internal reference. However, the facile fabrication of CDs with the aim of detecting multiple targets through mutually independent response channels is always a challenge. Herein, multifunctional label-free N-doped ratiometric fluorescence CDs (N-CDs) are developed from tea leaves extract and o-phenylenediamine by a mild solvothermal method. The prepared N-CDs are tailored with nitrogen- and oxygen-containing functional groups on the surface and contribute to splendid hydrophilia. Two completely independent ratiometric fluorescence channels of N-CDs, respectively, respond to Hg2+ and H2O in a mutually independent manner. Based on the interactions of N-Hg and O-Hg, N-CDs achieve an excellently sensitive and selective detection for Hg2+ in the channel of I387 nm/I351 nm, giving a linear relationship in the range of 0-50 µM. Also, a wide range of Hg2+ concentration (0-100 µM) is linear to A374 nm through UV-vis assay. Otherwise, the linear determination of H2O content (0-30%) is realized in another channel (Igreen/Iblue). The good performance in the independent testing of Hg2+ and H2O, demonstrate that the proposed N-CDs have potential in multifunctional detection.

Temperature Responsive Diblock Polymer Brushes as Nanoreactors for Silver Nanoparticles Catalysis.

Metal nanoparticles are widely used in catalysis. Loading metal nanoparticles into polymer brushes has aroused wide attention, but regulation of catalytic performance still needs to be improved. The novel diblock polymer brushes, polystyrene@sodium polystyrene sulfonate-b-poly (N-isopropylacrylamide) (PSV@PSS-b-PNIPA) and PSV@PNIPA-b-PSS with reversed block sequence, were prepared by surface initiated photoiniferter-mediated polymerization (SI-PIMP) and used as nanoreactors to load silver nanoparticles (AgNPs). The block sequence caused the difference of conformation and further affected the catalytic performance. PSV@PNIPA-b-PSS@Ag was found to be able to control the amount of AgNPs exposed to external reactant of 4-nitrophenol at different temperatures to achieve regulation of the reaction rate due to the hydrogen bonds and further physical crosslinking between PNIPA and PSS.

Cationic Nanogels Enable Gold Nanoparticle Immobilization and Regulated Catalytic Activity.

Polyelectrolyte nanogel consisting of charged network is a prospective platform for developing nanoreactor due to their integrated features of both polyelectrolyte and hydrogel. In this work, cationic poly (methacrylatoethyl trimethyl ammonium chloride) (PMETAC) nanogels with regulated size (30-82 nm) and crosslinking degree (10-50%), has been synthesized by Electrostatic Assembly Directed Polymerization (EADP) method and applied to load gold nanoparticles (AuNPs). Based on the typical reduction reaction of 4-nitrophenol (4-NP), the catalytic performance of the constructed nanoreactor was examined by studying their kinetic process, where the loaded AuNPs exhibited dependent activity on crosslinking degree of nanogels, while independent catalytic activity on nanogel size. Our results validate that, polyelectrolyte nanogels are capable of loading metal NPs and regulating their catalytic performance, therefore demonstrates potential for developing functional nanoreactors.

Resculpting carbon dots via electrochemical etching.

Substantial efforts are directed into exploring the structure-properties relationships of photoluminescent Carbon dots (C-dots). This study unravels a resculpting mechanism in C-dots that is triggered by electrochemical etching and proceeds via extensive surface oxidation and carbon-carbon breakage. The process results in the gradual shrinkage of the nanoparticles and can enhance the quantum yield by more than half order of magnitude compared to the untreated analogues.

Synthesis of zwitterionic polyelectrolyte nanogels via electrostatic-templated polymerization.

Zwitterionic polyelectrolyte nanogels are prospective nanocarriers due to their soft loading pocket and regulated charges. We here report a facile strategy, namely, electrostatic-templated polymerization (ETP) for synthesizing zwitterionic nanogels with controlled size and properties. Specifically, with anionic-neutral diblock polymers as the template, zwitterionic monomers such as carboxybetaine methacrylate (CBMA) or carboxybetaine acrylamide (CBAA) are polymerized together with a cross-linker at pH 2 where the monomers exhibit only positive charge due to the protonation of the carboxyl group. The obtained polyelectrolyte complex micelles dissociate upon introducing a concentrated salt. The subsequent separation yields the released template and zwitterionic nanogels with regulated size and swelling ability, achieved by tuning the salt concentration and cross-linker fraction during polymerization. The obtained PCBMA nanogels exhibit charges depending on the pH, which enables not only the selective loading of different dye molecules, but also encapsulation and intracellular delivery of cytochrome c protein. Our study develops a facile and robust way for fabricating zwitterionic nanogels and validates their potential applications as promising nanocarriers for load and delivery of functional charged cargos.

Continuous Synthesis of Spherical Polyelectrolyte Brushes by Photo-Emulsion Polymerization in a Microreactor.

Nanosized spherical polyelectrolyte brushes (SPBs) are ideal candidates for the preparation of nanometal catalysts, protein separation, and medical diagnostics. Until now, SPBs have been synthesized by photo-emulsion polymerization in a batch reactor, which remains challenging to scale up. This paper reports a successful continuous preparation of SPBs by photo-emulsion polymerization in a self-made microreactor. The effects of residence time, monomer concentration, and feed ratios on the conversion of monomers and SPB structures are systematically investigated by dynamic lighting scattering and transmission electron microscopy. Poly(acrylic acid) (PAA) SPBs obtained in a microreactor exhibiting a narrow size distribution with a short reaction time are very effective in inhibiting the calcium carbonate scale and are comparable to those produced in a batch reactor. This work confirms the feasibility of continuous preparation and scaled-up production of SPBs.

Ultrasmall Pt Nanozymes Immobilized on Spherical Polyelectrolyte Brushes with Robust Peroxidase-like Activity for Highly Sensitive Detection of Cysteine.

Distinct platinum (Pt) nanozymes as peroxidase mimics have received extensive interest owing to their outstanding catalytic activity, high environmental tolerance, lower consumption, and great potential in replacing natural enzymes. However, easy agglomeration of Pt nanoparticles (Pt NPs) resulting from the high surface free energy significantly decrease their peroxidase-like activity. Herein, spherical polyelectrolyte brush (SPB)-stabilized ultrasmall Pt NPs (SPB@Pt NPs) were prepared by a novel synthetic strategy where the SPB not only performed as a nanoreactor for the synthesis of ultrasmall Pt NPs but also greatly stabilized Pt NPs against aggregation. The well-defined SPB@Pt NP nanozymes exhibited outstanding peroxidase-like activity for the catalytic oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB and were then used to establish a colorimetric sensor for rapid detection of cysteine, giving a limit of detection of 0.11 µM. Moreover, the colorimetric detection system was demonstrated with outstanding performance in sensitive and selective detection of cysteine in the presence of several interference molecules. From these results, SPB@Pt NPs have been regarded as promising peroxidase mimics for a large number of applications such as in biosensing, biomedicine, the food industry, and environmental chemistry.