Polyvinyl alcohol/chitosan quaternary ammonium salt composite hydrogel with directional macroporous structure for photothermal synergistic antibacterial and wound healing promotion.

After skin tissue trauma, wound infections caused by bacteria posed a great threat to skin repair. However, resistance to antibiotics, the current treatment of choice for bacterial infections, greatly affected the efficiency of anti-infection and wound healing. Therefore, there has been a critical need for the development of novel antimicrobial materials and advanced therapeutic methods to aid in skin repair. In this paper, rGO-PDA@ZIF-8 nanofillers were prepared by coating graphene oxide (GO) with dopamine (DA), followed by in situ growth of zeolite imidazolate framework-8 (ZIF-8). Using polyvinyl alcohol (PVA) and chitosan quaternary ammonium salt (CS) as matrix materials, along with polyethylene glycol (PEG) as a pore-forming agent, and rGO-PDA@ZIF-8 as an antimicrobial nano-filler, we successfully prepared rGO-PDA@ZIF-8/PVA/CS composite hydrogels with a directional macroporous structure using bidirectional freezing method and phase separation technique. This hydrogel exhibited excellent mechanical properties, good solubility and water retention capabilities. In addition, the hydrogel demonstrated excellent biocompatibility. Most notably, it not only exhibited excellent bactericidal effect against E. coli and S. aureus (99.1 % and 99.0 %, respectively) under the synergistic effect of intrinsic antibacterial activity and photothermal antibacterial, but also exhibited the ability to promote wound healing, making it a promising candidate for wound healing applications.

Soft Millirobot Capable of Switching Motion Modes on the Fly for Targeted Drug Delivery in the Oviduct.

Small-scale magnetic robots with fixed magnetizations have limited locomotion modes, restricting their applications in complex environments in vivo. Here we present a morphology-reconfigurable millirobot that can switch the locomotion modes locally by reprogramming its magnetizations during navigation, in response to distinct magnetic field patterns. By continuously switching its locomotion modes between the high-velocity rigid motion and high-adaptability soft actuation, the millirobot efficiently navigates in small lumens with intricate internal structures and complex surface topographies. As demonstrations, the millirobot performs multimodal locomotion including woodlouse-like rolling and flipping, sperm-like rotating, and snake-like gliding to negotiate different terrains, including the unrestricted channel and high platform, narrow channel, and solid-liquid interface, respectively. Finally, we demonstrate the drug delivery capability of the millirobot through the oviduct-mimicking phantom and ex vivo oviduct. The magnetization reprogramming strategy during navigation represents a promising approach for developing self-adaptive robots for performing complex tasks in vivo.

An extracellular matrix-mimicking magnetic microrobot for targeted elimination of circulating cancer cells.

Cancer cells disseminate through the bloodstream, leading to metastasis in distant sites within the body. One promising strategy to prevent metastasis is to eliminate circulating tumor cells. However, this remains challenging due to the lack of an active and targeted biomedical tool for efficient cancer cell elimination. Here, we developed a magnetic microrobot by using natural materials derived from the extracellular matrix (ECM) to mimic the ligand-receptor interaction between cancer cells and the ECM, offering targeted elimination of cancer cells. The ECM-mimicking microrobot is designed with a biodegradable hydrogel matrix, incorporating a cancer cell ligand and magnetic microparticles for cancer cell capture and active locomotion. This microrobot was fabricated based on an interface-shearing method, enabling controllable magnetic response and size scalability (30 µm-500 µm). The presented ECM-mimicking microrobot can actively approach and capture single cancer cells and cell clusters under the control of specific magnetic fields. The experiment was conducted in a blood vessel-mimicking simulator. The microrobot demonstrates an outstanding elimination efficacy of 92.3% on MDA-MB-231 cancer cells and a stable transport capability of the captured cells over long distances to a designed recycling site, inhibiting cell metastasis. This magnetic ECM-mimicking microrobot based on a bioinspired binding mechanism represents a promising candidate for the efficient elimination of cancer cells and other biological waste in the blood.

A novel ZIF-8@IL-MXene/poly (N-isopropylacrylamide) nanocomposite hydrogel toward multifunctional adsorption.

Phenols, dyes, and metal ions present in industrial wastewater can adversely affect the environment and leach biological carcinogens. Given that the current research focuses only on the removal of one or two of those categories. Herein, this work reports a novel ZIF-8@IL-MXene/Poly(N-isopropylacrylamide) (NIPAM) nanocomposite hydrogel that can efficiently and conveniently absorb and separate multiple pollutants from industrial wastewater. Ionic liquid (IL) was grafted onto MXene surfaces using a one-step method, and then incorporated into NIPAM monomer solutions to obtain the IL-MXene/PNIPAM composite hydrogel via in-situ polymerization. ZIF-8@IL-MXene/PNIPAM nanocomposite hydrogels were obtained by in-situ growth of ZIF-8 on the pore walls of composite hydrogels. As-prepared nanocomposite hydrogel showed excellent mechanical properties and can withstand ten repeated compressions without any damage, the specific surface area increased by 100 times, and the maximum adsorption capacities for p-nitrophenol (4-NP), crystal violet (CV), and copper ion (Cu2+) were 198.40, 325.03, and 285.65 mg g-1, respectively, at room temperature. The VPTTs of all hydrogels ranged from 33 to 35 °C, so the desorption process can be achieved in deionized water at 35-40 °C, and its adsorption capacities after five adsorption-desorption cycles decreased to 79%, 91%, and 29% for 4-NP, CV, and Cu2+, respectively. The adsorption data fitting results follow pseudo-second-order kinetics and Freundlich models, which is based on multiple interactions between the functional groups contained in hydrogels and adsorbent molecules. The hydrogel is the first to realize the high-efficiency adsorption of phenols, dyes and metal ions in industrial wastewater simultaneously, and the preparation process of hydrogels is environmentally friendly. Also, giving hydrogel multifunctional adsorption is beneficial to promote the development of multifunctional adsorption materials.

Nitrogen-Rich Porous Organic Polymers from an Irreversible Amine-Epoxy Reaction for Pd Nanocatalyst Carrier.

Nitrogen-rich porous organic polymers were fabricated through a nonreversible ring-opening reaction from polyamines and polyepoxides (PAEs). The epoxide groups reacted with both primary and secondary amines provided by the polyamines at different epoxide/amine ratios with polyethylene glycol as the solvent to form the porous materials. Fourier-transform infrared spectroscopy confirmed the occurrence of ring opening between the polyamines and polyepoxides. The porous structure of the materials was confirmed through N2 adsorption-desorption data and scanning electron microscopy images. The polymers were found to possess both crystalline and noncrystalline structures, as evidenced by X-ray diffraction and high-resolution transmission electron microscopy (HR-TEM) results. The HR-TEM images revealed a thin, sheet-like layered structure with ordered orientations, and the lattice fringe spacing measured from these images was consistent with the interlayer of the PAEs. Additionally, the selected area electron diffraction pattern indicated that the PAEs contained a hexagonal crystal structure. The Pd catalyst was fabricated in situ onto the PAEs support by the NaBH4 reduction of the Au precursor, and the size of the nano-Pd was about 6.9 nm. The high nitrogen content of the polymer backbone combined with Pd noble nanometals resulted in excellent catalytic performance in the reduction of 4-nitrophenol to 4-aminophenol.

Ionic liquid decorated MXene/Poly (N-isopropylacrylamide) composite hydrogel with high strength, chemical stability and strong adsorption.

Organic phenolic pollutants in industrial wastewater cause severe environmental pollution and physiological damage. Poly (N-isopropylacrylamide) (PNIPAM) hydrogels generally have poor mechanical strength and are also intrinsically frangible, limiting their widespread applications in wastewater treatment. Combining them with 2-dimensional materials can also only improve the mechanical properties of hydrogels. Here, we report a high-strength, chemical stability and strong adsorption MXene/poly (N-isopropylacrylamide) (PNIPAM) thermosensitive composite hydrogel for efficient removal of phenolic pollutants from industrial wastewater. Ionic liquids (ILs) were grafted onto the surface of MXenes and introduced into NIPAM monomer solution to obtain composite hydrogels by in-situ polymerization for improved mechanical strength and adsorption capacity of the composite hydrogel. Compared with the MXene/PNIPAM composite hydrogel, the introduction of ILs simultaneously improves the mechanical and adsorption properties of the composite hydrogel. The ILs bind to the surface of MXene flakes through electrostatic interactions, which improved the thermal stability and oxidation resistance of MXenes while maintaining its good dispersion. Using 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) modified MXene (MXene-EMIMBF4) did not change significantly were observed after aging for 45 days. As-prepared composite hydrogels demonstrated excellent mechanical properties, reusability, and high adsorption capacity for p-Nitrophenol (4-NP). The MXene-EMIMBF4/PNIPAM hydrogel could recover after ten 95% strain compression cycles under the synergistic effect of chemical bonding and electrostatic attraction. Its maximum adsorption capacity for 4-NP was 200.29 mg g-1 at room temperature, and the adsorption capacity maintained at ∼90% of its initial value after five adsorption cycles, which was related to the introduction of EMIMBF4 to form a denser network structure. The adsorption data followed the pseudo-second-order kinetics and Freundlich models.

In-situ formed Cyclodextrin-functionalized graphene oxide / poly (N-isopropylacrylamide) nanocomposite hydrogel as an recovery adsorbent for phenol and microfluidic valve.

Phenolic compounds are important industrial raw materials for various industrial applications, but phenol-containing wastewater creates significant environmental and biological hazards. To address these issues, a three-dimensional network graphene oxide-cyanoethyltriethoxysilane-ß-cyclodextrin/poly (N-isopropylacrylamide) (GO-CTES-ß-CD/PNIPAM) nanocomposite hydrogel as a phenol recovery adsorbent is prepared herein by in-situ polymerization. Double graft modification on the graphene oxide (GO) via the silane coupling agent 2-cyanoethyltriethoxysilane (CTES) and single (6-tetraethylenepentamine-6-deoxy)-ß-cyclodextrin (NH-ß-CD) compensated the loss of the active sites on both GO and N-isopropylacrylamide (NIPAM), and the hydrogel shows excellent mechanical properties as the chemical crosslinking and physical entanglement of the two components. Consequently, the composite hydrogel achieved an adsorption capacity of 131.64 mg·g-1 for the common environmental toxin 4-NP. After five repeated adsorption-desorption cycles, the hydrogel retained 74% of the initial 4-NP removal ratio. The adsorption results followed pseudo-first-order kinetics, corresponding to heterogeneous multilayer adsorption, which was regulated by a combination of surface adsorption and intra-particle diffusion mechanisms. In general, the nanocomposite hydrogel shows promising application in the field of recycling phenols from wastewater. Also, high photothermal conversion and temperature-sensitive properties are also demonstrated, which makes the hydrogel possessing great potential to be applied in smart microvalves.

Construction of Porous Starch-Based Hydrogel via Regulating the Ratio of Amylopectin/Amylose for Enhanced Water-Retention.

The performance of hydrogels prepared with traditional natural starch as raw materials is considerable; the fixed ratio of amylose/amylopectin significantly limits the improvement of hydrogel structure and performance. In this paper, starch hydrogels were prepared by physical blending and chemical grafting, with the aid of ultrasonic heating. The effects of different amylose/amylopectin ratios on the microstructure and water retention properties of starch hydrogels were studied. The results show that an increase in amylopectin content is beneficial to improve the grafting ratio of acrylamide (AM). The interaction between the AM grafted on amylopectin and amylose molecules through hydrogen bonding increases the pores of the gel network and thins the pore walls. When the amylopectin content was 70%, the water absorption (swelling 45.25 times) and water retention performance (16 days water retention rate 44.17%) were optimal. This study provides new insights into the preparation of starch-based hydrogels with excellent physical and chemical properties.

Pyrene derivative-functionalized mesoporous silica-Cu2+ hybrid ensemble for fluorescence "turn-on" detection of H2S and logic gate application in aqueous media.

The ensemble system PyH-SBA-15-Cu2+ was obtained via coordination interaction of pyrene derivative-functionalized mesoporous SBA-15 and Cu2+, and applied for the selective and sensitive detection of H2S over pH 6.0-12.0 in aqueous media. The sensing strategy was designed on the basis of the H2S-induced dissolution of Cu2+ from PyH-SBA-15-Cu2+. Cu2+ has good binding affinity to N atoms in PyH-SBA-15; therefore, the organic-inorganic hybrid ensemble PyH-SBA-15-Cu2+ was formed, which is nonfluorescent in aqueous solution because of the Cu2+-promoted emission quenching of PyH-SBA-15. The addition of H2S induces the dissolution of PyH-SBA-15-Cu2+ by the formation of stable CuS, thereby producing fluorescence revival of PyH-SBA-15. The correlative "turn-on" fluorescence signals of this ensemble system are linearly proportional to [H2S] in the concentration region of 0-1.0 × 10-4 M, showing a low detection limit of 3.7 × 10-7 M. Other common anions do not induce distinct fluorescence changes. When using the fluorescence intensity signal changes of PyH-SBA-15 as outputs and Cu2+ and S2- as inputs, PyH-SBA-15 can act as an XNOR logic gate.

Metal Organic Framework@Polysilsesequioxane Core/Shell-Structured Nanoplatform for Drug Delivery.

Modern pharmaceutics requires novel drug loading platforms with high drug loading capacity, controlled release, high stability, and good biocompacity. Metal-organic frameworks (MOFs) show promising applications in biomedicine owing to their extraordinarily high surface area, tunable pore size, and adjustable internal surface properties. However, MOFs have low stability due to weak coordinate bonding and limited biocompatibility, limiting their bioapplication. In this study, we fabricated MOFs/polysilsesquioxane (PSQ) nanocomposites and utilized them as drug carriers. Amine-functionalized MOF (UiO-66-NH2) nanoparticles were synthesized and encapsulated with epoxy-functionalized polysilsesquioxane layer on the surface via a facile process. MOFs possessed high surface area and regular micropores, and PSQs offered stability, inertness, and functionality. The obtained UiO-66-NH2@EPSQ nanocomposites were utilized as carriers for ibuprofen, a drug with carboxylic groups on the surface, and demonstrated high drug loading capacity and well-controlled release property. The UiO-66-NH2@EPSQ nanocomposite exhibited low cytotoxicity to HeLa cells within a wide concentration range of 10-100 µg/mL, as estimated by the MTT method. The UiO-66-NH2@EPSQ drug release system could be a potential platform in the field of controlled drug delivery.

Mercapto-Functionalized Porous Organosilica Monoliths Loaded with Gold Nanoparticles for Catalytic Application.

Porous organosilica monoliths have attracted much attention from both the academic and industrial fields due to their porous structure; excellent mechanical property and easily functionalized surface. A new mercapto-functionalized silicone monolith from a precursor mixture containing methyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane; and 3-mercaptopropyl(dimethoxy)methylsilane prepared via a two-step acid/base hydrolysis-polycondensation process was reported. Silane precursor ratios and surfactant type were varied to control the networks of porous monolithic gels. Gold nanoparticles were loaded onto the surface of the porous organosilica monolith (POM). Versatile characterization techniques were utilized to investigate the properties of the synthesized materials with and without gold nanoparticles. Scanning electron microscopy was used to investigate the morphology of the as-synthesized porous monolith materials. Fourier transform infrared spectroscopy was applied to confirm the surface chemistry. 29Si nuclear magnetic resonance was used to investigate the hydrolysis and polycondensation of organosilane precursors. Transmission electron microscopy was carried out to prove the existence of well-dispersed gold nanoparticles on the porous materials. Ultraviolet-visible spectroscopy was utilized to evaluate the high catalytic performance of the as-synthesized Au/POM particles.

Functional Metal Organic Framework/SiO2 Nanocomposites: From Versatile Synthesis to Advanced Applications.

Metal organic frameworks (MOFs), also called porous coordination polymers, have attracted extensive attention as molecular-level organic-inorganic hybrid supramolecular solid materials bridged by metal ions/clusters and organic ligands. Given their advantages, such as their high specific surface area, high porosity, and open active metal sites, MOFs offer great potential for gas storage, adsorption, catalysis, pollute removal, and biomedicine. However, the relatively weak stability and poor mechanical property of most MOFs have limited the practical application of such materials. Recently, the combination of MOFs with inorganic materials has been found to provide a possible strategy to solve such limitations. Silica, which has excellent chemical stability and mechanical properties, shows great advantages in compounding with MOFs to improve their properties and performance. It not only provides structured support for MOF materials but also improves the stability of materials through hydrophobic interaction or covalent bonding. This review summarizes the fabrication strategy, structural characteristics, and applications of MOF/silica composites, focusing on their application in chromatographic column separation, catalysis, biomedicine, and adsorption. The challenges of the application of MOF/SiO2 composites are addressed, and future developments are prospected.

Raspberry-Like Polysilsesquioxane Particles with Hollow-Spheres-on-Sphere Structure: Rational Design, Controllable Synthesis, and Catalytic Application.

Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors with stabilized polystyrene (PS) nanoparticles as both a sacrifice template and a Pickering emulsifier. The PSQ particles were fabricated in an ice bath with methyltrimethoxysilane and mercaptopropyltrimethoxysiane as a co-precursor, tetramethylammonium hydroxide (TMAH) as a catalyst, polyvinylpyrrolidone (PVP) and sodium lignosulfonat as co-stabilizers and PS latex as a hard template. The formation mechanism of the hierarchical particles was investigated in detail by the time study through imaging the particles at regular time intervals during the reaction process. Various effect factors on the morphology were studied systematically which showed that the precursor composition, the content of PS, TMAH and PVP are the most important factors. The hierarchical structure combined with the mercaptopropyl groups on both the surface and the skeleton to make it possible to adsorb guest molecules. Au nanoparticles were immobilized on the particles for the catalytic reduction of 4-nitrophenol to 4-aminophenol. The unique PSQ colloids with hollow-spheres-on-sphere extended the family of the hierarchical structures and has shown the potential applications in separations, drug delivery and heterogeneous catalysts.

Recycled-Oil-Based Polyurethane Modified with Organic Silicone for Controllable Release of Coated Fertilizer.

Fertilizer is very important for increasing food yield, but the extensive use of fertilizer will cause environmental pollution. To enhance the effectiveness of fertilizer, we developed the double organic silicone-modified recycled-oil-based polyurethane as a coating material to prepare degradable polymer coating urea for constant fertilizer release. The moisture, heat resistance, and sustained release properties of polyurethane coating materials were investigated by modification with hydroxyl-terminated polydimethyl silicone (HTPMS) and γ-Aminopropyl triethoxy silane (KH550). The content and distribution of the siloxane groups were effectively controlled by adjusting the content ratio of two kinds of organosilicon. Meanwhile, the organic⁻inorganic hybrid structure was further controlled to form three-dimensional networks with a uniform distribution and a small scale. The moisture and heat resistance of polyurethane were thus improved, resulting in reduced porosity and an excellent sustained release performance. Observably, the best sustained release property of modified polyurethane coated urea was obtained when the ratio of KH550 to HTPMS is 0.3:0.7.

Thiazoline-pyrene selective and sensitive fluorescence "turn-on" sensor for detection of Cu2.

A thiazoline and pyrene containing sensor 1 was synthesized via one-pot reaction and utilized as a highly selective and sensitive fluorescence "turn-on" sensor for Cu2+ detection, via the fluorescence enhancement of pyrene monomer emission. The 2:1 stoichiometry of 1 and Cu2+ was calculated from Job's plots based on fluorescent titrations, and the complexation of 1 with Cu2+ was also supported by mass spectra, Fourier transform infrared spectra, proton NMR spectra and density functional theory analysis. The fluorescence intensity of 1 at 389 nm and 410 nm increased significantly upon the addition of Cu2+. Limit of detection and association constant value of 1-Cu2+ were calculated using standard deviations and linear fittings, respectively. Results showed that 1 was active for Cu2+ detection in the wide pH range of 2.0-11.0.

Controlled synthesis of novel cyanopropyl polysilsesquioxane hollow spheres loaded with highly dispersed Au nanoparticles for catalytic applications.

The design and synthesis of novel cyanopropyl polysilsesquioxane hollow spheres lead to production of a highly active and stable catalyst in the reduction of 4-nitrophenol catalyzed by Au nanoparticles.

Highly porous, water-soluble, superparamagnetic, and biocompatible magnetite nanocrystal clusters for targeted drug delivery.

Magnetic particles have become very promising materials for drug delivery. However, preparation of magnetite particles with high surface area, biocompatibility, strong magnetic response, and suitable particle size still remains a major challenge. In this report, magnetite nanocrystal clusters with high surface areas were fabricated through a solvothermal process by introducing ammonium acetate as a porogen and trisodium citrate as a surface modification agent. The porosity, which was controlled by the reactant concentration, has been investigated in detail. The surface area of the nanocrystal clusters was as high as 141 m(2) g(-1). Ibuprofen, as a model drug, was entrapped into the magnetite carriers. The interfacial interaction between the carboxylic groups on the drug molecules and the carboxylate groups on the carriers enhanced the loading efficiency. Low cytotoxicity in MCF-7 cell and in vitro constant drug release behavior combined with the high drug loading efficiency and high saturation magnetization values demonstrated the potential of the as-synthesized magnetite materials in targeted drug release systems.

Novel fluorinated polysilsesquioxane hollow spheres: synthesis and application in drug release.

Fluorinated polysilsesquioxane (FPSQ) hollow spheres with a large empty interior were synthesized in an aqueous medium by using (trifluoropropyl)trimethoxysilane as the sole precursor. The drug release applications of these spheres were demonstrated, and the materials have great potential as fluorinated drug release carriers.