Identification of QTLs responsible for culturability, and fine-mapping of QTL qCBT9 related to callus browning derived from Dongxiang common wild rice (Oryza rufipogon Griff.).

Compared to japonica, the lower genetic transformation efficiency of indica is a technical bottleneck for rice molecular breeding. Specifically, callus browning frequently occurs during the culture of the elite indica variety 93-11, leading to poor culturability and lower genetic transformation efficiency. Here, 67 QTLs related to culturability were detected using 97 introgression lines (designated as 9DILs) derived from Dongxiang common wild rice (DXCWR, Oryza rufipogon Griff.) with 93-11 genetic background, explaining 4% ~12% of the phenotypic variations. The QTL qCBT9 on chromosome 9 was a primary QTL for reducing callus browning derived from DXCWR. Five 9DILs with light callus browning and high differentiation were screened. We evaluated the callus browning index (CBI) of 100 F2 population crossed of 93-11 and 9DIL71 and the recombinant plants screened from 3270 individuals. The qCBT9 was delimited to a ~148kb region between the markers X16 and X23. RNA-seq analysis of DEGs between 9DIL71 and 93-11 showed three upregulated DEGs (Os09g0526500, Os09g0527900, Os09g0528200,) and three downregulated DEGs (Os09g0526700, Os09g0526800, Os09g0527700) were located in the candidate region of qCBT9. Furthermore, callus browning may be involved in cell senescence and death caused by oxidative stress. The differentiation of indica and japonica in this region suggested that qCBT9 was possibly a vital QTL contributed to better culturability of japonica. Our results laid a foundation for further cloning of the gene for reduced callus browning in O. rufipogon, and also provided a new genetic resource and material basis for improving the culturability and genetic transformation efficiency of cultivated rice. Supplementary Information: The online version contains supplementary material available at 10.1007/s11032-024-01470-z.

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.

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.

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.

Mutli-modal straight flow matching for accelerated MR imaging.

Diffusion models have garnered great interest lately in Magnetic Resonance (MR) image reconstruction. A key component of generating high-quality samples from noise is iterative denoising for thousands of steps. However, the complexity of inference steps has limited its applications. To solve the challenge in obtaining high-quality reconstructed images with fewer inference steps and computational complexity, we introduce a novel straight flow matching, based on a neural ordinary differential equation (ODE) generative model. Our model creates a linear path between undersampled images and reconstructed images, which can be accurately simulated with a few Euler steps. Furthermore, we propose a multi-modal straight flow matching model, which uses relatively easily available modalities as supplementary information to guide the reconstruction of target modalities. We introduce the low frequency fusion layer and the high frequency fusion layer into our multi-modal model, which has been proved to produce promising results in fusion tasks. The proposed multi-modal straight flow matching (MMSflow) achieves state-of-the-art performances in task of reconstruction in fastMRI and Brats-2020 and improves the sampling rate by an order of magnitude than other methods based on stochastic differential equations (SDE).

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.

Water resistant, biodegradable and flexible corn starch/carboxymethyl cellulose composite film for slow-release fertilizer coating materials.

The inherent limitations of Cornstarch (CS) and Carboxymethyl Cellulose (CMC) membranes, such as brittleness, fragility, and water solubility, limit their use in controlled-release fertilizers. This study reports on the synthesis of crosslinked CMC/CS-20-E composite membranes using the casting technique, with epichlorohydrin (ECH) as the crosslinking agent in an acidic environment to crosslink CS and CMC. The synthesized composite film demonstrates remarkable water resistance, as evidenced by the insignificant alteration in its morphology and structure post 72 h of water immersion. Its flexibility is reflected in its capacity to endure knotting and bending, with an elongation at break reaching 78.1 %. Moreover, the degradation rate surpasses 90 % within a span of seven days. The CMC/CS-20-E-x-urea controlled-release fertilizer was subsequently produced using a layer-by-layer self-assembly technique, where urea particles were incorporated into the crosslinked composite solution. This CMC/CS-20-E-x-urea controlled-release fertilizer displayed superior controlled-release performance over a duration of seven days when juxtaposed with pure urea. In particular, the CMC/CS-20-E-3 %-urea controlled-release fertilizer showed a cumulative release rate of 84 % by the seventh day. The controlled-release fertilizers developed in this study offer a promising strategy for creating eco-friendly options that are crucial for fertilizing crops with short growth cycles.

Progress of high performance Ti3C2Tx MXene nanocomposite films for electromagnetic interference shielding.

With the rapid growth of 5G communication technology, it is imperative to produce electromagnetic interference (EMI) shielding materials to combat the growing electromagnetic radiation pollution. For new shielding applications, EMI shielding materials with high flexibility, light weight and good mechanical strength are in high demand. Due to their light weight, high flexibility, excellent EMI shielding performance, high mechanical properties, and multifunctionality, Ti3C2Tx MXene nanocomposite films have shown absolute benefits in EMI shielding in recent years. Consequently, numerous lightweight and flexible high-performance Ti3C2Tx MXene nanocomposite films have been generated quickly. In this article, we discuss not only the present state of EMI shielding material research, but also the synthesis and electromagnetic properties of Ti3C2Tx MXene. In addition, the loss mechanism of EMI shielding is described, with an emphasis on the analysis and summary of the research progress of diverse layer structured Ti3C2Tx MXene nanocomposite films for EMI shielding. Finally, the current issues of design and fabrication for Ti3C2Tx MXene nanocomposite films that need to be addressed are proposed, as well as the future research direction for Ti3C2Tx MXene nanocomposite films.

Application of "Click" Chemistry in Biomedical Hydrogels.

Since "click" chemistry was first reported in 2001, it has remained a popular research topic in the field of chemistry due to its high yield without byproducts, fast reaction rate, simple reaction, and biocompatibility. It has achieved good applications in various fields, especially for the preparation of hydrogels. The development of biomedicine presents new challenges and opportunities for hydrogels, and "click" chemistry provides a library of chemical tools for the preparation of various innovative hydrogels, including cell culture, 3D bioprinting, and drug release. This article summarizes several common "click" reactions, including copper-catalyzed azide-alkyne cycloaddition reactions, strain-promoted azide-alkyne cycloaddition (SPAAC) reaction, thiol-ene reaction, the Diels-Alder reaction, and the inverse electron demand Diels-Alder (IEDDA) reaction. We introduce the "click" reaction in the nucleic acid field to expand the concept of "click" chemistry. This article focuses on the application of "click" chemistry for preparing various types of biomedical hydrogels and highlights the advantages of "click" reactions for cross-linking to obtain hydrogels. This review also discusses applications of "click" chemistry outside the field of hydrogels, such as drug synthesis, targeted delivery, and surface modification, hydrogels have great application potential in these fields in the future and hopefully inspire other applications of hydrogels.

In Situ Growth of Zeolitic Imidazolate Framework-L in Macroporous PVA/CMC/PEG Composite Hydrogels with Synergistic Antibacterial and Rapid Hemostatic Functions for Wound Dressing.

Although many advances have been made in medicine, traumatic bleeding and wound infection are two of the most serious threats to human health. To achieve rapid hemostasis and prevent infection by pathogenic microbes, the development of new hemostatic and antibacterial materials has recently gained significant attention. In this paper, safe, non-toxic, and biocompatible polyvinyl alcohol (PVA); carboxymethyl cellulose (CMC), which contains several carboxyl and hydroxyl groups; and polyethylene glycol (PEG), which functions as a pore-forming agent, were used to prepare a novel PVA/CMC/PEG-based composite hydrogel with a macroporous structure by the freeze-thaw method and the phase separation technique. In addition, a PVA/CMC/PEG@ZIF-L composite hydrogel was prepared by the in situ growth of zeolitic imidazolate framework-L (ZIF-L). ZIF-L grown in situ on hydrogels released Zn2+ and imidazolyl groups. They elicited a synergistic antibacterial effect in hemostasis with PVA and CMC, rendering the PVA/CMC/PEG@ZIF-L hydrogel with a good antibacterial effect against Staphylococcus aureus. At the same time, the macroporous structure enabled the rapid release of Zn2+ and imidazolyl groups in ZIF-L and promoted cell proliferation at an early stage, enhancing the coagulation efficiency. A rat liver injury model was used to confirm its rapid hemostasis capacity.

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.

Multiple Intermolecular Interaction to Improve the Abrasion Resistance and Wet Skid Resistance of Eucommia Ulmoides Gum/Styrene Butadiene Rubber Composite.

A rubber composite was prepared by using methyltriethoxysilane (MTES) to modify silica (SiO2) and epoxidized eucommia ulmoides gum (EEUG) as rubber additives to endow silica with excellent dispersion and interfacial compatibility under the action of processing shear. The results showed that compared with the unmodified silica-reinforced rubber composite (SiO2/EUG/SBR), the bound rubber content of MTES-SiO2/EEUG/EUG/SBR was increased by 184%, and its tensile strength, modulus at 100% strain, modulus at 300% strain, and tear strength increased by 42.1%, 88.5%, 130.8%, and 39.9%, respectively. The Akron abrasion volume of the MTES-SiO2/EEUG/EUG/SBR composite decreased by 50.9%, and the wet friction coefficient increased by 43.2%. The wear resistance and wet skid resistance of the rubber composite were significantly improved.

Synergistic Effect of Hydrogen Bonds and Chemical Bonds to Construct a Starch-Based Water-Absorbing/Retaining Hydrogel Composite Reinforced with Cellulose and Poly(ethylene glycol).

The hydrogel prepared by graft copolymerization of starch (ST) and acrylamide (AM) is a commonly used absorbent material; however, due to their irregular network structure and a limited number of hydrophilic groups, starch-based hydrogels have poor water absorption and water retention. To overcome this, here, we provide a new preparation method for starch-based hydrogels. Using cerium ammonium nitrate (CAN) as an initiator, the starch-acrylamide-cellulose (CMC)/poly(ethylene glycol) (S-A-M/PEG) superabsorbent hydrogel was prepared by graft copolymerization. The starch-acrylamide-cellulose/poly(ethylene glycol) hydrogel network is constructed through the synergistic effect of hydrogen bonds and chemical bonds. The experimental results showed that the starch-acrylamide-cellulose/poly(ethylene glycol) superabsorbent hydrogel has a complete network structure that does not easily collapse due to its superior mechanical properties. The water swelling rate reached 80.24 times, and it reached 50.61% water retention after 16 days. This hydrogel has excellent water-absorbing and water-retaining properties, biocompatibility, and degradability, making it useful for further studies in medical, agricultural, and other fields.

A functional modified graphene oxide/nanodiamond/nano zinc oxide composite for excellent vulcanization properties of natural rubber.

A modified graphene oxide/nanodiamond/nanozinc oxide (MGO/ND/nanoZnO) functional hybrid filler is designed and prepared to improve the vulcanization efficiency of a rubber composite and to reduce the use of ZnO. ND was grafted onto graphite oxide with the aid of 4,4'-methylene diphenyl diisocyanate (MDI). NanoZnO, with high surface activity, was then loaded onto the MGO/ND complex through the wet chemical method, in order to synthesize the MGO/ND/nanoZnO functional hybrid filler. Rubber composites were prepared using the rubber latex composite method and their vulcanization behaviors were investigated. Our results show that the MGO/ND/nanoZnO functional hybrid filler can remarkably improve the vulcanization behaviors of the rubber composite. Compared with that of pure natural rubber (NR), the vulcanization activation energy of the rubber composite was reduced by approximately 16%. Moreover, the vulcanization efficiency can be improved by 63% (i.e., the optimum cure time is shortened from the original 405 s to 150 s) after the same amount of traditional ZnO was replaced by the functional hybrid filler loaded with 1 wt% nanoZnO. The prepared MGO/ND/nanoZnO functional hybrid filler thus provides a promising alternative to improve the vulcanization efficiency of rubber composites.

Rivet-Inspired Modification of Aramid Fiber by Decorating with Silica Particles to Enhance the Interfacial Interaction and Mechanical Properties of Rubber Composites.

A rivet-inspired method of decorating aramid fiber (AF) with silica particles (SiO2) is proposed to produce SiO2@AF hybrid materials that have largely enhanced interfacial interaction with the rubber matrix. AF was firstly surface-modified with polyacrylic acid (PAA) to obtain PAA-AF, and SiO2 was silanized with 3-aminopropyltriethoxysilane to obtain APES-SiO2. Then, SiO2@AF was prepared by chemically bonding APES-SiO2 onto the surface of PAA-AF in the presence of dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP). With the incorporation of SiO2@AF into the rubber matrix, SiO2@AF hybrid materials with high surface roughness can play a role as 'rivets' to immobilize large numbers of rubber chains on the surface. The tear strength and tensile strength of rubber composite that filling 4 phr SiO2@AF are dramatically increased by 97.8% and 89.3% compared to pure rubber, respectively. Furthermore, SiO2@AF has superiority in enhancing the cutting resistance of rubber composites, in contrast with unmodified AF and SiO2. SiO2@AF is suitable to be applied as a novel reinforcing filler in rubber composites for high performance.

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.

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.