Organic-inorganic Hybrid Nanomaterials Research Articles

Perovskite photoinitiated RAFT-mediated polymerization-induced self-assembly for organic–inorganic hybrid nanomaterials

An efficient strategy is proposed to construct PQD/polymer organic–inorganic nanohybrids by PET-RAFT polymerization-mediated PISA and the nanohybrid assemblies can maintain excellent luminescence originating from PQDs with enhanced stability.

Controlling Silicification on DNA Origami with Polynucleotide Brushes.

DNA origami has been used as biotemplates for growing a range of inorganic materials to create novel organic-inorganic hybrid nanomaterials. Recently, the solution-based silicification of DNA has been used to grow thin silica shells on DNA origami. However, the silicification reaction is sensitive to the reaction conditions and often results in uncontrolled DNA origami aggregation, especially when growth of thicker silica layers is desired. Here, we investigated how site-specifically placed polynucleotide brushes influence the silicification of DNA origami. Our experiments showed that long DNA brushes, in the form of single- or double-stranded DNA, significantly suppress the aggregation of DNA origami during the silicification process. Furthermore, we found that double-stranded DNA brushes selectively promote silica growth on DNA origami surfaces. These observations were supported and explained by coarse-grained molecular dynamics simulations. This work provides new insights into our understanding of the silicification process on DNA and provides a powerful toolset for the development of novel DNA-based organic-inorganic nanomaterials.

MXenes and Clay Minerals in the Framework of the 2D Organic–Inorganic Hybrid Nanomaterials

MXenes and Clay Minerals in the Framework of the 2D Organic–Inorganic Hybrid Nanomaterials

Controllable Synthesis of Hemoglobin-Metal Phosphate Organic-Inorganic Hybrid Nanoflowers and Their Applications in Biocatalysis.

In recent years, organic-inorganic hybrid nanoflower technology has become an effective method for enzyme immobilization. Here, seven hierarchical flower-like hemoglobin-phosphate organic-inorganic hybrid nanomaterials (Hb-M3(PO4)2·nH2O HNFs) were synthesized through an improved universal one-pot wet-chemical method, with Ca2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+ as inorganic components. In this synthesis process, the metal cations are successively involved in the coordination reaction with Hb and the metathesis reaction to generate phosphate precipitation. The coordination ability of metal cations and the generation rate of phosphate precipitations were evaluated, then the progress of the two chemical reactions was controlled synchronously by adjusting the phosphate buffer (PB) concentration, and finally a flower-like structure conducive to substrate diffusion and transport was obtained. Due to the conformational transformation of hemoglobin and the abundant Cu2+/Fe3+ active sites, the hemoglobin-Cu3(PO4)2·3H2O nanoflowers have extremely high catalytic activity, which is ∼14 times that of Hb. Importantly, this method is suitable for the monometallic-ionic, polymetallic-ionic and polyvalent metal-ion nanoflowers, which broadens the chemical composition and structural diversity of nanoflowers.

Quaternary ammonium silane modified Nanolime for the consolidation and antifungal of stone relics

Cultural relics such as wall paintings and stone relics face a decrease in mechanical strength and contamination from microbial growth. Nanolime (NL), as an exceptional inorganic nanomaterial used in the consolidation of cultural heritages, has been investigated for more than two decades. However, it has limited antibacterial properties. Here, we opted for dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DC5700) to modify the surface of NL particles, praparing an organic–inorganic hybrid nanomaterial (NL-DC5700) that provides long-lasting antifungal effects for stone samples without sacrificing its consolidation effect. Characterizations demonstrate that DC5700 grafts onto the surface of NL particles through the formation of covalent bonds via dehydration condensation between the siloxane of DC5700 and the hydroxyl of NL, forming an organic shell layer that uniformly wraps the NL particles. NL-DC5700 can endow stone samples with near superhydrophobicity (NL, 25.4° and NL-DC5700, 142.0°) and durable antifungal effects over 90 days, superior to those of pure NL. NL-DC5700 shows no unacceptable impact on the appearance, porosity, or microstructure of the stone specimens. Our work explores the antifungal effect of NL-based materials and provides fresh insights into the development of versatile conservation materials for stone relics.

Engineering the Morphostructural Properties and Drug Loading Degree of Organic-Inorganic Fluorouracil-MgAl LDH Nanohybrids by Rational Control of Hydrothermal Treatment.

Layered double hydroxides (LDHs) or hydrotalcite-like compounds have attracted great attention for the delivery of anticancer drugs due to their 2D structure, exhibiting a high surface-to-volume ratio and a high chemical versatility. The drug is protected between the layers from which it is slowly released, thus increasing the therapeutic effect and minimizing the side effects associated to nonspecific targeting. This work aimed to design LDHs with Mg and Al (molar ratio of 2/1) in brucite-like layers, which retained fluorouracil (5-FU; 5-FU/Al = 1, molar ratio) in the interlayer gallery as the layers grow during the co-precipitation step of the synthesis. To rationally control the physicochemical properties, particularly the size of the crystallites, the aging step following the co-precipitation was performed under carefully controlled conditions by changing the time and temperature (i.e., 25 °C for 16 h, 100 °C for 16 h, and 120 °C for 24 h). The results revealed the achievement of the control of the size of the crystals, which are gathered in three different agglomeration systems, from tight to loose, as well as the loading degree of the drug in the final organic-inorganic hybrid nanomaterials. The role played by the factors and parameters affecting the drug-controlled release was highlighted by assessing the release behavior of 5-FU by changing the pH, solid mass/volume ratio, and ionic strength. The results showed a pH-dependent behavior but not necessarily in a direct proportionality. After a certain limit, the mass of the solid diminishes the rate of release, whereas the ionic strength is essential for the payload discharge.

Engineering inorganic interfaces using molecular nanolayers

Advances in interface science over the last 20 years have demonstrated the use of molecular nanolayers (MNLs) at inorganic interfaces to access emergent phenomena and enhance a variety of interfacial properties. Here, we capture important aspects of how a MNL can induce multifold enhancements and tune multiple interfacial properties, including chemical stability, fracture energy, thermal and electrical transport, and electronic structure. Key challenges that need to be addressed for the maturation of this emerging field are described and discussed. MNL-induced interfacial engineering has opened up attractive opportunities for designing organic–inorganic hybrid nanomaterials with high interface fractions, where properties are determined predominantly by MNL-induced interfacial effects for applications.

Periodic Mesoporous Organosilica Nanomaterials with Unconventional Structures and Properties.

Periodic mesoporous organosilicas (PMOs) are high surface area organic-inorganic hybrid nanomaterials that have found broad applications in various fields of research such as in (bio)chemistry or material science. By choosing suitable organic groups in the framework of these materials, their surface properties such as polarity, optical/electrical characteristics and adsorption capacity can be tuned. This critical review provides an overview of the current state of the art in the developments and applications of some PMO nanomaterials in diverse fields of research. This is placed in the context of four leading areas of PMO nanomaterials, including chiral PMOs, plugged PMO nanomaterials, Janus PMOs and PMO-based nanomotors. The review briefly discusses the recent and key findings on these PMO nanomaterials as well as their potential applications for future developments.

Structurally Flexible Au-Cu Alloy Nanoclusters Enabling Efficient Triplet Sensitization and Photon Upconversion.

Ligand-protected noble-metal nanoclusters exhibit an innately triplet nature and have been recently recognized as emerging platforms for triplet sensitizers of photon upconversion (UC) via triplet-triplet annihilation. Herein, we report that a structurally flexible Au-Cu alloy nanocluster, [Au4Cu4(S-Adm)5(DPPM)2]+ (Au4Cu4; S-Adm = 1-adamantanethiolate, DPPM = bis(diphenylphosphino)methane), exhibited favorable sensitizer properties and superior UC performance. Contrary to the structurally rigid Au2Cu6(S-Adm)6(TPP)2 (Au2Cu6, TPP = triphenylphosphine), Au4Cu4 exhibited significantly better sensitizer characteristics, such as a near-unity quantum yield for intersystem crossing (ISC), long triplet lifetime (ca. 8 μs), and efficient triplet energy transfer (TET). The efficient ISC of Au4Cu4 was attributed to the practically negligible activation barriers during the ISC process, which was caused by the spin-orbit interaction between the two isoenergetic isomers predicted by theoretical calculations. A series of aromatic molecules with different triplet energies were used as acceptors to reveal the driving force dependence of the TET rate constant (kTET). This dependency was analyzed to evaluate the triplet energy and sensitization ability of the alloy nanoclusters. The results showed that the maximum value of kTET for Au4Cu4 was seven times larger than that for Au2Cu6, which presumably reflects the structural/electronic fluctuations of Au4Cu4 during the triplet state residence. The combination of the Au4Cu4 sensitizer and the 9,10-diphenylanthracene (DPA) annihilator/emitter achieved UC with internal quantum yields of 14% (out of 50% maximum) and extremely low threshold intensities (2-26 mWcm-2). This performance far exceeds that of Au2Cu6 and is also outstanding among the organic-inorganic hybrid nanomaterials reported so far.

Metal nanoparticles capped with plant polyphenol for oxygen reduction electrocatalysis

The development of a convenient and universal strategy for the synthesis of inorganic–organic hybrid nanomaterials with phenolic coating on the surface is of special significance for the preparation of electrocatalysts. In this work, we report an environmentally friendly, practical, and convenient method for one-step reduction and generation of organically capped nanocatalysts using natural polyphenol tannic acid (TA) as reducing agents and coating agents. TA coated metal (Pd, Ag and Au) nanoparticles are prepared by this strategy, among which TA coated Pd nanoparticles (PdTA NPs) show excellent oxygen reduction reaction activity and stability under alkaline conditions. Interestingly, the TA in the outer layer makes PdTA NPs methanol resistant, and TA acts as molecular armor against CO poisoning. We propose an efficient interfacial coordination coating strategy, which opens up new way to regulate the interface engineering of electrocatalysts reasonably and has broad application prospects.

A Facile Method to Coat Nanoparticles with Lipid Bilayer Membrane: Hybrid Silica Nanoparticles Disguised as Biomembrane Vesicles by Particle Penetration of Concentrated Lipid Layers.

Natural membrane vesicles, including extracellular vesicles and enveloped viruses, participate in various events in vivo. To study and manipulate these events, biomembrane-coated nanoparticles inspired by natural membrane vesicles are developed. Herein, an efficient method is presented to prepare organic-inorganic hybrid materials in high yields that can accommodate various lipid compositions and particle sizes. To demonstrate this method, silica nanoparticles are passed through concentrated lipid layers prepared using density gradient centrifugation, followed by purification, to obtain lipid membrane-coated nanoparticles. Various lipids, including neutral, anionic, and cationic lipids, are used to prepare concentrated lipid layers. Single-particle analysis by imaging flow cytometry determines that silica nanoparticles are uniformly coated with a single lipid bilayer. Moreover, cellular uptake of silica nanoparticles is enhanced when covered with a lipid membrane containing cationic lipids. Finally, cell-free protein expression is applied to embed a membrane protein, namely the Spike protein of severe acute respiratory syndrome coronavirus 2, into the coating of the nanoparticles, with the correct orientation. Therefore, this method can be used to develop organic-inorganic hybrid nanomaterials with an inorganic core and a virus-like coating, serving as carriers for targeted delivery of cargos such as proteins, DNA, and drugs.

Recent advances of triplet–triplet annihilation upconversion in solvent-free solid materials

This review summarized the outstanding solid-state TTA-UC materials developed recently, including matrix-free UC films, sensitizer-doped annihilator crystals and MOFs, UC components doped polymer films and organic–inorganic hybrid nanomaterials.

Designing Fe-containing polyhedral oligomeric silsesquioxane to endow superior mechanical and flame-retardant performances of polyamide 1010

With increasing attention to environmental safety and health, long-chain biologically-based polyamides (PA) are considered to be promising materials owing to their biocompatibility and combining the dual advantages of polyolefins and short-chain petroleum-based polyamides. However, poor flame retardancy severely impedes long-chain biologically-based polyamides’ application in versatile high-standard fields. Herein, we introduced Fe element into the polyhedral oligomeric silsesquioxane (POSS) cage to obtain iron-containing hepta-phenyl POSS (Fe-Ph-POSS), deriving from the chemical reaction between Li-Ph-POSS and FeCl3. The chemical structure of Fe-Ph-POSS was fully characterized and confirmed by FTIR, 1H NMR, 13C NMR, Solid state 29Si NMR, XPS and MALDI-TOF MS. Thereafter, Li-Ph-POSS and Fe-Ph-POSS were adopted to flame retarded biologically-based PA1010. The addition of 10 wt% Fe-Ph-POSS distinctly enhanced the thermal stability without affecting the melting and crystallization temperature of PA1010 composites. Additionally, the introduction of Fe-Ph-POSS did not cause embrittlement for PA1010 and almost completely maintained its excellent mechanical properties (elongation at break, tensile and impact strength were reached 473.8%, 46.87 MPa and 4.52 kJ/m2, respectively). The burning tests results suggested that 10 wt% Fe-Ph-POSS increased the LOI value of PA1010 from 22.6 to 28.4%, and the generation of red-brown char layers rich in iron-containing silicates and carbonates, which effectively hindered the release of heat, smoke and toxic volatiles. Thereby imparting the resultant PA1010 composites to superior flame-retardant performances. Therefore, our work offers an exceptional thought for construction of high-performance biologically-based polyamide composites based on environmentally friendly organic-inorganic hybrid nanomaterials.

Synthesis of {P2W18}-based coated structured nano materials with supercapacitors and H2O2 sensing

The combination of metal-organic frameworks (MOFs) with large specific surface area and high stability and Dawson-type polyoxometalates (POMs) with excellent electron transfer ability to build a new inorganic-organic hybrid as energy storage materials can give full play to the advantages of both. Therefore, the inorganic organic hybrid nano material {Ag4K2P2W18O62}@[Ag3(μ-Hbtc)(μ-H2btc)]n (which became {Ag4K2P2W18O62}@Ag-BTC, where BTC = 1,3,5-benzenetricarboxylic acid) was synthesized by liquid-assisted grinding. The XRD, SEM, TEM characterization show that {Ag4K2P2W18O62}@Ag-BTC is a coating structure. The specific capacitance is 378.9 F g−1 at a current density of 1 A g−1, with a retention rate of 93.5 % for 5000 cycles. An energy density of 7.8 Wh kg−1 and the power density of 500.0 W kg−1 are obtained in water-based symmetric two-electrode supercapacitor system. In addition, when used as an H2O2 sensor, it has a broad detection range of 1.5 μM to 1.5 mM and the small detection limit of 0.206 μM, also offers excellent interference immunity and stability. Moreover, by applying this nano material to the detection of H2O2 in human serum, results are acceptable. The above result shows that the composite material synthesized by the liquid-assisted grinding method adequately combines properties of both parent materials is a viable strategy for achieving performance enhancement.

Chitosan-regulated biomimetic hybrid nanoflower for efficiently immobilizing enzymes to enhance stability and by-product tolerance

Organic-inorganic hybrid nano-materials have been considered to be promising immobilization matrixes for enzymes due to their significantly enhanced reusability and stability of enzymes. Herein, we constructed a novel organic-inorganic hybrid nanoflower via biomacromolecule-regulated biomimetic mineralization to immobilize sucrose phosphorylase (SPase). It was found that chitosan (CS) effectively regulated the biomimetic mineralization of calcium phosphate (CaP), leading to the formation of flower-like hybrid materials for the entrapment of SPase via self-assembly to establish a nano-biocatalyst (CS-CaP@SPase). Upon immobilization, the obtained CS-CaP@SPase exhibited excellent pH, by-product and organic solvents tolerance, and storage stability. Specifically, at acidic condition (pH 4), CS-CaP@SPase performed over 80 % of initial activity, which was 2.42-folds higher than that of free SPase. The catalytic activity of free SPase was severely inhibited about 30 % in the presence of fructose (1.2 M), but CS-CaP@SPase only lost 5 % relative activity. The CS-CaP@SPase retained over 80 % of its relative activity, while the free SPase maintained <20 % of its relative activity in acetonitrile. The relative activity of CS-CaP@SPase was still retained about 80 % after 10 cycles and maintained 75 % after 15 days. Based on Raman spectra analysis, it was also found that the increased β-folding component of SPase in the secondary structure after immobilization was the main factor for its enhanced stability. It is reasonable to believe that biomacromolecule-regulated biomimetic mineralization could be potentially used as a promising method to immobilize enzymes with excellent stability and recyclability, thereby facilitating the preparation of highly efficient catalysts for industrial biocatalysts, biosensing, and biomedicine.

Selective Sensing and Removal of Mercury Ions by Encapsulating Dansyl Appended Calix[4]Conjugate in a Zeolitic Imidazolate Framework as an Organic–Inorganic Hybrid Nanomaterial

Selective Sensing and Removal of Mercury Ions by Encapsulating Dansyl Appended Calix[4]Conjugate in a Zeolitic Imidazolate Framework as an Organic–Inorganic Hybrid Nanomaterial

POSS‐based fluorescence sensor for rapid analysis of β‐carotene in health products

In recent years, fluorescent organic-inorganic hybrid nanomaterials have received much interest as potential fluorescent sensor materials. In this study, fluorescent organic-inorganic hybrid nanomaterials (POSS@ANT) were created using polyhedral oligomeric silsesquioxane as the precursor and 9,10-bromoanthracene as the monomer. The morphology and composition of POSS@ANT, as well as its pore characteristics and fluorescence properties were studied. POSS@ANT displayed steady fluorescence emission at an excitation wavelength of 374 nm. Next, a β-carotene fluorescence sensor was developed using the capacity of β-carotene to quench the fluorescence of POSS@ANT. The quenching process is linked to acceptor electron transfer and energy transfer, and the sensor has a high selectivity for β-carotene. This β-carotene fluorescence analysis method that we established has a linear range of 0.2-4.3mg/L and a detection limit of 0.081 mg/L. Finally, it was used to quantify β-carotene in health products, the recovery rate was 91.1-109.9%, the relative standard deviation (RSD) was 2.2-4.3%, and the results were comparable with the results of high-performance liquid chromatography. The approach is reliable and can be used to determine β-carotene in health products.

The Rise and Future of Discrete Organic-Inorganic Hybrid Nanomaterials.

Hybrid nanomaterials (HNs), the combination of organic semiconductor ligands attached to nanocrystal semiconductor quantum dots, have applications that span a range of practical fields, including biology, chemistry, medical imaging, and optoelectronics. Specifically, HNs operate as discrete, tunable systems that can perform prompt fluorescence, energy transfer, singlet fission, upconversion, and/or thermally activated delayed fluorescence. Interest in HNs has naturally grown over the years due to their tunability and broad spectrum of applications. This Review presents a brief introduction to the components of HNs, before expanding on the characterization and applications of HNs. Finally, the future of HN applications is discussed.

Biomimetic Organic-Inorganic Hybrid Membranes for Removal of Fluoride Ions.

Carbon nanofibers (CaNFs) exhibit promising applications in the fields of environmental science and nanotechnology, and self-assembled peptide nanofibers (PNFs) are useful for the biomimetic synthesis of organic-inorganic hybrid nanomaterials and the fabrication of functional hybrid membranes for the removal of various pollutants from water. In this work, we report the biomimetic synthesis of hybrid nanomaterials by the interweaving of CaNFs and PNFs. Using the biomimetic mineralization properties of PNFs, ZrO2 nanoparticles were synthesized along the nanofiber surface, and then functional nanohybrid porous membranes were prepared by the vacuum filtration technology. For the fabrication of membranes, the amount of PNFs and ZrO2 precursors in the hybrid membrane were optimized. The designed organic-inorganic hybrid membranes exhibited high removal performance for fluorine ion (F−) from water, and the removal efficiency of the fabricated membranes towards F− ion-containing aqueous solution with a concentration of 50–100 mg/L reached more than 80%. In addition, the nanofiltration membranes revealed good adsorption capacity for F− ions. It is expected that the strategies shown in this study will be beneficial for the design, biomimetic synthesis, and fabrication of nanoporous membranes for economic, rapid, and efficient water purification.

Preparation and multiple applications of integrated Zn-Al layered double hydroxide@polydopamine nanocomposites

The preparation and application of inorganic-organic hybrid nanomaterials is a hot research topic at present. Herein, we combined Zn-Al layered double hydroxide (Zn-Al LDH) with mesoporous polydopamine (MPDA) to prepare two integrated Zn-Al LDH@MPDA nanocomposites under the modification of linker (1,3,5-benzoyl chloride (TMC) or (3-aminopropyl) trimethoxysilane (APTMS)), namely Composite T (modified by TMC) and Composite A (modified by APTMS), which were then evaluated for dye adsorption, adriamycin hydrochloride (DOX) loading, photothermal conversion experiment, and antibacterial test. The characterization results showed that MPDA can be successfully loaded on Zn-Al LDH with the modification of the two linkers, but the specific surface area, pore-volume, average pore size, and electronegativity of Composite T were all higher than those of composite A, thus being more advantageous in adsorption of cationic dye. Composite T possesses a high loading capacity for DOX, whose loading efficiency and encapsulation efficiency are 478.3% and 95.7%, respectively. In addition, Composite T also shows a high photothermal conversion efficiency of 27.9%. Furthermore, Composite T exhibits excellent antibacterial activity against Escherichia coli (E. coli) and Staphylococus aureus (S. aureus). Therefore, the designed Zn-Al LDH@MPDA nanocomposites would be a promising candidate for a myriad of industrial application fields.