Organic Inorganic Nanohybrid Research Articles

Carbazole-decorated fluorescent CdS quantum dots: A potential light-harvesting material

An organic-inorganic nanohybrid system (AMC-CdS QD) comprised of a fluorescent carbazole analog, AMC (3-amino-N-methyl carbazole), and CdS QDs has been synthesized, which shows promise as a sustainable energy harvesting material. FT-IR and 1H NMR spectroscopy have ascertained the covalent grafting of the carbazole moieties onto the mercaptopropionic acid (MPA)-capped surface of the CdS QDs. Detailed photophysical characterization of this nanohybrid system have confirmed the occurrence of efficient Fӧrster resonance energy transfer (FRET) from its organic to inorganic counterpart. This phenomenon was also demonstrated using SCC-DFTB-based quantum chemical calculations. As explored in the present work, the photoelectron transfer efficiency of AMC-CdS QDs signifies their plausible future applications as light-harvesting materials.

Mystery of Organic-Inorganic Nano Hybrid “All-Rounder” POSS

Mystery of Organic-Inorganic Nano Hybrid “All-Rounder” POSS

Nanohybrids as a tool to control the dispersion of organic emitters in solution-processed electroluminescent layers

Fluorescent organic–inorganic nanohybrids based on π-extended hydroxyoxophosphole emitters grafted onto ZnO nanocrystals, have been introduced as an efficient way to control the spatial arrangement of the organic emitters within a host material.

A Plasmonic Supramolecular Nanohybrid as a Contrast Agent for Site‐Selective Computed Tomography Imaging of Tumor

AbstractDesign of organic–inorganic hybrids by anchoring of plasmonic materials such as gold nanoparticles (AuNPs) on self‐assembled organic substrates is useful but challenging. Herein, in situ anchoring of plasmonic nanoparticles on the surface of a designed spherical assembly via AuS bond formation is presented. First, a thiol tailed pyrene derivative (2) undergoes solvent dependent self‐assembly, transforming into an organic spherical aggregate (2agg). The thiol (‐SH) rich surface of the organic assembly allows cumulative anchoring of AuNPs on the surface to form an organic–inorganic hybrid (Au@2agg). Further coating of biocompatible polyethylene glycol (PEG) leads to the construction of the final multicomponent system (PEG‐Au@2agg) exhibiting morphological and spectroscopic features. The potential of PEG‐Au@2agg as a bioprobe and a contrast agent is investigated by X‐ray computed tomography (CT) experiments in vivo. High X‐ray attenuation of directly anchored AuNP clusters on the surface of this supramolecular nanohybrids enhances the X‐ray CT contrast and allows tracing of site‐selective accumulation in mouse 4T1 breast tumor. Thus, this approach of designing organic–inorganic nanohybrids paves the way for developing future intelligent multifunctional nanosystems capable of cancer detection and imaging.

Investigations on amidoxime grafted sepiolite based chitosan organic–inorganic nanohybrid composite beads towards wastewater detoxification

This work explores the fabrication of organic–inorganic nanohybrid based biopolymer composite systems for the cleaning of different contaminants from wastewater. This system involves the simultaneous radiation grafting techniques for sepiolite (SP) modification and the simple mixing of modified-SP with biopolymer matrix, chitosan (CS). The SP beads were chemically modified with amidoxime prior to its use in composite systems. The synthesized composite beads were characterized using scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), nitrogen physical adsorption (BET) investigations, Fourier transform infrared (FT-IR), atomic absorption and UV–visible spectroscopy. Hydrolytic stability of beads was also investigated in aqueous media, beads showed excellent stability in aqueous medium and in acidic environment. Here, the sorption profile of copper over amidoxime grafted SP-nanohybrid (MSP) incorporating CS-beads is reported. Furthermore, the key adsorptive variables, i.e. contact time, adsorbent dose, and concentration of adsorbate are discussed. Different isothermal (Langmuir and Freundlich) and kinetics model were also elaborated. Langmuir isotherm and pseudo-second-order models are proved to be the best fit models for Cu (II) removal in aqueous system. To explore the efficacy of the material towards organic pollutants, methylene blue (MB) was selected as model compound and adsorbed on nanohybrid beads. The results revealed that organic–inorganic nanohybrid incorporating CS beads are quite effective for contaminated water remediation, owing to their better adsorptive performance, high stability and easy application.

One-Step Multi-Doping Process for Producing Effective Zinc Oxide Nanofibers to Remove Industrial Pollutants Using Sunlight

Doping processes for optical materials are one of the driving forces for developing efficient and clean technologies for decontamination of aquatic effluents through lowering their band gap energy to become effective in sunlight. The current study has used a non-conventional technique for doping zinc oxide by multi metals, non-metals and organic dyes through a one-step process. In this trend, Zn-Al nanolayered structures have been used as hosts for building host–guest interactions. Organic dyes that have inorganic species of iron, nitrogen and sulfur have been used as guests in the intercalation reactions of Zn-Al layered double hydroxides. By intercalating green dyes, organic–inorganic nanohybrids were formed as nanolayered structures with expanding interlayered spacing to 2.1 nm. By changing the concentration of green dyes and thermal treatment, series of nanofibers and nanoplates of zinc oxides were formed and doped by aluminum, iron and sulfur in addition to colored species. The optical properties of the multi-doped zinc oxide indicated that it became suitable for solar applications because its band gap energy decreased from 3.30 eV to 2.80 eV. The experimental and kinetic results of the multi-doped zinc oxide concluded that the colored pollutants were effectively removed during 50 min of sunlight irradiation.

Frontier luminous strategy of functional silica nanohybrids in sensing and bioimaging: From ACQ to AIE

AbstractFluorescent silica organic–inorganic nanohybrids which combine designable luminescence performance of organic fluorescent dyes and various outstanding advantages of silica nanomaterials have attracted increasing research interests in these fascinating areas. Optical transparency and facile functional modification properties of silica material provide great opportunities to integrate desired fluorescent molecules for various frontier luminous applications. However, conventional organic dyes are typically subject to aggregation‐caused quenching due to their aggregation in silica matrix, which could be detrimental for their performance in sensing and biomedical applications. The appearance of aggregation‐induced emission luminogens (AIEgens) paves a new way for developing highly efficient fluorescent silica nanohybrids (FSNs). FSNs with intensive luminescence could be obtained due to the formation of aggregates and the restricted intramolecular motion of AIEgens in silica inorganic matrix. In this review, the reported fabrication methodologies of various FSNs based on colloidal silica nanoparticles (SNs) and mesoporous SNs including physical entrapment and covalent strategies are summarized. Especially, the AIEgens‐functionalized silica hybrid nanomaterials are introduced in detail. Furthermore, chemical sensing, biosensing, and bioimaging applications of resultant FSNs are also discussed.

Smartly implanted reduced graphene oxide into graphic carbon nitride and copper species for enhanced photoelectric performance

A special organic–inorganic nanohybrid, graphic carbon nitride (g-C3N4)/copper species by smartly implanted reduced graphene oxide was fabricated. The nanohybrid (g-C3N4/rGo/CuxO) exhibited lower interface resistance and higher photoelectric response. It was found that the implanted reduced graphene oxide played an important role in promoting electron transfer in the nanohybrid by improving the linkage of the inorganic copper species and the organic graphic carbon nitride. By solid diffuse reflection spectra, fluorescence spectra, and electron paramagnetic resonance (EPR) spectra, it was confirmed that the excellent performance of the nanohybrid was originated from strong visible absorption, effective separation of photogenerated charges and more oxygen vacancies in the nanohybrid. It will provide a favorable way for constructing organic–inorganic hybrid with high photoelectronic performance.

Preparation and Application of Fluorine-Free Finishing Agent with Excellent Water Repellency for Cotton Fabric.

Water repellent is an important functional finish for cotton fabric. However, cotton fabrics often have poor washing resistance and other performances after actual finishing. In this study, based on the structural characteristics of cotton fiber and durability of water repellent, a cross-linked amino long-chain alkyl polysiloxane (CAHPS) was first prepared, and then reacted with modified silica. Finally, a chemically bonded organic–inorganic nanohybrid cross-linked polysiloxane (rSiO2–CAHPS) was fabricated. Furthermore, the rSiO2–CAHPS was emulsified to obtain a durable fluorine-free water repellent. The water repellent finishing for cotton fabric was carried out by the pad–dry–cure process. After finishing, the cotton fabric had good resistance to conventional liquids and excellent washing resistance, and still maintained good water repellency after 30 rounds of soaping. Moreover, properties including air permeability, mechanical property and whiteness are hardly affected after finishing. SEM and XPS characterization show that a layer of dense silicon film is formed on the surface of cotton fabric by rSiO2–CAHPS water repellent. The existence of nanosilica can improve the surface roughness of cotton fibers. The synergistic effect of fiber matrix, nanoparticles and CAHPS endows the fabric with a micro/nano-multi-scale micro-rough structure, which improves the water repellency of cotton fabric after water repellent finishing.

Injectable catalyst-free “click” organic-inorganic nanohybrid (click-ON) cement for minimally invasive in vivo bone repair

Injectable polymers have attracted intensive attention in tissue engineering and drug delivery applications. Current injectable polymer systems often require free-radical or heavy-metal initiators and catalysts for the crosslinking process, which may be extremely toxic to the human body. Here, we report a novel polyhedral oligomeric silsesquioxane (POSS) based strain-promoted alkyne-azide cycloaddition (SPAAC) “click” organic-inorganic nanohybrids (click-ON) system that can be click-crosslinked without any toxic initiators or catalysts. The click-ON scaffolds supported excellent adhesion, proliferation, and osteogenesis of stem cells. In vivo evaluation using a rat cranial defect model showed outstanding bone formation with minimum cytotoxicity. Essential osteogenic alkaline phosphatase (ALP) and vascular CD31 marker expression were detected on the defect site, indicating excellent support of in vivo osteogenesis and vascularization. Using salt leaching techniques, an injectable porous click-ON cement was developed to create porous structures and support better in vivo bone regeneration. Beyond defect filling, the click-ON cement also showed promising application for spinal fusion using rabbits as a model. Compared to the current clinically used poly (methyl methacrylate) (PMMA) cement, this click-ON cement showed great advantages of low heat generation, better biocompatibility and biodegradability, and thus has great potential for bone and related tissue engineering applications.

Iron doped carbon dots based nanohybrids as a tetramodal imaging agent for gene delivery promotion and photothermal-chemodynamic cancer synergistic theranostics

Nonviral gene delivery vectors for cancer therapy still confronts great challenges as their low transfection efficiency, vague tracing and poor therapeutic effects. Recently, organic–inorganic nanohybrids show complementary and synergistic effects in nano-scaled delivery system, inspiring their applications in gene delivery exploration. A liposomal carbon dots nanohybrids system (PEG-RLS/Fe@CDs) have been fabricated, which was composed of iron-doped carbon dots (Fe@CDs) derived from iron (II) phthalocyanine and amphiphilic lipopeptide assemblies (DSPE-mPEG2000/RLS). With its excellent photothermal conversion capability (η = 63.4%), gene transfection efficiency was increased by 3.5-fold in 4T1 tumor cell and 2-fold in animal model. Introduction of Fe@CDs in the nanohybrids could also serve as a tetramodal contrast agent for fluorescence/photoacoustic/photothermal/magnetic resonance imaging, showing up to 3 orders of magnitude enhancement in photoacoustic signal, as well as 16 °C temperature increasement after 5 min irradiation inside tumor tissue. Furthermore, both in vitro and in vivo studies confirmed the bioactivity of PEG-RLS/Fe@CDs as nanozyme for photothermal and chemodynamic synergistic therapy, leading to a noticeable inhibited tumor growth with 80% survival for at least 50 days in a breast tumor model. These revealed the PEG-RLS/Fe@CDs is a promising candidate platform for improving gene therapy by transfection enhancement, real-time tracing and tumor synergistic destruction.

Fabrication and Characterization of NiO Nanoparticle–Porphyrin-Based Organic–Inorganic Nanohybrid Assembly: a Sustainable Redox Mediator in Dye-Sensitized Solar Cell Construction

Fabrication and Characterization of NiO Nanoparticle–Porphyrin-Based Organic–Inorganic Nanohybrid Assembly: a Sustainable Redox Mediator in Dye-Sensitized Solar Cell Construction

A novel magnetically recyclable semi‐dendrimer catalyst‐based ethanolpyridole supported on ferrite nanoparticles (HNPs@Py) for the synthesis of biscoumarin and dihydropyrano[3,2‐c]chromene derivatives

The novel organic–inorganic nanohybrid magnetic nanoparticles (HNPs@Py) were prepared by a simple method and characterized by FT‐IR, XRD, FE‐SEM, TGA, VSM, EDX, and MAP. The catalytic activity of this new (HNPs@Py) was studied for green synthesis of biscoumarin and 3,4‐dihydropyrano[c]chromene derivatives. The short reaction time, high yields, simple workup, and easy separation of catalyst from the reaction mixture by an external magnetic field are the main advantages of the present protocol.

Modulating carbon-supported transition metal oxide by electron-giving and electron-absorbing functional groups towards efficient overall water splitting

The efficiency of splitting water into hydrogen and oxygen is highly depended on the catalyst used. Enhancing the thermodynamics and/or kinetics of electrocatalytic reactions and redox property through organic–inorganic nanohybrids represents one of the most powerful strategies to boost the electrocatalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a rational design of carbon-supported transition metal oxide grown on a nickel foam surface is reported, which synergistically integrates the thermodynamics and/or kinetics through modification of electronic structures with accelerated kinetics by adjusting electron-giving and electron-absorbing groups. SCN– modification experiment and pre - and post-catalytic analysis manifest that the Co/Fe-N formed between the Co/Fe metal and amino functional group serve as the center of HER. Operando Raman spectroscopy was utilized to explore the OER active intermediates present under catalytic conditions. Specifically, the catalyst requires only an overpotential of 1.466 V to reach 10 mA cm−2 with good stability over 100 h at various current densities between 20, 40, 60, 80 and 100 mA cm−2, superior to controlled transition metal oxides and noble metals. This is a viable and systematic strategy to prepare metal organic framework catalysts with appropriate functional groups that can be used for energy storage and conversion in multiple applications.

Polyaniline@Au organic-inorganic nanohybrids with thermometer readout for photothermal immunoassay of tumor marker.

A photothermal immunoassay using a thermometer as readout based on polyaniline@Au organic-inorganic nanohybrids was built. Temperature output is acquired due to the photothermal effect of the photothermal nanomaterial. Polyaniline@Au organic-inorganic nanohybrids were synthesized by interfacial reactions with high photothermal conversion efficiency. A sandwich structure of the immunocomplex was prepared on a microplate for determination of carcinoembryonic antigen (CEA) by polyaniline@Au organic-inorganic nanohybrids as nanolabel. The released heat based on light-to-heat conversion from the photothermal nanolabel under NIR irradiation is detectable using the thermometer. The increased temperature is directly proportional to CEA concentration. The linear range of the photothermal immunoassay is 0.20 to 25ngmL-1 with determination limit of 0.17ngmL-1. Polyaniline@Au organic-inorganic nanohybrids with high photothermal conversion efficiency was synthesized as labels to construct photothermal immunosensor. The sandwich-type immunoassay was built on 96 hole plate based on specific binding of antigen and antibody. Carcinoembryonic antigen in sample was detected quantitatively by thermometer readout.

An electrochemical sensor for enantiorecognition of tyrosine based on a chiral macrocycle functionalized rGO

A novel chiral sensor was developed to produce the distinguishing response to the enantiomers of tyrosine (Tyr), with high sensitivity and selectivity. The electrochemical sensor was modified by the inorganic-organic nanohybrid material with the functionalization of reduced graphene oxide (rGO) to be the amplifier and a chiral hetero-multifarene[3,2,1] (CHMF[3,2,1]) as the chiral receptor. The as-prepared rGO-CHMF was characterized by transmission electron microscopy (TEM), atomic force microscope (AFM), infrared spectroscopy (IR), thermogravimetric analysis (TGA), Raman spectroscopy and electrochemical methods. It was observed that the composites exhibited different binding ability for Tyr enantiomers. The proposed sensor presented significant difference with peak potential separation value (ΔEp = 70 mV) and the ratio of peak current (IL-Tyr/ID-Tyr = 1.58) for Tyr enantiomers by differential pulse voltammetry. In addition, the peak currents increased linearly with the concentration of Tyr enantiomers in the concentration range 0.1–10 μM with detection limits of 78 nM and 83 nM for l-Tyr and d-Tyr (S/N = 3), respectively. It also exhibited the ability to determine the percentage of one Tyr enantiomer in the racemic mixture. Moreover, the selectivity, reproducibility, and stability of the chiral sensor were investigated to give satisfactory results. The above discoveries offered an alternative technology for chiral recognition with electrochemical response to actualize a real-time and quantitative determination.

Biogenic silver nanowires for hybrid silver functionalized benzothiazolilthiomethanol as a novel organic–inorganic nanohybrid

This article involves the synthesis of a new organic compound, benzothiazolilthiomethanol (BTTM) which derived from the reaction of 2-mercaptobenzothiazole with formaldehyde in ethanol. The resulting compound (BTTM) was diagnosed using the following techniques: FTIR, elemental analysis and 1 H NMR. The research also included the preparation of silver nanowires depending on using green method. To enhance the idea even further, both as-prepared materials were spatially used to prepare new nanocomposite of the type organic–inorganic nanohybrid where silver was used to form the core while the organic matter was the shell. The resulting organic–inorganic nanohybrid was characterized using FTIR, XRD, EDX, SEM and TEM. The results of characterization techniques prove that a stable and sufficient amount of BTTM can be attached to the metal surface.

Organic–inorganic nanohybrids based on an AIE luminogen-functional polymer and CdTe/ZnS QDs: morphologies, optical properties, and applications

Dual-emissive organic–inorganic nanohybrid self-assemblies were constructed by binding red-emitting CdTe/ZnS QDs to blue-emitting AIE-active polymeric micelles in water as a fluorescent probe for PA with interesting assembly behaviour.

Novel organic-inorganic nanohybrids (MnO2 and Ag nanoparticles functionalized 5-methoxy-2-mercaptobenzimidazole): One step synthesis and characterization

The study included the synthesis of manganese dioxide nanoparticles using the nitric acid by oxidation method. Moreover, the work involved the chemical synthesis of Ag metal nanoparticles using sodium citrate for reducing Ag ion into Ag metal in its nanoscale form. These nanoparticles were diagnosed using FTIR, XRD, and AFM. The maximum height was 5 nm and 2.5 nm for Ag NPs and MnO 2 NPs, respectively. In addition, the novelty lies in the use of the organic compound 5-methoxy-2-mercaptobenzimidazole (MMBI) to synthesis the organic–inorganic nanohybrids which were characterized using FTIR and XRD.

A novel superparamagnetic powerful guanidine-functionalized γ-Fe2O3 based sulfonic acid recyclable and efficient heterogeneous catalyst for microwave-assisted rapid synthesis of quinazolin-4(3H)-one derivatives in Green media.

The novel organic–inorganic nanohybrid superparamagnetic (γ-Fe2O3@CPTMS–guanidine@SO3H) nanocatalyst modified with sulfonic acid represents an efficient and green catalyst for the one-pot synthesis of quinazolin-4(3H)-one derivatives via three-component condensation reaction between anthranilic acid, acetic anhydride and different amines under microwave irradiation and solvent-free conditions (4a–q). XRD, FT-IR, FE-SEM, TGA, VSM and EDX were used to characterize this new magnetic organocatalyst. Outstanding performance, short response time (15–30 min), simple operation, easy work-up procedure, and avoidance of toxic catalysts can be regarded as its significant advantages. Moreover, it can be easily separated from the reaction solution through magnetic decantation using an external magnet, and recycled at least six times without notable reduction in its activity.