Cu/Graphene/Clay Nanohybrid: A Highly Efficient Heterogeneous Nanocatalyst for Synthesis of New 5‐Substituted‐1H‐Tetrazole Derivatives Tethered to Bioactive N‐Heterocyclic Cores

A series of new 5‐substituted 1H‐tetrazoles bearing bioactive N‐heterocyclic cores were synthesized through [3 + 2] cycloaddition reactions between alkyl nitriles (RCN) and NaN₃ in the presence of Cu/aminoclay/reduced graphene oxide nanohybrid (Cu/AC/r‐GO nanohybrid) as a heterogeneous nanocatalyst in water/i‐PrOH (50:50, V/V) media at reflux condition. The influence of factors on a sample reaction including solvent type, temperature, and catalyst amount was discussed. This current protocol has many advantages including inexpensiveness, environmentally benign, broad substrate scope, excellent yields, and easy work‐up procedure. The Cu/AC/r‐GO used in this protocol is a low‐cost catalyst that proved to have considerable chemical and thermal stabilities. This non‐hygroscopic catalyst can be easily recycled, reused, and stored for many consecutive reaction runs without significant loss in its reactivity.     

Highly Efficient One‐Pot Three Component Synthesis of 2H‐Indazoles by Consecutive Condensation,C–N and N–N Bond Formations Using Cu/Aminoclay/Reduced Graphene Oxide Nanohybrid

A simple and straightforward one‐pot three‐component synthesis of 2H‐indazoles through copper‐catalyzed consecutive condensation, C–N and N–N bond formations of easily accessible starting materials under ligand‐free conditions is described. In this protocol, treatment of substituted 2‐bromobenzaldehydes, structurally diverse amines, and [bmim]N₃ in the presence of Cu/aminoclay/reduced graphene oxide nanohybrid (Cu/AC/r‐GO nanohybrid) as an efficient heterogeneous catalyst affords the corresponding 2H‐indazoles in good to excellent yields. The influence of effective parameters on the efficient progress of the reaction was studied. The Cu/AC/r‐GO nanohybrid is a stable and inexpensive catalyst that could be simply prepared, recovered, and reused for several reaction runs with no significant decrease in its reactivity.     

Synthesis of polydopamine‐coated graphene–polymer nanocomposites via RAFT polymerization

Graphene‐polymer nanocomposites have significant potential in many applications such as photovoltaic devices, fuel cells, and sensors. Functionalization of graphene is an essential step in the synthesis of uniformly distributed graphene‐polymer nanocomposites, but often results in structural defects in the graphitic sp² carbon framework. To address this issue, we synthesized graphene oxide (GO) by oxidative exfoliation of graphite and then reduced it into graphene via self‐polymerization of dopamine (DA). The simultaneous reduction of GO into graphene, and polymerization and coating of polydopamine (PDA) on the reduced graphene oxide (RGO) surface were confirmed with XRD, UV–Vis, XPS, Raman, TGA, and FTIR. The degree of reduction of GO increased with increasing DA/GO ratio from 1/4 to 4/1 and/or with increasing temperature from room temperature to 60 °C. A RAFT agent, 2‐(dodecylthiocarbonothioylthio)?2‐methylpropionic acid, was linked onto the surface of the PDA/RGO, with a higher equivalence of RAFT agent in the reaction leading to a higher concentration of RAFT sites on the surface. Graphene‐poly(methyl methacrylate), graphene‐poly(tert‐butyl acrylate), and graphene‐poly(N‐isopropylacrylamide) nanocomposites were synthesized via RAFT polymerization, showing their characteristic solubility in several different solvents. This novel synthetic route was found facile and can be readily used for the rational design of graphene‐polymer nanocomposites, promoting their applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3941–3949     

A new efficient adsorbent in the preconcentration studies of the Cr(III) and Fe(III) ions

In this study, the imine‐graphene hybrid material (HM) was used as an adsorbent for removal of Fe(III) and Cr(III) metal ions from the drinking waters. The adsorbent material (HM) was prepared at three steps. At the first step, the graphite was oxidized by Hummer's method for preparation of graphene oxide (GO), in the second step, the silanization derivative (GO‐APTES) was obtained from the reaction of the 3‐(trimethoxysilyl) propylamine and GO. In the final step, the hybrid material (HM) was synthesized from the reaction of the 3,5‐diiodosalicylaldehyde and GO‐APTES. The chemical structures of three materials GO, GO‐APTES and HB were characterized by using the FT‐IR, XRD, EDX, SEM, TEM and UV‐vis methods. Thermal properties of the materials GO, GO‐APTES and HB were investigated by TGA/DTA methods in the 25–1000°C temperature range. Adsorption and desorption studies of the hybrid material toward Fe(III) and Cr(III) metal ions were investigated using the Batch method. The effect of pH, contact time, temperature, concentration on the adsorption properties of the hybrid material were investigated by ICP‐OES. The Fe(III) and Cr(III) ions have the maximum adsorption at the pH 7. The adsorption capacity decreases with the increase in pH values because above pH 9 the adsorption decreases due to the precipitation of metal hydroxide.     

Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission

A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.     

Copper/Graphene/Clay Nanohybrid: A Highly Efficient Heterogeneous Nanocatalyst for the Synthesis of Novel 1,2,3‐Triazolyl Carboacyclic Nucleosides via ‘Click’ Huisgen 1,3‐Dipolar Cycloaddition

A very mild and highly efficient synthesis of some novel 1H‐1,2,3‐triazolyl carboacyclic nucleosides via a ‘Click’ Huisgen cycloaddition of N‐propargyl nucleobases and azido alcohols using Cu/aminoclay/reduced graphene oxide nanohybrid (Cu/AC/r‐GO nanohybrid) as nanocatalyst is described. The preparation and characterization of Cu/AC/r‐GO nanohybrid are discussed. This catalyst was characterized by X‐ray diffraction, FT‐IR, TEM, and energy‐dispersive analysis of X‐ray techniques. Cu/AC/r‐GO nanohybrid is a stable and highly efficient heterogeneous nanocatalyst that can be easily prepared, used, and restored from the reaction mixture by simple filtration, and reused for many consecutive trials without significant decrease in activity.     

Functional Graphene by Thiol‐ene Click Chemistry

Thiol‐ene click reaction was successfully employed for chemical modification of graphene oxide (GO) by one‐step synthesis. Herein, 2,2‐azobis(2‐methylpropionitrile) (AIBN) was used as thermal catalyst and cysteamine hydrochloride (HS?(CH₂)₂?NH₂HCl) was used as thiol‐containing compound, which is incorporated to GO surface upon reaction with the C=C bonds. The hydrochloride acts as protecting group for the amine, which is finally eliminated by adding sodium hydroxide. The modified GO contains both S‐ and N‐containing groups (NS‐GO). We found that NS‐GO sheets form good dispersion in water, ethanol, and ethylene glycol. These graphene dispersions can be processed into functionalized graphene film. Besides, it was demonstrated that NS‐GO was proved to be an excellent host matrix for platinum nanoparticles. The developed method paves a new way for graphene modification and its functional nanocomposites.     

Complex amphiphilic networks derived from diamine‐terminated poly(ethylene glycol) and benzylic chloride‐functionalized hyperbranched fluoropolymers

Amphiphilic copolymer networks were prepared from hyperbranched fluoropolymer (HBFP*, M_n = 38 kDa, by atom transfer radical‐self condensing vinyl copolymerization) and linear diamine‐terminated poly(ethylene glycol) (DA‐PEG, M_n = 1,630 Da). Model studies found that the crosslinking mechanism occurred at ambient temperature as a result of reaction between DA‐PEG and the benzylic chlorides of HBFP*. These networks underwent covalent attachment to glass microscope slides derivatized with 3‐aminopropyltriethoxysilane, whereupon gel percent studies at various weight percentages of DA‐PEG to HBFP* found that curing could be achieved at lower temperatures and shortened time periods relative to the previously reported parent HBFP–PEG system. Thermogravimetric analysis revealed that the crosslinked materials gave no evident mass loss up to 250 °C. Differential scanning calorimetry of the complex amphiphilic networks showed a suppressed glass transition temperature, relative to that observed for neat HBFP*, and multiple melting DA‐PEG endotherm(s) near 30 °C. The films possessed a topographically‐complex surface with features that increased in tandem with an increase in the ratio of DA‐PEG to HBFP*, as detected by atomic force microscopy and quantified by increased rms roughness values. Internal reflection infrared imaging revealed a heterogeneous surface composition and confirmed that the domain sizes increased as the weight percent of DA‐PEG increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4782–4794, 2006     

Green and efficient cycloaddition of CO_2 toward epoxides over thiamine derivatives/GO aerogels under mild and solvent-free conditions

Thiamine derivatives that are cheap, readily available, non-toxic and green are used as heterogeneous catalyst for the generation of cyclic carbonates through cycloaddition of CO_2 to epoxides without the need of co-catalyst and solvent. The interaction between thiamine hydrochloride(VB_1-Cl) and substrates(CO_2 and propylene oxide) was proven by ultraviolet-visible spectroscopy and ~1H nuclear magnetic resonance analysis, and it is deduced that the synergistic action among multi-functional groups(hydroxyl, halide anion and amine) is a favorable factor for cycloaddition reaction. A series of VB_1/GO aerogels were facilely prepared through the addition of aqueous VB_1 derivatives to a suspension of GO in ethanol at room temperature. It was found that the aerogel generated through the interaction of VB_1-Cl with GO shows catalytic activity and stability higher than those of VB_1-Cl. It is because the electrostatic interaction between GO and VB_1-Cl enhances the nucleophilicity and leaving ability of anion. The effects of reaction temperature, catalyst loading, CO_2 pressure and reaction time on CO_2 cycloaddition to propylene oxide were thoroughly studied.     

Phosphomolybdic acid supported on Schiff base functionalized graphene oxide nanosheets: Preparation,characterization, and first catalytic application in the multi‐component synthesis of tetrahydrobenzo[a]xanthene‐11‐ones

New Schiff base (SB) functionalized graphene oxide (GO) nanosheets containing phosphomolybdic counter‐anion H₂PMo₁₂O₄₀^¯ (H₂PMo) were successfully prepared by grafting of 3‐aminopropyltriethoxysilane (APTS) on GO nanosheets followed by condensation with benzil and finally reaction with phosphomolybdic acid (H₃PMo₁₂O₄₀, denoted as H₃PMo) and characterized using Fourier transform infrared (FT‐IR) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), particle size distribution, energy‐dispersive X‐ray (EDX) analysis, EDX elemental mapping, and inductively coupled plasma optical emission spectrometry (ICP‐OES). The prepared new nanomaterial, denoted as GO‐SB‐H₂PMo, was shown to be an efficient heterogeneous catalyst in one‐pot, three‐component reaction of β‐naphthol, aldehydes, and dimedone, giving high yields of tetrahydrobenzo[a]xanthene‐11‐ones within short reaction times. The catalyst is readily recovered by simple filtration and can be recycled and reused several times with no significant loss of catalytic activity.     

Buchwald‐Hartwig amination reaction of aryl halides using heterogeneous catalyst based on Pd nanoparticles decorated on chitosan functionalized graphene oxide

In this work, graphene oxide was functionalized with chitosan (GO‐Chit) followed by a simple approach for immobilization of palladium nanoparticles onto a chitosan grafted graphene oxide surface. The Pd‐nanocomposite (GO‐Chit‐Pd) was characterized using Transmission Electron Microscopy (TEM), Fourier transforms infrared spectroscopy (FT‐IR), and X‐ray diffraction (XRD) measurements. The catalytic activity of the prepared heterogeneous graphene oxide functionalized chitosan‐palladium (GO‐Chit‐Pd) was investigated in term of C‐N coupling reaction (Buchwald‐Hartwig amination reaction of aryl halides) yielding products of N‐arylamines. The easy purification, convenient operation, and environmental friendliness, combined with a high yield, render this method viable for use in both laboratory research and larger industrial scales. Studying the reusability of the catalyst in this work showed that it could be reused for five times without obvious loss in catalytic activity.     

Zirconium (IV) porphyrin graphene oxide: a new and efficient catalyst for the synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones

A covalently cross‐linked graphene oxide (GO) as a catalyst was prepared by a cross‐linking process using the nucleophilic reaction of zirconium (IV)‐coordinated 5,10,15,20‐tetrakis (aminophenyl)porphyrin (ZrPPh) with carboxyl groups of the edges of GO (GO‐ZrPPh). The chemical structure of catalyst was characterized by different analyses such as FT‐IR, SEM, TEM, EDS, ICP, TGA and UV. All analyses confirm the occurrence of successfully covalent immobilization of ZrPPh on the GO. Also, TEM and SEM images show that ZrPPh has been immobilized in the both of the edges and the basal plane of GO. The activity of the catalyst was studied for the synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones via Biginelli reaction. The cross‐linked catalyst is able to catalyze the reaction in short reaction times and good to excellent yields.     

Label‐Free Detection of MicroRNA: Two‐Step Signal Enhancement with a Hairpin‐Probe‐Based Graphene Fluorescence Switch and Isothermal Amplification

A label‐free approach with multiple enhancement of the signal for microRNA detection has been introduced. The key idea of this strategy is achieved by taking advantage of a novel graphene oxide (GO)/intercalating dye based fluorescent hairpin probe (HP) and an isothermal polymerization reaction. In this paper, we used microRNA‐21 (mir‐21) as the target to examine the desirable properties of this assay. When the target, as a “trigger”, was hybridized with the HP and caused a conformation change, an efficient isothermal polymerization reaction was activated to achieve the first step of the “signal” amplification. After incubation with the platform of GO/intercalating dye, the formed complex of DNA interacted with the high‐affinity dye and then detached from the surface of the GO, a process that was accompanied by distinguishable fluorescence recovery. Further signal enhancement has been accomplished by a mass of intercalating dye inserting into the minor groove of the long duplex replication product. Due to the efficient and multiple amplification steps, this approach exerted a substantial enhancement in sensitivity and could be used for rapid and selective detection of Mir‐21 at attomole levels. Proof‐of‐concept evidence has been provided for the proposed cost‐effective strategy; thus, this strategy could expand the application of GO‐material‐based bioanalysis for nucleic acid studies.     

Influence of surface modified graphene oxide on the mechanical performance and curing kinetics of epoxy resin

In this study, the hyperbranched polyester were successfully grafted onto graphene oxide (GO). The mechanical performance and curing kinetics of epoxy resin (EP), EP/ graphene oxide (EP/GO), and EP/ hyperbranched polyester grafted GO (EP/GO‐B) were investigated by means of mechanical tests and differential scanning calorimetry (DSC). Results revealed that the presence of GO lowered the cure temperature and accelerated the curing of EP, and the addition of GO‐B exhibited a stronger effect in accelerating the cure of EP compared with GO. Activation energies were calculated using Kissinger approach, and Ozawa approach, respectively. Results revealed lowered activation energy after the addition of GO or GO‐B at low degrees of cure, indicating that GO had a large effect on the curing reaction. The presence of GO facilitated the curing reaction, especially the initial epoxy‐amine reaction. Moreover, GO‐B exhibited better performance. Related mechanism was proposed.     

Layer-by-layer inkjet printing of fabricating reduced graphene-polyoxometalate composite film for chemical sensors

Graphene oxide (GO) nanosheets and polyoxometalate such as H(3)PW(12)O(40) (PTA) are prepared into a multilayer film via a layer-by-layer inkjet printing method. The GO/PTA composite thin film shows linear, uniform and regular layer-by-layer growth. Under UV-irradiation, a photoreduction reaction takes place in the film which converts GO to reduced GO (rGO) due to the photoreduction activity of polyoxometalate clusters. According to the cyclic voltammograms measurement, the rGO/PTA composite film displays good electrocatalytic activity for the oxidation of dopamine (DA). The oxidation peak current (I(pa)) increases gradually with increasing the dopamine concentration, which may be used in electrochemical biosensors.     

Effect of polycarbonate structure and reduction time on graphene oxide dispersion

Polycarbonate (PC)/graphene oxide (GO) composites with different GO reduction time and PC types were prepared by using a twin screw extruder at 260 °C after solution mixing with chloroform. The chemical reaction degree of PC/GO composites with GO reduction time was confirmed by C–H stretching peak at 3000 cm ^?1, and the chemical reaction degree decreased with GO reduction time. The slope for storage (G′) versus loss (G″) modulus plot decreases with an increase in heterogeneous property of the polymer melts. So we can check the GO dispersion of the PC/GO composites using by the slop for G′–G″ plot. According to the G′–G″ slopes for PC/GO composite with GO reduction time, GO was well dispersed within PC matrix when the reduction time decreased. It was re‐confirmed by atomic force microscope (AFM) results. Based on the degradation temperature by Thermogravimetric analysis, G′–G″ slopes, and surface roughness by AFM, the branched PC was better than linear PC for the GO dispersion within PC matrix. The fact was also confirmed by tensile test results that the Young's modulus increased with the improvement of GO dispersion. Copyright © 2015 John Wiley & Sons, Ltd.     

Functionalization of graphene oxide towards thermo‐sensitive nanocomposites via moderate in situ SET‐LRP

A mild and efficient strategy is presented for growing thermo‐sensitive polymers directly from the surface of exfoliated graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of GO sheets followed by in situ growing poly[poly(ethylene glycol) ethyl ether methacrylate] (PPEGEEMA) via single‐electron‐transfer living radical polymerization (SET‐LRP). Considering the lack of reactive functional groups on the surface of GO, exfoliated GO sheets were subjected to an epoxide ring opening reaction with tris(hydroxymethyl) aminomethane (TRIS) at room temperature. The initiating groups were grafted onto TRIS‐GO sheets by treating hydroxyls with 2‐bromo‐2‐methylpropionyl bromide at room temperature. PPEGEEMA chains were synthesized by in situ SET‐LRP using CuBr/Me₆TREN as catalytic system at 40 °C in H₂O/THF. The resulting materials were characterized using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of GO sheets. After grafting with PPEGEEMA, the modified GO sheets still maintained the separated single layers and the dispersibility was significantly improved. This TRIS‐GO‐PPEGEEMA hybrid material shows reversible self‐assembly and deassembly in water by switching temperature at about 34 °C. Such smart graphene‐based materials promise important potential applications in thermally responsive nanodevices and microfluidic switches. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Ozonated Graphene Oxide Film as a Proton‐Exchange Membrane

Graphene oxide (GO) contains several chemical functional groups that are attached to the graphite basal plane and can be manipulated to tailor GO for specific applications. It is now revealed that the reaction of GO with ozone results in a high level of oxidation, which leads to significantly improved ionic (protonic) conductivity of the GO. Freestanding ozonated GO films were synthesized and used as efficient polymer electrolyte fuel cell membranes. The increase in protonic conductivity of the ozonated GO originates from enhanced proton hopping, which is due to the higher content of oxygenated functional groups in the basal planes and edges of ozonated GO as well as the morphology changes in GO that are caused by ozonation. The results of this study demonstrate that the modification of dispersed GO presents a powerful opportunity for optimizing a nanoscale material for proton‐exchange membranes.     

Preparation and Electrochemiluminescence of a Graphene Oxide/Selenium Nanocomposite

A novel amplification system for electrochemiluminescence (ECL) was developed by combining graphene oxide (GO) and Se nanoparticles, in which the chitosan (CHIT) was used as improver. Based on a series of experiments, the influencing factors and mechanism for ECL emission were determined. Under optimal conditions, the GO/Se nanocomposite produced an intense ECL emission and maintained long-term ECL stability. Significantly, the electrode modified with GO/Se nanocomposite was used to detect the biomolecule dopamine (DA), and showed a linear range from 0.1 to 100 µM, with a detection limit of 0.025 µM.     

New functionalization of graphene oxide with N2O2 ligand for efficient loading of Cu nanostructures as a heterogeneous nanocatalyst for the synthesis of β-hydroxy-1,2,3-triazoles

A new and heterogeneous copper complex immobilized on graphene oxide (GO) was prepared. This was achieved through organic functionalization of GO using 1,8-diamino-3,6-dioxaoctane (DADO) and then inorganic coordination of copper on the edges and basal plane of the functionalized GO (GO-DADO-Cu), which was reduced to Cu(0). The chemical structure of the prepared nanocatalyst was analyzed using various techniques. Most of the analyses confirmed the successful anchoring of copper and organic ligand on the GO surface. Moreover, the synthesized nanocatalyst has shown high catalytic activity in the synthesis of β-hydroxy-1,2,3-triazole derivatives under mild reaction conditions (water and room temperature) resulting in good to excellent yields.