Environmentally friendly synthesis of noble metal nanoparticles assisted by biodegradable dextran‐graft‐lactone copolymers

A simple “green synthesis” of noble metal nanoparticles by direct reaction between Dextran‐graft‐lactone copolymers and metal salts without the need to separately add reducing and stabilizing agents was carried out. The effects of the composition, molecular weights of copolymers and solvents on the characteristics of the nanoparticles were considered. The amphiphilic character of the copolymers seems to be an important factor in the results of the synthesis. According to the results, general correlations between experimental parameters of synthesis and characteristics of the obtained nanoparticles were established. Techniques such as, transmission electron microscopy, scanning electron microscopy, UV–visible spectroscopy, Zeta Potential, dynamic light scattering and Fourier transform Infrared Spectroscopy, were used for the characterization of the products. The results indicate the possibility of control of the characteristics of the nanostructured material. Copyright © 2014 John Wiley & Sons, Ltd.     

Transition‐metal nanoparticles: synthesis,stability and the leaching issue

This perspective examines the state‐of‐the‐art of catalysis by metal nanoparticles. We outline various methods for preparing metal nanoparticle suspensions, and highlight the role of the stabilizers and the stabilizing principles. Subsequently, we examine some catalytic applications of homometallic and bimetallic nanoparticle suspensions in a variety of reactions. The cases are divided according to the stabilizing agent: polymers, dendrimers, ionic liquids, surfactants, micelles and micoremulsions, ligands and solid supports. We explain the importance of atom/ion leaching (all too frequent in nanoparticle catalysis, especially for the catalytically active group VIII metals) and consider ways of minimizing it. The future perspectives of nanoparticles as catalysts are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation of size‐controlled In2O3 nanoparticles

Highly crystalline and monodisperse In₂O₃ nanoparticles were successfully prepared by thermal decomposition of In(dipy)₃Cl₃·2H₂O in oleylamine and oleic acid under inert atmosphere. The size of In₂O₃ nanoparticles could be readily tuned from 10–15 nm to 40–50 nm, depending on the molar ratio of precursor to combined solvent in the reaction system. As‐synthesized In₂O₃ nanoparticles have a center‐body cubic structure as characterized by powder X‐ray diffraction and selected‐area electron diffraction. Transmission electron microscopy images showed that In₂O₃ nanoparticles have a narrow size distribution. A relatively strongly PL peak centered at 378 nm could be clearly seen when 10–15 nm In₂O₃ nanoparticles redispersed in cyclohexane were excited at 275 nm at room temperature. Copyright © 2007 John Wiley & Sons, Ltd.     

AgPt nanoparticles supported on magnetic graphene oxide nanosheets for catalytic reduction of 4‐nitrophenol: Studies of kinetics and mechanism

Ag_x Pt_100−x (x  = 0, 25, 50, 75 and 100) nanoparticles were grown on the surface of magnetic graphene oxide nanosheets (Fe₃O₄@GO) for the first time. The as‐prepared nanocomposites were characterized using various techniques such as Fourier transform infrared spectroscopy, powder X‐ray diffraction, field emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy, Brunauer–Emmett–Teller surface area analysis, vibrating sample magnetometry and thermogravimetric analysis. The Fe₃O₄@GO‐Ag_x Pt_100−x catalysts were applied in the reduction of 4‐nitrophenol (4‐NP) to 4‐aminophenol using sodium borohydride (NaBH₄). The synthesized nanocomposites exhibited excellent catalytic performance in the reduction of 4‐NP with high recyclability for five consecutive runs. The Fe₃O₄@GO‐Ag₇₅Pt₂₅ nanocomposite exhibited the best catalytic activity with a rate constant as high as 140.6 × 10⁻³ s⁻¹. The obtained kinetic data were modelled with the Langmuir–Hinshelwood equation. The energy of activation and thermodynamic parameters including enthalpy, entropy of activation and activation Gibbs free energy were calculated.     

Facile synthesis of Ti4+‐immobilized affinity silica nanoparticles for the highly selective enrichment of intact phosphoproteins

Currently, great challenges to top‐down phosphoproteomics lie in the selective enrichment of intact phosphoproteins from complex biological samples. Herein, we developed a facile approach for synthesis of Ti⁴⁺‐immobilized affinity silica nanoparticles and applied them to the selective separation and enrichment of intact phosphoproteins based upon the principle of metal(IV) phosphate/phosphonate chemistry. The as‐prepared affinity materials exhibited high selectivity and adsorption capacities for model phosphoproteins (328.9 mg/g for β‐casein, 280.5 mg/g for ovalbumin, and 225.8 mg/g for α‐casein), compared with nonphosphoproteins (79.28 mg/g for horseradish peroxidase, 72.70 mg/g for BSA, and 27.28 mg/g for lysozyme). In addition, the resuability of the affinity silica nanoparticles was evaluated, and the results demonstrated a less than 10% loss of adsorption capacity after six adsorption–regeneration cycles. The practicability of the affinity materials was demonstrated by separating phosphoproteins from protein mixtures and drinking milk samples, and the satisfactory results indicated its potential in phosphoproteomics analysis.     

Chemo‐selective reduction of nitro and nitrile compounds using Ni nanoparticles immobilized on hyperbranched polymer‐functionalized magnetic nanoparticles

The nitro and nitrile groups in aromatic and aliphatic compounds containing various reducible substituents such as carboxylic acid, ketone, aldehyde and halogen are selectively reduced to the corresponding amines in water as a green solvent with excellent yields by employing NaBH₄ in the presence of Fe₃O₄@PAMAM/Ni(0)‐b‐PEG nanocatalyst. The morphology and structural features of the catalyst were characterized using various microscopic and spectroscopic techniques. The designed catalyst system because of it being covered with hydrophilic polymers is soluble in a wide range of solvents (e.g. water and ethanol) and suitable for immobilizing and stabilizing Ni nanoparticles in aqueous mediums. In addition, the catalyst can be easily recovered from a reaction mixture by applying an external magnetic field and can be reused up to six runs without significant loss of activity.     

Catalytic reduction of 4‐nitrophenol using silver nanoparticles‐engineered poly(N‐isopropylacrylamide‐co‐acrylamide) hybrid microgels

Nearly monodisperse poly(N ‐isopropylacrylamide‐co ‐acrylamide) [P(NIPAM‐co‐AAm)] microgels were synthesized using precipitation polymerization in aqueous medium. These microgels were used as microreactors to fabricate silver nanoparticles by chemical reduction of silver ions inside the polymer network. The pure and hybrid microgels were characterized using Fourier transform infrared and UV–visible spectroscopies, dynamic light scattering, X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry and transmission electron microscopy. Results revealed that spherical silver nanoparticles having diameter of 10–20 nm were successfully fabricated in the poly(N ‐isopropylacrylamide‐co ‐acrylamide) microgels with hydrodynamic diameter of 250 ± 50 nm. The uniformly loaded silver nanoparticles were found to be stable for long time due to donor–acceptor interaction between amide groups of polymer network and silver nanoparticles. Catalytic activity of the hybrid system was tested by choosing the catalytic reduction of 4‐nitrophenol as a model reaction under various conditions of catalyst dose and concentration of NaBH₄ at room temperature in aqueous medium to explore the catalytic process. The progress of the reaction was monitored using UV–visible spectrophotometry. The pseudo first‐order kinetic model was employed to evaluate the apparent rate constant of the reaction. It was found that the apparent rate constant increased with increasing catalyst dose due to an increase of surface area as a result of an increase in the number of nanoparticles.     

Determination of maximum loading capacity of polyamidoamine (PAMAM) dendrimers and evaluation of Cu55 dendrimer‐encapsulated nanoparticles for catalytic activity

Spectrophotometric titrations provide information about the interior of the polyamidoamine (PAMAM) dendrimers, and therefore how nanoparticles are encapsulated. In this work, binding studies were performed to determine maximum loading capacities (N) of hydroxyl terminated G4, G5, and G6 PAMAM dendrimers with Cu²⁺ ions. The values of N found via spectrophotometric titrations were 16.22, 31.86, and 57.36 for G4‐OH, G5‐OH, and G6‐OH, respectively. The determination of loading capacity was also done using Viva spin filtration, and the results were found to be in agreement with those found via spectrophotometric titrations. From the binding isotherm, the values of equilibrium constant (K′) were determined and found to be 0.0488 (G4‐OH), 0.0291 (G5‐OH), and 0.0158 (G6‐OH). Owing to instability of G4‐OH (Cu₁₆), G5‐OH (Cu₃₂), and G6‐OH (Cu₅₇) dendrimer‐encapsulated nanoparticles (DENs) synthesized, G6‐OH (Cu₅₅) DENs of average size 2.6 ± 0.3 nm were prepared and were found to be relatively stable. Thus G6‐OH (Cu₅₅) catalyst was evaluated for the reduction of 4‐nitrophenol and was found to be catalytically active toward reduction of 4‐nitrophenol. Reaction kinetics of 4NP reduction was thoroughly studied in light of the Langmuir‐Hinshelwood kinetic model, and surface rate k, and the adsorption rates K_4NP, and K_BH4 were determined. The reaction was performed at different temperatures, which further expanded the study into determination of thermodynamic (ΔH^‡, ΔS^‡, ΔG^‡, and E_A) parameters.     

金属纳米结构的氧化刻蚀调控与催化性能优化

金属纳米结构的可控合成,对其性能优化和高效应用至为关键．氧化刻蚀作为金属纳米晶可控合成中的新兴有效调控手段之一,受到越来越多的关注．本文以本课题组近期的研究工作为例,说明了氧化刻蚀对金属纳米晶的形貌、尺寸、结构及组成等合成参数的有效调控作用．由此总结认为,在金属纳米晶可控合成的一般过程,尤其是成核和生长过程中,氧化刻蚀的本质是有效调控“两个速率”和“两个力学”,即减缓原子的生成速率与晶种的形成速率、选择性接受反应热力学和反应动力学的控制作用．我们将通过氧化刻蚀法调控合成得到的具有独特结构的Pd,Pt纳米晶,用于氧活化和电催化这两个重要的催化体系,获得了理想的催化结果,表明氧化刻蚀在金属纳米晶的功能改性和应用拓展方面,具有令人称奇的广阔应用前景．     

Encapsulation of Pd(II) into superparamagnetic nanoparticles grafted with EDTA and their catalytic activity towards reduction of nitroarenes and Suzuki–Miyaura coupling

A robust, safe and magnetically recoverable palladium catalyst was synthesized by anchoring Pd(II) onto ethylenediaminetetraacetic acid‐coated Fe₃O₄ (Fe₃O₄@EDTA) magnetic nanoparticles. The Fe₃O₄ magnetic nanoparticle‐supported Pd(II)–EDTA complex catalyst thus obtained was characterized using scanning and transmission electron microscopies, thermogravimetric analysis, vibrating sample magnetometry, X‐ray diffraction, and inductively coupled plasma atomic emission and Fourier transform infrared spectroscopies. Fe₃O₄@EDTA–Pd(II) was screened for the Suzuki reaction and reduction of nitro compounds in water. The Pd content of the catalyst was measured to be 0.28 mmol Pd g^?1. In addition, the Fe₃O₄@EDTA–Pd catalyst can be easily separated and recovered with an external permanent magnet. The anchored solid catalyst can be recycled efficiently and reused five times with only a very slight loss of catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Ionic‐liquid‐assisted desorption of DNA from polyamidoamine‐grafted silica nanoparticles surface by a low‐salt solution

We studied the influences of imidazolium‐based ionic liquids as additives in low ionic strength phosphate solution on releasing DNA from polyamidoamine dendrimer‐grafted silica nanoparticle surfaces. The effects of the side‐chain length of the imidazolium group, the anion and the concentration of the ionic liquid, the generation of the dendrimer, and the pH and the concentration of the release solution were investigated. It was found that addition of 4 mM 1‐hexyl‐3‐methylimidazolium bromide to 5 mM phosphate at pH 11 could markedly promote the desorption of DNA fragments, with a desorption efficiency of 99.0%. Compared with the conventional strategies employing high‐salt solutions or elevated temperature for acceptable recoveries, the method described here enabled quick release of DNA fragments that permitted direct, accurate analysis, and further treatment without desalting.     

One‐pot dual size‐ and shape selective synthesis of tetrahedral Pt nanoparticles

One‐pot dual size‐ and shape‐selective synthesis of tetrahedral Pt nanoparticles is achieved using the pre‐prepared Pt nanoparticles as the ‘external seeds’, and controlling the slow diffusional growth under hydrogen reduction in the presence of PVP as the capping agent. Copyright © 2006 John Wiley & Sons, Ltd.     

Silica‐Supported Silver Nitrate as a Highly Active Dearomatizing Spirocyclization Catalyst: Synergistic Alkyne Activation by Silver Nanoparticles and Silica

Silica‐supported AgNO₃ (AgNO₃–SiO₂) catalyzes the dearomatizing spirocyclization of alkyne‐tethered aromatics far more effectively than the analogous unsupported reagent; in many cases, reactions which fail using unsupported AgNO₃ proceed effectively with AgNO₃–SiO₂. Mechanistic studies indicate that this is a consequence of silver nanoparticle formation on the silica surface combined with a synergistic effect caused by the silica support itself. The remarkable ease with which the reagent can be prepared and used is likely to be of much synthetic importance, in particular, by making nanoparticle catalysis more accessible to non‐specialists.     

A Simple and Fast Aqueous‐Phase Synthesis of Ultra‐Highly Concentrated Silver Nanoparticles and Their Catalytic Properties

A simple and fast synthetic route to ultra‐highly concentrated silver nanoparticles with long‐term stability by reducing AgNO₃ with ascorbic acid in the presence of polyethyleneimine (PEI) as a stabilizer in an aqueous phase is reported. The concentration of silver precursor was as high as 2000 mm (200 g of Ag nanoparticle per liter of water) and the reaction time was less than 10 min. The resulting silver nanoparticles show long‐term stability after two months of storage at room temperature without any signs of particle aggregation or precipitation in an aqueous phase. The successful ligand exchange of PEI‐stabilized silver nanoparticles to polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) without particle aggregation is also demonstrated. In addition, the catalytic activities of silver nanoparticles stabilized by various stabilizers prepared by the ligand exchange method was investigated. The PEI‐stabilized silver nanoparticles exhibited a higher stability than those of PEG‐ and PVP‐stabilized silver nanoparticles in the diffusion‐controlled catalytic reduction of 4‐nitrophenol to 4‐aminophenol by NaBH₄.     

"Click" dendrimers: synthesis, redox sensing of Pd(OAc)2, and remarkable catalytic hydrogenation activity of precise Pd nanoparticles stabilized by 1,2,3-triazole-containing dendrimers

"Click" dendrimers containing 1,2,3-triazolyl ligands that coordinate to PdII(OAc)2 have been synthesized in view of catalytic applications. Five of these dendrimers contain ferrocenyl termini directly attached to the triazole ligand in order to monitor the number of PdII that are introduced into the dendrimers by cyclic voltammetry. Reduction of the PdII-triazole dendrimers by using NaBH4 or methanol yields Pd nanoparticles (PdNPs) that are stabilized either by several dendrimers (G0, DSN) or by encapsulation inside a dendrimer (G1 and G2: DEN), as confirmed by TEM. Relative to PAMAM-DENs (PAMAM=poly(amidoamine)), the "click" DSNs and DENs show a remarkable efficiency and stability for olefin hydrogenation under ambient conditions of various substrates. The influence of the reductant of PdII bound to the dendrimers is dramatic, reduction with methanol leading to much higher catalytic activity than reduction with NaBH4. The most active NPs are shown to be those derived from dendrimer G1, and variation of its termini groups (ferrocenyl, alkyl, phenyl) allowed us to clearly delineate, optimize, and rationalize the role of the dendrimer frameworks on the catalytic efficiencies. Finally, hydrogenation of various substrates catalyzed by these PdNPs shows remarkable selectivity features.     

Silver nanoparticles immobilized onto poly(4‐vinylpyridine)‐functionalized magnetic nanoparticles: A robust magnetically recyclable catalyst for oxidant‐free alcohol dehydrogenation

A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4‐vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques.     

Tea polyphenol-assisted green synthesis of Ag-nanodiamond hybrid and its catalytic activity towards 4-nitrophenol reduction

Herein, we describe an environmentally friendly strategy to synthesize Ag nanoparticles on Nanodiamond (ND) by utilizing natural adhering and reduction properties of tea polyphenols (TPs). Firstly, the surface of ND was modified by TPs through their natural adhering ability. Then, the modified TPs functioned as reducing agents for reducing Ag precursor in situ. The synthesis process, structure and its physicochemical properties of the nanohybrid were tracked and characterized by UV-Vis, FTIR, TGA, HRTEM, XRD and XPS. It has been shown that Ag nanoparticles with uniform size and distribution were anchored successfully on the surface of ND. The ND supported Ag nanoparticles displayed highly water dispersibility due to the hydrophilicity of TPs, as is very important in heterogeneous catalysis. The catalytic performance of this nanohybrid was evaluated comprehensively by catalyzing 4-nitrophenol reduction by sodium borohydride, which is often used as a model reaction, showing excellent catalytic activity and recycling stability.     

Facile synthesis of nanoparticles via assembly of photopolymerized and self‐crosslinked random copolymers in selective organic media

We report the facile synthesis of vesicular nanoparticles via self‐assembly of random copolymers in selective organic solvents. The polymers were synthesized via photopolymerization in bulk from acryloyl chloride (AC) containing a small amount of hydrolyzed acrylic acid (AA) at ambient condition. Fourier transform infrared spectroscopy of the photopolymerized product revealed two main chemical components: poly(acryloyl chloride) (PAC) and acid anhydride. The later peak intensified when increasing the initial AA composition in the monomer solution, suggesting that the hydrolyzed AC contributed to the formation of crosslinked anhydride, leading to amphiphilicity of the polymer with solvophobic anhydride and solvophilic PAC chains. At an optimal UV dosage (2000 mJ cm^?2), vesicular nanoparticles (～90 nm in diameter) were obtained from polymers assembled in acetone. The particle size and morphology were confirmed by scanning electron microscopy, transmission electron microscopy, and dynamic and static light‐scattering measurements. Further, we found that the random copolymers self‐organized into vesicles in merely good solvents of PAC chains, including acetonitrile, tetrahydrofuran, and 1,4‐dioxane, but became aggregated and precipitated out in poor solvents of PAC, such as isopropanol, ethanol, toluene, xylene, and hexane. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012