Facile synthesis of metal nanoparticles using conducting polymer colloids

We report a simple method to synthesize Ag, Au, and Pt nanoparticles with a reasonable size dispersity using water-dispersible conducting polymer colloids composed of polyaniline (PANI) and conventional polyelectrolyte. This facile synthesis results in single crystalline metal nanoparticles that are stable in an aqueous solution for at least several weeks. The process involves incrementally adding a metal ion solution to aqueous conducting polymer colloids and does not require reducing agents such as NaBH₄. In addition, the complete synthetic and purification procedure is carried out in an aqueous solution; therefore, it is environmentally benign and potentially suitable for large-scale production. We have also demonstrated synthesis of larger nanoparticles and nanosheets by varying the experimental parameters. With the tunable oxidation states of conducting polymers, we expect this synthetic platform can synthesize a wide range of nanostructured metals with specific size, shape and properties. Finally, the nanoparticles embedded in the conducting polymer matrix, the metal-polyaniline nanocomposite itself may be interesting since it represents a type of materials where metallic nanoislands are embedded in a semiconducting matrix.     

Facile size-controlled synthesis of well-dispersed spherical amorphous alumina nanoparticles via homogeneous precipitation

Well-dispersed spherical amorphous alumina nanoparticles with a narrow size distribution were obtained by facile homogeneous precipitation and subsequent calcination. In the synthesis, formamide was used as the precipitant, and mixtures of aluminum sulfate and aluminum nitrate with different molar ratios were used as the aluminum sources. The average size of the amorphous alumina nanoparticles was successfully controlled by adjusting the amount of formamide and the sulfate/nitrate molar ratio. The particle size decreased with increasing amount of formamide and decreasing sulfate/nitrate molar ratio. Dispersed spherical amorphous alumina nanoparticles with average sizes of 23, 34, 45, and 57 nm were prepared using 100 mL formamide at sulfate/nitrate molar ratios of 1:9, 2:8, 3:7, and 4:6, respectively.     

Monodispersed and size-controlled multibranched gold nanoparticles with nanoscale tuning of surface morphology

A novel seed-mediated synthetic route to produce multibranched gold nanoparticles is reported, in which it is possible to precisely tune both their size and nanostructuration, while maintaining an accurate level of monodispersion. The nanoscale control of surface nanoroughness/branching, ranging from small bud-like features to elongated spikes, allows to obtain fine tuning of the nanoparticle optical properties, up to the red and near-IR region of the spectrum. Such anisotropic nanostructures were demonstrated to be excellent candidates for SERS applications, showing significantly higher signals with respect to the standard spherical nanoparticles.     

Facile preparation of curved polymer composite nanosheets

A facile no-template approach for fabricating curved polystyrene (PS) nanosheets by miniemulsion polymerization technique was developed. Two essences of the high hydrophobicity of oil phase and the existence of cross-linking comonomer were found to ensure the stable curved sheet-like morphology. Here, when choosing tetradecane as the hydrophobic oil phase and divinylbenzene as cross-linker, the curved PS nanosheets with stable structure were obtained. Furthermore, after introducing functional groups by sulfonation reaction, these curved PS nanosheets can be used as a general template for preparing curved sheet-like inorganic/organic nanocomposites with broadly varied inorganic ingredients, such as metal Ag nanoparticles, inorganic titania, silica, etc. Otherwise, when calcining or carbonizing these inorganic/organic nanocomposites under air or nitrogen, novel mesoporous or microporous pure inorganic nanomaterials with curved sheet-like morphology were obtained conveniently further.     

Selective determination of dopamine using quantum-sized gold nanoparticles protected with charge selective ligands

We report here the selective determination of dopamine (DA) using quantum-sized gold nanoparticles coated with charge selective ligands. Glutathione protected gold nanoparticles (GS-Au(25)) were synthesized and immobilized into a sol-gel matrix via thiol linkers. The GS-Au(25) modified sol-gel electrode was found to show excellent electrocatalytic activity towards the oxidation of DA but no activity towards the oxidation of ascorbic acid. The role of electrostatic charge in the selective electrocatalytic activity of GS-Au(25) was verified by voltammetry of redox markers carrying opposite charges. The pH dependent sensitivity for the determination of DA further confirmed the charge screening effect of GS-Au(25). Mechanistic investigation revealed that the selectivity is attained by the selective formation of an electrostatic complex between the negatively charged GS-Au(25) and DA cation. The GS-Au(25) modified sol-gel electrode also showed excellent selectivity for DA in the presence of an interferent, ascorbic acid.     

One-step preparation and characterization of PDDA-protected gold nanoparticles

Poly(diallyl dimethylammonium) chloride (PDDA), an ordinary and watersoluble cationic polyelectrolyte, was investigated for its ability to generate and stabilize gold colloids from a chloroauric acid precursor. In this reaction, PDDA acted as both reducing and stabilizing agents for gold nanoparticles (AuNPs). More importantly, PDDA is a quaternary ammonium polyelectrolyte, which shows that the scope of the reducing and stabilizing agents for metal nanoparticles can be extended from the amine-containing molecules to quaternary ammonium polyelectrolytes or salts. UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and Fourier transform infrared (FTIR) were used to characterize the synthetic AuNPs. The PDDA-protected AuNPs obtained are very stable and have relative narrow size distribution.     

Nanocomposites of size-controlled gold nanoparticles and graphene oxide: formation and applications in SERS and catalysis

In this paper, we describe the formation of Au nanoparticle-graphene oxide (Au-GO) and -reduced GO (Au-rGO) composites by noncovalent attachment of Au nanoparticles premodified with 2-mercaptopyridine to GO and rGO sheets, respectively, viaπ-π stacking and other molecular interactions. Compared with in situ reduction of HAuCl4 on the surface of graphene sheets that are widely used to prepare Au-GO composites, the approach developed by us offers well controlled size, size distribution, and morphology of the metal nanoparticles in the metal-GO nanohybrids. Moreover, we investigated surface enhanced Raman scattering (SERS) and catalysis properties of the Au-graphene composites. We have demonstrated that the Au-GO composites are superior SERS substrates to the Au NPs. Similarly, a comparative study on the catalytic activities of the Au, Au-GO, and Au-rGO composites in the reduction of o-nitroaniline to 1,2-benzenediamine by NaBH4 indicates that both Au-GO and Au-rGO composites exhibit significantly higher catalytic activities than the corresponding Au nanoparticles.     

Facile synthesis of novel zinc-based infinite coordination polymer nanoparticles

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Facile preparation of water-soluble fluorescent gold nanoclusters for cellular imaging applications

We report a facile strategy to synthesize water-soluble, fluorescent gold nanoclusters (AuNCs) in one step by using a mild reductant, tetrakis(hydroxymethyl)phosphonium chloride (THPC). A zwitterionic functional ligand, D-penicillamine (DPA), as a capping agent endowed the AuNCs with excellent stability in aqueous solvent over the physiologically relevant pH range. The DPA-capped AuNCs displayed excitation and emission bands at 400 and 610 nm, respectively; the fluorescence quantum yield was 1.3%. The effect of borohydride reduction on the optical spectra and X-ray photoelectron spectroscopy (XPS) results indicated that the AuNC luminescence is closely related to the presence of Au(I) on their surfaces. In a first optical imaging application, we studied internalization of the AuNCs by live HeLa cells using confocal microscopy with two-photon excitation. A cell viability assay revealed good biocompatibility of these AuNCs. Our studies demonstrate a great potential of DPA-stabilized AuNCs as fluorescent nanoprobes in bioimaging and related applications.     

高分子改性纳米氧化镁的制备和表征

采用溶胶-凝胶法,以MgCl2·6H2O和NH4OH为原料,以聚乙二醇(PEG)为改性剂进行了纳米MgO的改性研究,并用X-射线衍射仪(XRD)和透射电子显微镜(TEM)及比表面分析仪(ASAP2020)对产物进行了表征。结果表明,PEG不但控制了纳米MgO粒子的形状和大小,还使粒子的结晶度、分散性提高,并且基本上无团聚现象。     

Facile synthesis of processable aromatic polyamides containing thioether units

Aromatic polyamides containing thioether units were synthesized by interfacial polycondensation of 4,4′‐thiodibenzoyl chloride (or 4,4′‐bis(4‐chloroformylphenylthio)benzene) with aromatic diamines containing a nitrile unit. Their structure was established using ¹H NMR and Fourier transform infrared spectroscopy. The inherent viscosities of the polyamides prepared with optimum synthesis conditions were in the range 0.71–0.84 dL g^?1. These polyamides showed excellent thermal properties with glass transition temperatures of 210.5–219.6 °C, melting temperatures of 313.8–315.0 °C and initial degradation temperatures of 440–459 °C. They could be processed by melting due to their relatively wide processing window. Their tensile strengths were 71.3–79.1 MPa, water absorption was 0.17–0.22 wt%, and melt flowability was in the range 64.5 to 315.2 Pa s and 68.5 to 422.3 Pa s at different shear rates. At the same time, they were soluble in aprotic solvents such as N‐methyl‐2‐pyrrolidone, dimethylformamide and dimethylsulfoxide. The results suggest that these aromatic polyamides containing thioether units represent a promising type of heat‐resistant and processable engineering plastic. © 2012 Society of Chemical Industry     

金膜上聚合吡咯层的制备工艺研究

研究了一种拟用于SPR生物传感器的聚吡咯衍生物的制备工艺.以丙烯酰氯和吡咯钾盐合成丙烯酰吡咯,然后以偶氮二异丁腈(AIBN)为引发剂,通过自由基聚合为聚丙烯酰吡咯(PAP);将PAP溶于N,N-二甲基甲酰胺(DMF),然后将其旋涂到金膜上形成涂膜表面;最后涂膜表面与吡咯在三氯化铁溶液中进行化学法聚合,形成聚合吡咯层.结果表明.聚合膜的厚度随着时间的延长和单体浓度的增加而变厚.     

Facile preparation of thermosensitive and water-soluble fluorescent polymer containing curcumin and its cell imaging

A novel thermosensitive and water-soluble fluorescent polymer PNIPAM-curcumin (P2) containing curcumin unit was synthesized through one-pot method. The chemical structure and optical properties of compounds and polymer were characterized and tested. As the results turned out that P2 displayed excellent water solubility, thermosensitivity and exhibited strong fluorescence emission band in water. Moreover, P2 was further investigated by MTT assay and live cell imaging with HeLa cells. P2 did not have cytotoxicity in concentration of 200?µg?·?mL^?1 within 48?h and the intracellular fluorescence intensity enhanced with the concentration of P2 varying from 0 to 500?µg?·?mL^?1. According to the experimental results, as a fluorescence probe, P2 synthesized does not only possess nice water solubility but also has the advantage of no cytotoxicity, and it can easily enter the cells, which indicates that it is a characteristic of high sensitivity and responsiveness. Therefore, P2 will have immense potential to be applied in biomedical fields.     

Synthesis of carbon nanotube composites with size-controlled silicon nanoparticles

A new route for the synthesis of silicon nanoparticle (Si NP)/carbon nanotube (CNT) composites by a low-temperature magnesiothermic reduction process is presented. The size of the Si NPs can be controlled by varying the silica (SiO₂) thickness of SiO₂/CNT precursors. The structural and morphological characterizations of the Si NP/CNT composites have been carried out using powder X-ray diffraction and transmission electron microscopy.     

Organosilicon-functionalized polyolefins,a kind of designable and versatile polymer: From preparation to applications

Functionalization of polyolefins has been a challenging but promising issue since their invention, with the promise of retaining inherent properties and overcoming the low reactivity and poor compatibility. Organosilicons are widely used for polymer modification to improve thermal stability, hydrophobicity, compatibility, and permeability. Since the advent of alkoxysilane-grafted polyethylene in 1960s, organosilicon-functionalized polyolefins (Si-PO) have been extensively prepared, investigated, and developed. The structure of Si-PO is designable due to the flexible chemistry of organosilicons; crosslinked, long chain branched, and star-shaped polyolefins are available after the introduction of alkoxysilanes, chlorosilanes, hyrdosilanes, or alkylsilanes into polyolefins, and generally these polymers are more compatible to fillers than commercial polyolefins due to stronger interaction. In addition, functionalization of polyolefins with stable organosilicon components such as polysiloxane and polysilsesquioxane can improve thermostability, hydrophobicity, gas permeability, and aging resistance; such polyolefins are usually grafted or block polymers. In this review, Si-PO is classified according to the functional organosilicon component, namely alkoxysilane, chlorosilane, hydrosilane, alkylsilane, polysiloxane, and polysilsesquioxane; their preparations are discussed minutely and summarized with manifold examples. Silicon-containing structures impart the unique properties of organosilicons to polyolefins; applications of Si-PO as compatibilizers, processing aids, battery separators, and separating membranes have been widely reported and are discussed here.     

Facile preparation of Bi nanoparticles by novel cathodic dispersion of bulk bismuth electrodes

A novel electrochemical approach has been developed to prepare clean bismuth nanoparticles (NPs) with a bulk Bi electrode in a 0.5 mol dm⁻³ NaOH solution under highly cathodic polarization of −8 V versus a saturated mercurous sulfate electrode, requiring no any precursor ions and organic protective agents. The bulk Bi electrode can be facilely dispersed into Bi NPs at the condition of intensive hydrogen evolution. This cathodic dispersion of the bulk Bi electrode involves the formation and decomposition of unstable bismuth hydrides and the aggregation of atomic bismuth from the decomposition. Moreover, Bi₂O₃ NPs have also been achieved by heating the precursor Bi NPs. Field-emission scanning electron microscopy, transmission electron microscope and X-ray diffraction were used to characterize these NPs. The as-prepared Bi NPs mainly existed in rhombohedral phase.     

超重力反溶剂沉淀法快速制备疏水药物纳米颗粒

The nanoparticles of the hydrophobic drug of danazol with narrow size distribution are facilely prepared by controlled high-gravity anti-solvent precipitation (HGAP) process. Intensified micromixing and uniform nucleation environment are created by the high-gravity equipment (rotating packed bed) in carrying out the anti-solvent precipitation process to produce nanoparticles. The average particle size decreases from 55 µm of the raw danazol to 190 nm of the nanoparticles. The Brunauer-Emmett-Teller (BET) surface area sharply increases from 0.66 m2•g－1 to 15.08 m2•g－1. Accordingly, the dissolution rate is greatly improved. The molecular state, chemical composition, and crystal form of the danazol nanoparticles remains unchanged after processing according to Fourier transform infrared (FTIR) and X-ray diffraction (XRD). The high recovery ratio and continuous production capacity are highly appreciated in industry. Therefore, the HGAP method might offer a general and facile platform for mass production of hydrophobic pharmaceutical danazol particles in nanometer range.     

Facile purification of colloidal NIR-responsive gold nanorods using ions assisted self-assembly

Anisotropic metal nanoparticles have been paid much attention because the broken symmetry of these nanoparticles often leads to novel properties. Anisotropic gold nanoparticles obtained by wet chemical methods inevitably accompany spherical ones due to the intrinsically high symmetry of face-centred cubic metal. Therefore, it is essential for the purification of anisotropic gold nanoparticles. This work presents a facile, low cost while effective solution to the challenging issue of high-purity separation of seed-mediated grown NIR-responsive gold nanorods from co-produced spherical and cubic nanoparticles in solution. The key point of our strategy lies in different shape-dependent solution stability between anisotropic nanoparticles and symmetric ones and selective self-assembly and subsequent precipitation can be induced by introducing ions to the as-made nanorod solution. As a result, gold nanorods of excellent purity (97% in number density) have been obtained within a short time, which has been confirmed by SEM observation and UV-vis-NIR spectroscopy respectively. Based on the experimental facts, a possible shape separation mechanism was also proposed.