One‐step Synthesis of AuAg Alloy Nanodots and its Electrochemical Studies towards Nitrobenzene Reduction and Sensing

Efficient, stable, and low‐cost electrocatalysts for the degradation and sensing of environment pollutants are essential components of clean environment monitoring. Here we report, one‐step synthesis and characterization of 1–3 nm diameter sized bi‐metallic AuAg nanodots (NDs) embedded in amine functionalized silicate sol‐gel matrix (SSG) and its electrochemical studies toward nitrobenzene. The SSG was used as a reducing agent as well as stabilizer for the prepared mono‐ and bi‐metallic nanoparticles (NPs). From the HRTEM, STEM‐EDS and XPS analyses, the bi‐metallic AuAg NDs were identified as an alloy and not the mixtures of Au and Ag NPs. Characteristic surface plasmon resonance (SPR) band between the Au and Ag NPs SPR absorption region was noticed for the prepared AuAg NDs. The AuAg alloy NDs with different concentrations of Au and Ag (Au₂₅Ag₇₅, Au₅₀Ag₅₀ and Au₇₅Ag₂₅ NDs) modified electrodes exhibited synergistic electrocatalytic effect than did the Au and Ag NPs towards nitrobenzene reduction and detection. Together with ultra‐small size and exceptional colloidal stability features within these SSG‐AuAg NDs pave convenient way for nanotechnology‐based catalysts development and sensor applications.     

Colloidal Stability of TiO2 Nanoparticles: The Roles of Phosphonate Ligand Length and Solution Temperature

Surface ligands are essential tools for the stabilization of colloidal nanoparticles (NPs) in solvents. However, knowledge regarding the effects of the ligand shell, especially the ligand length, is insufficient and controversial. Here we demonstrate solution-based experiments on n-alkylphosphonate-capped TiO₂ NPs to investigate the effects of ligand length and solution temperature on colloidal stability. A robust ligand-exchange process is achieved that draws free ligands and impurities away from the colloidal solution. In the case of 8 nm anatase NPs in toluene, the dodecylphosphonate ligand provided better colloidal stability than all the other n-alkylphosphonate ligands. In addition, relaxation studies suggested there is kinetic hysteresis in the dispersion/agglomeration transition. The proposed method is applicable to a wide range of surface ligands designed to maximize the colloidal stability of NPs.     

Multifunctional PES fabrics modified with colloidal Ag and TiO2 nanoparticles

This study is aimed to highlight the possibility of engineering the multifunctional textile nanocomposite material based on the polyester (PES) fabric modified with colloidal Ag and TiO₂ nanoparticles (NPs). The effects of concentration of NPs as well as the order of Ag and TiO₂ NPs loading on antimicrobial, UV protective, and photocatalytic properties of PES fabrics were examined. The antimicrobial activity of differently modified PES fabrics was tested against Gram‐negative bacterium Escherichia coli, Gram‐positive bacterium Staphylococcus aureus, and fungus Candida albicans. The concentration of Ag colloid and the order of Ag and TiO₂ NPs loading considerably affected the antimicrobial efficiency of PES fabrics. The fabrics provided maximum UV protection upon surface modification with Ag and TiO₂ NPs. Ag NPs enhanced Ag NPs enhanced the photodegradation activity of TiO₂ NPs and total photodegradation of methylene blue was achieved after 24 hr of UV illumination. Copyright © 2010 John Wiley & Sons, Ltd.     

One‐Dimensional Carbon Nanotube/SnO2/Noble Metal Nanoparticle Hybrid Nanostructure: Synthesis,Characterization, and Electrochemical Sensing

Herein we report a facile and efficient method for self‐assembling noble‐metal nanoparticles (NPs) to the surface of SnO₂‐coated carbon nanotubes (CNT@SnO₂) to construct CNT@SnO₂/noble metal NP hybrids. By using SnCl₄ as the precursor of the SnO₂ shell on the surface of CNTs, the hydrolysis speed of SnCl₄ was slowed down in ethanol containing a trace amount of urea and water. The coaxial nanostructure of CNT@SnO₂ was confirmed by using X‐ray powder diffraction (XRD) and transmission electron microscopy (TEM). It was found that the coating layer of SnO₂ was homogeneous with the mean thickness of 8 nm. The CNT@SnO₂/noble‐metal NP hybrids were obtained by mixing noble‐metal NPs with as‐prepared CNT@SnO₂ coaxial nanocables by means of a self‐assembly strategy. With the amino group terminated, the CNT@SnO₂ coaxial nanocable can readily adsorb the as‐prepared noble‐metal NPs (Au, Ag, Au? Pt, and Au? Pd NPs). The presence of an amino group at the surface of SnO₂ was proved by use of X‐ray photoelectron spectroscopy (XPS). In addition, H₂O₂ sensing by amperometric methods could serve as detection models for investigating the electrocatalytic ability of as‐prepared hybrid materials. It was found that wide linear ranges and low detection limits were obtained by using the enzyme‐free CNT@SnO₂@Au? Pt modified electrode, which indicated the potential utilizations of the hybrid based on CNT@SnO₂ for electrochemical sensing.     

Colorimetric Sensing of Adenosine Based on Aptamer Binding Inducing Gold Nanoparticle Aggregation

A simple and rapid colorimetric approach for the determination of adenosine has been developed via target inducing aptamer structure switching, thus leading to Au colloidal solution aggregation. In the absence of the analytes, the aptamer/gold nanoparticle (Au NP) solution remained well dispersed under a given high ionic strength condition in that the random‐coil aptamer was readily wrapped on the surface of the Au NPs, which resulted in the enhancement of the repulsive force between the nanoparticles due to the high negative charge density of DNA molecules. While in the presence of adenosine, target‐aptamer complexes were formed and the conformation of the aptamer was changed to a folded structure which disfavored its adsorption on the Au NP surface, thus leading to the reduction of the negative charge density on each Au NP and then the reduced degree of electrostatic repulsion between Au nanoparticles. As a result, the aggregation of the Au colloidal solution occurred. The changes of the absorption spectrum could be easily monitored by a UV‐Vis spectrophotometer. A linear correlation exists between the ratio of the absorbance of the system at 522 to 700 nm (A_{522 nm}/A_{700 nm}) and the concentration of adenosine between 100 nmol·L^?1 and 10 µmol·L^?1, with a detection limit of 51.5 nmol·L^?1.     

Full Characterization of Colloidal Solutions of Long‐Alkyl‐Chain‐Amine‐Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State,Equilibria, and Affinity

Full NMR characterization of ZnO nanoparticles (NPs) stabilized by various amines (hexadecylamine, dodecylamine, and octylamine) in C₇D₈ demonstrated that the surface of this apparently simple system was very complex. Using different NMR spectroscopic techniques (¹H, PGSE‐NMR, diffusion‐filtered ¹H NMR, NOESY, ROESY), we observed at least three different modes of interaction of the amines at the surface of the NPs, in thermodynamic equilibrium with the free amines, the relative populations of which varied with their concentration. The first mode corresponded to a strong interaction between a small amount of amine and the ZnO NPs (k_desorp≈13 s^?1). The second mode corresponded to a weak interaction between the amines and the surface of the ZnO NPs (k_off(2)≈50–60 s^?1). The third, and weakest, mode of interaction corresponded to the formation of a second ligand shell by the amine around the NPs that was held together through van der Waals interactions (k_off(1)≈25×10⁵ s^?1). The second and third modes were in fast exchange on the NMR timescales with the free amines. The strongly interacting amines at the NPs surface (first mode) were in slow exchange with the other modes. A complex hydrogen‐bonding network at the NPs surface was also observed, which did not only involve the coordinated amine but also THF and water molecules that remained from the synthesis.     

Colloidal Nanocrystals of Lithiated Group 14 Elements

The synthesis of colloidal nanocrystals (NCs) of lithiated group 14 elements (Z=Si, Ge, and Sn) is reported, which are Li_4.4Si, Li_3.75Si, Li_4.4Ge, and Li_4.4Sn. Li_xZ compounds are highly reactive and cannot be synthesized by existing methods. The success relied on separating the surface protection from the crystal formation and using a unique passivating ligand. Bare Li_xZ crystals were first produced by milling elemental Li and Z in an argon‐filled jar. Then, under the assistance of additional milling, hexyllithium was added to passivate the freshly generated Li_xZ NCs. This ball‐milling‐assisted surface protection method may be generalized to similar systems, such as Na_xZ and K_xZ. Moreover, Li_4.4Si and Li_4.4Ge NCs were conformally encapsulated in carbon fibers, providing great opportunities for studying the potential of using Li_xZ to mitigate the volume‐fluctuation‐induced poor cyclability problem confronted by Z anodes in lithium‐ion batteries.     

Synthesis and characterization of antibacterial chromium iron oxide nanoparticle‐loaded activated carbon for ultrasound‐assisted wastewater treatment

The aim of this study was to evaluate the surface adsorption capacity of CrFeO₃ nanoparticle‐loaded activated carbon (CrFeO₃‐NPs–AC) for the removal of a cationic dye (methyl violet, MV). CrFeO₃‐NPs were hydrothermally synthesized and loaded on AC followed by characterization using X‐ray diffraction, field‐emission scanning electron microscopy and energy‐dispersive and Fourier transform infrared spectroscopies. The CrFeO₃‐NPs were tested for in vitro antibacterial activities against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Pseudomonas aeruginosa) bacteria. Minimum inhibitory and minimum bactericidal concentrations of CrFeO₃‐NPs–AC were obtained to be 50 and 100 μg ml^?1, respectively, against S. aureus and 25 and 50 μg ml^?1 against P. aeruginosa. These results indicated the antibacterial properties of CrFeO₃‐NPs–AC. To investigate the adsorption process, several systematic experiments were designed by varying parameters such as adsorbent mass, pH, initial MV concentration and sonication time. The adsorption process was modelled and the optimal conditions were determined to be 0.013 g, 7.4, 15 mg l^?1 and 8 min for adsorbent mass, pH, MV concentration and sonication time, respectively. The real experimental data were found to be efficiently explained by response surface methodology and genetic algorithm model. Kinetic studies for MV adsorption showed rapid sorption dynamics described by a second‐order kinetic model, suggesting a chemisorption mechanism. Then, the experimental equilibrium data obtained at various concentrations of MV and adsorbent masses were fitted to conventional Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Dye adsorption equilibrium data were fitted well to the Langmuir isotherm. From the Langmuir model, the maximum monolayer capacity was calculated to be 65.67 mg g^?1 at optimum adsorbent mass.     

普鲁士蓝/CdS纳米复合物电致化学发光及其H2O2传感应用

通过一定体积比的CdS和普鲁士蓝(PB)胶体纳米溶液的简单混合,制备了PB/CdS纳米复合物。在共反应剂存在条件下,PB纳米粒子含量较低时,在ITO电极上CdS纳晶的电致化学发光(ECL)强度可以增强3倍左右。PB纳米粒子含量较高时,CdS纳晶的ECL强度则显著降低。详细讨论了PB纳米粒子对CdS纳晶ECL影响的机理。PB纳米粒子对CdS纳晶的ECL增强可用于H2O2传感。该传感器对H2O2响应的线性范围为3.3×10-8～6.5×10-3 mol.L-1(R=0.999 2),检测限为12 nmol.L-1(S/N=3),传感器具有良好的稳定性和重现性。     

Highly Ordered Mesoporous Tungsten Oxides with a Large Pore Size and Crystalline Framework for H2S Sensing

An ordered mesoporous WO₃ material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymers as a structure‐directing agent through a solvent‐evaporation‐induced self‐assembly method combined with a simple template‐carbonization strategy. The obtained mesoporous WO₃ materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m² g^?1). The mesoporous WO₃‐based H₂S gas sensor shows an excellent performance for H₂S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H₂S sensing.     

Comparison of USAXS information with RMSA prediction for the effect of added salt on colloidal crystal structure

Charged colloidal particles form so‐called colloidal crystals in dispersions because of electrostatic interparticle interactions between them. We performed a systematic and quantitative investigation of the effect of salt on the interparticle distance in colloidal crystals with the ultra‐small‐angle X‐ray scattering (USAXS) technique. We accumulated a great deal of significant information about the mechanism of the colloidal crystal formation by USAXS. We found that the interparticle distance in colloidal crystals shows a maximum as a function of the added salt concentration. The maximum position of the interparticle distance was located around κa = 1.3 (κ⁻¹ is the Debye length, and a is the particle radius). The behavior of the decrease of the interparticle distance with the increase of the added salt concentration at κa > 1.3 could be explained not quantitatively but qualitatively with the effective hard‐sphere theory. Thus, it was suggested that the dependence of the interparticle distance on the salt concentration at κa > 1.3 was reasonable according to the classical theories, such as the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. In this article, we advance this theoretical approach with the classical theory, that is, with the assumption of the only repulsive force for the interparticle interaction, to elucidate the origin of the curious behavior of the interparticle distance. We estimated the structure factor by the rescaled mean spherical approximation (RMSA) with a Yukawa‐type interparticle interaction potential. A comparison between the prediction of the RMSA data and USAXS experimental data was performed. In this analysis, the charge renormalization procedure was applied. Although the origin of the behavior of the interparticle distance at κa < 1.3 is still a mystery, we concluded that the behavior at κa > 1.3 could be interpreted as a result from the DLVO manner. The effective surface charge number was on the order of several percentages of the analytical surface charge number. This experimental fact certainly proves the validly of our USAXS observation quantitatively and also predicts the existence of novel factors for κa ≤ 1.3, the real origin of colloidal crystal formation, which have never been taken into account previously. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 78–90, 2001     

MOF‐Derived Hollow CoS Decorated with CeOx Nanoparticles for Boosting Oxygen Evolution Reaction Electrocatalysis

Transition‐metal sulfides (TMSs) have emerged as important candidates for oxygen evolution reaction (OER) electrocatalysts. Now a hybrid nanostructure has been decorated with CeO_x nanoparticles on the surface of ZIF‐67‐derived hollow CoS through in situ generation. Proper control of the amount of CeO_x on the surface of CoS can achieve precise tuning of Co²⁺/Co³⁺ ratio, especially for the induced defects, further boosting the OER activity. Meanwhile, the formation of protective CeO_x thin layer effectively inhibits the corrosion by losing cobalt ion species from the active surface into the solution. It is thus a rare example of a hybrid hetero‐structural electrocatalyst with CeO_x NPs to improve the performance of the hollow TMS nanocage.     

Preparation of chitosan functionalized end‐capped Ag‐NPs and composited with Fe3O4‐NPs: Controlled release to pH‐responsive delivery of progesterone and antibacterial activity against pseudomonas aeruginosa (PAO‐1)

In this work, functionalized chitosan end‐capped Ag nanoparticles (NPs) and composited with Fe₃O₄‐NPs was prepared as pH‐responsive controlled release carrier for gastric‐specific drug delivery. The structure of prepared material was characterized by FE‐SEM, XRD, EDS and FT‐IR analysis. The loading behavior of the progesterone onto this novel material was studied in aqueous medium at 25°C and their release was followed spectrophotometrically at 37°C in seven different buffer solutions (pH 1.2, 2.2, 3.2, 4.2, 5.2, 6.2 and 7.2) to simulate intestine and gastric media which experimental results reveal more release rate in pH 1.2 (gastric medium) with respect to other buffers. This observation is attributed to dependency of the CS‐IMBDO‐Ag‐Fe₃O₄‐NPs and progesterone structure with buffer pH that candidate this new material as prospective pH‐sensitive carrier for gastric‐targeted drug delivery. On the other hand, the antibacterial properties of this material against gram‐negative bacterium pseudomonas aeruginosa (PAO‐1) in agar plates was studied and accordingly based on broth micro dilution the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) with respect to standard CLSI in different concentrations of CS‐IMBDO‐Ag‐Fe₃O₄‐NPs was calculated. The results reveal that MIC and MBC values are 50 and 1250 μg/mL, respectively. In addition, extracts of Portulaca oleracea leaves was prepared and its antibacterial activity in single and binary system with CS‐IMBDO‐Ag‐Fe₃O₄‐NPs as synergies effect against PAO‐1 was tested and results shown that these materials have significant synergistic effect for each other.     

Anhydrous Lanthanide MOFs and Direct Photoluminescent Sensing for Polyoxometalates in Aqueous Solution

New anhydrous lanthanide metal–organic frameworks (MOFs) [Pr(tip)_1.5]_2n ( tip‐Pr ), [Nd(tip)_1.5]_2n ( tip‐Nd ), [Eu(tip)_1.5]_2n ( tip‐Eu ), and [Eu(OH)(mip)]_n ( mip‐Eu ) (tip=5‐tert‐butylisophthalate anion, mip=5‐methylisophthalate ion), have been hydrothermally synthesized and structurally characterized by elemental analyses, FT‐IR spectroscopy, single‐crystal X‐ray diffraction, thermal gravimetric analysis/differential thermal analysis (TG/DTA), and X‐ray powder diffraction (XRPD) techniques. MOFs tip‐Pr , tip‐Nd , and tip‐Eu are isostructural anhydrous compounds, and exhibit an unprecedented 3D microporous structure with hexagonal channel arrays. The selectively prepared MOF mip‐Eu presents an interpenetrated 3D microporous architecture containing the hydroxyl cluster chains. Solid‐state photoluminescence properties at room temperature indicate that both tip‐Eu and mip‐Eu display the characteristic of the Eu³⁺ ion spectrum dominated by the ⁵D₀→⁷F_J (J=0‐4) transition. Compared with mip‐Eu , tip‐Eu displays the very high solid‐state quantum yield (0.62±0.03) and longer lifetime value (0.94±0.01 ms), which is due to the absence of the hydroxyl groups from the solid‐state structure of tip‐Eu . More importantly, a new method to directly investigate the potential of solid‐state lanthanide MOFs for ionic sensing in aqueous solutions has been developed, and successfully applied it to study the potential sensing function of tip‐Eu for polyoxometalates (POMs). The possible mechanism for the quenching effect of POMs on the fluorescence of tip‐Eu is elucidated by the strongly competitive absorption of the excited light source energy between POMs and tip ligands. The very promise for the highly sensitive sensing for polyoxometalates, together with the characteristic of the reversible fluorescence response, suggest that solid‐state tip‐Eu can be an excellent candidate for the directly photoluminescent detection of POMs in aqueous solutions.     

Discrete Dipole Approximation Analysis of Plasmonic Core/Alloy Nanoparticles

The surface plasmon resonance (SPR) properties of Au/Au_xAg_1?x core/alloy nanoparticles (NPs) have been investigated by means of the discrete dipole approximation. The core/alloy microstructure was varied by changing the shell alloy composition x, its thickness t_S, and the shell thickness to core radius ratio (t_S/r_C) in the range of 0.05–1.0. These changes resulted in a novel tuning of SPR shape, frequency, and extinction. These models were compared with experimental results for Au/Au_xAg_1?x NPs prepared by a microwave‐mediated hydrothermal processing method, which produces core/alloy NPs with SPR signatures closely resembling those of the models.     

Activation of CdS nanoparticles by metallic ions and their selective interactions with PAMAM dendrimers

CdS nanoparticles (NPs) in colloidal dispersion were activated by metallic ions [Mn(II) and Cu(II)], employing a simple method under mild conditions. These metallic ions on the surface of the CdS NPs quench the red-shifted defect emission, and efficiently promote near band gap emission; they also enhance the photo stability and dispersability of the suspensions. Taking advantage of the chemical affinity of Mn(II) and Cu(II) for the CdS surface, we carried out a study of the interaction between [CdS-M(II) _n ] NPs and polyamidoamine dendrimers of 1 and 2.5 generations (G₁=8 amino, and G_2.5=32 carboxylic end-groups, respectively). The strong interaction between these two chemical species results in the formation of new [CdS-M(II) _n G _n ] nanocomposites. All colloidal systems were monitored by UV-visible electronic absorption and emission spectroscopies, and electronic paramagnetic resonance. The crystal structures of the nanocomposites, as well as their average diameters (2.0–3.3 nm), were determined by high-resolution transmission electron microscopy images.     

A Magnetically Tunable Colloidal Crystal Film for Reflective Display

A general approach to fabricate a magnetic field responsive colloidal crystal film has been developed. This is carried out by depositing monodisperse Fe₃O₄/PS composite magnetic nanospheres on the surface of an agarose‐gel coated substrate. The optical properties of the resultant film can be easily controlled by an external magnetic field, which is caused by assembly of the magnetic nanospheres and alteration of the interparticle distance. With the help of a designed array of small magnets, both the color and pattern of the film can be conveniently modulated and the tuning range covers almost the whole visible spectrum. This work will be important for the potential application of monodisperse magnetic nanospheres in fabricating novel sensors, displays and optoelectronic devices.

     

Dual‐fluorophore Raspberry‐like Nanohybrids for Ratiometric pH Sensing

We report on the development of raspberry‐like silica structures formed by the adsorption of 8‐hydroxypyrene‐1,3,6‐trisulfonate (HPTS)@silica nanoparticles (NPs) on rhodamine B isothiocyanate (RBTIC)@silica NPs for ratiometric fluorescence‐based pH sensing. To overcome the well‐known problem of dye leaching which occurs during encapsulation of anionic HPTS dye in silica NPs, we utilized a polyelectrolyte‐assisted incorporation of the anionic HPTS. The morphological and optical characterization of the as‐synthesized dye‐doped NPs and the resulting nanohybrids were carried out. The pH‐sensitive dye, HPTS, incorporated in the HPTS‐doped silica NPs provided a pH‐dependent fluorescence response while the RBITC‐doped silica provided the reference signal for ratiometric sensing. We evaluated the effectiveness of the nanohybrids for pH sensing; the ratio of the fluorescence emission intensity at 510 nm and 583 nm at excitation wavelengths of 454 nm and 555 nm, respectively. The results showed a dynamic response in the acidic pH range. With this approach, nanohybrids containing different dyes or receptors could be developed for multifunctioning and multiplexing applications.     

Green synthesis and characterization of monodispersed silver nanoparticles obtained using oak fruit bark extract and their antibacterial activity

Green synthesis of silver nanoparticles (Ag NPs) has been achieved using oak fruit bark extract as a reducing, capping and stabilizing agent. The biosynthesized Ag NPs were characterized using various techniques. UV–visible spectrum of prepared silver colloidal solution showed absorption maximum at 433 nm. X‐ray diffraction and transmission electron microscopy analysis revealed that Ag NPs have a face‐centred cubic structure being spherical in shape with an average particle size of 20–25 nm. The toxicity of the Ag NPs was tested on bacterial species such as Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli by comparison based on diameter of inhibition zone in disc diffusion tests and minimum inhibitory concentration and minimum bactericidal concentration of NPs dispersed in liquid cultures. The antimicrobial activity of Ag NPs was greater towards Gram‐positive bacteria (S. aureus and B. subtilis) compared to Gram‐negative bacteria as determined using standard Kirby–Bauer disc diffusion assay and serial dilution. Copyright © 2016 John Wiley & Sons, Ltd.     

Ionophore‐Based Biphasic Chemical Sensing in Droplet Microfluidics

Droplet microfluidics is an enabling platform for high‐throughput screens, single‐cell studies, low‐volume chemical diagnostics, and microscale material syntheses. Analytical methods for real‐time and in situ detection of chemicals in the droplets will benefit these applications, but they remain limited. Reported herein is a novel heterogeneous chemical sensing strategy based on functionalization of the oil phase with rationally combined sensing reagents. Sub‐nanoliter oil segments containing pH‐sensitive fluorophores, ionophores, and ion‐exchangers enable highly selective and rapid fluorescence detection of physiologically important electrolytes (K⁺, Na⁺, and Cl^?) and polyions (protamine) in sub‐nanoliter aqueous droplets. Electrolyte analysis in whole blood is demonstrated without suffering from optical interference from the sample matrix. Moreover, an oil phase doped with an aza‐BODIPY dye allows indication of H₂O₂ in the aqueous droplets, exemplifying sensing of targets beyond ionic species.