The Signal‐Enhanced Label‐Free Immunosensor Based on Assembly of Prussian Blue‐SiO2 Nanocomposite for Amperometric Measurement of Neuron‐Specific Enolase

A signal‐enhanced label‐free electrochemical immunosensor was constructed by the employment of Prussian blue doped silica dioxide (PB‐SiO₂) nanocomposite. At first, PB‐SiO₂ nanocomposite which was produced by using a microemulsion method was used to obtain a nanostructural monolayer on a glassy carbon electrode (GCE) surface. Next amino‐functionalized interface were prepared by self‐assembling 3‐aminopropyltriethoxy silane (APTES) on the PB‐SiO₂ nanoparticle surface. Then chitosan stabled gold nanoparticle (CS‐nanoAu) was subsequently attached, while the entire surface was finally loaded with neuron‐specific enolase antibody (anti‐NSE) via the adsorption of gold nanoparticle. The sensitivity of the proposed immunosensor has greatly improved as the PB‐SiO₂ nanostructural sensing film provides plenty of active sites which might catalyze the reduction of H₂O₂. The immunosensor exhibited good linear behavior in the concentration range from 0.25–5.0 and 5.0–75 ng/mL for the quantitative analysis of neuron‐specific enolase (NSE), a putative serum marker of small‐cell lung carcinoma (SCLC), with a limit of detection of 0.08 ng/mL. The resulting NSE immunosensor showed high sensitivity and long‐term lifetime which can be attributed to the extremely high catalytic activity and biocompatibility of CS‐nanoAu/APTES/PB‐SiO₂ nanostructural multilayers.     

Photochemical Preparation of Nanoparticles of Ag in Aqueous-Alcoholic Solutions and on the Surface of Mesoporous Silica

Stable nanoparticle colloids of silver were obtained by irradiation of aqueous-alcoholic solutions of AgNO₃ in the presence of mesoporous SiO₂ powder and films modified with benzophenone (BP/SiO₂). Colloidal solutions of Ludox silica were used to stabilize the photochemically produced nanoparticles of silver in solution. Formation of nanoparticles of Ag on the surface of mesoporous silica occurred on irradiation of SiO₂ modified with silver ions (Ag⁺/SiO₂) in the presence of benzophenone solution.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 100–104, March–April, 2005.     

A Silica Bilayer Supported on Ru(0001): Following the Crystalline‐to Vitreous Transformation in Real Time with Spectro‐microscopy

The crystalline‐to‐vitreous phase transformation of a SiO₂ bilayer supported on Ru(0001) was studied by time‐dependent LEED, local XPS, and DFT calculations. The silica bilayer system has parallels to 3D silica glass and can be used to understand the mechanism of the disorder transition. DFT simulations show that the formation of a Stone–Wales‐type of defect follows a complex mechanism, where the two layers show decoupled behavior in terms of chemical bond rearrangements. The calculated activation energy of the rate‐determining step for the formation of a Stone—Wales‐type of defect (4.3 eV) agrees with the experimental value. Charge transfer between SiO₂ bilayer and Ru(0001) support lowers the activation energy for breaking the Si?O bond compared to the unsupported film. Pre‐exponential factors obtained in UHV and in O₂ atmospheres differ significantly, suggesting that the interfacial ORu underneath the SiO₂ bilayer plays a role on how the disordering propagates within the film.     

Confined crystallization behaviors in polyethylene/silica nanocomposites: Synergetic effects of interfacial interactions and filler network

The confinement effects introduced by nanoparticles have been reported to influence the phase behaviors thus the properties of polymer nanocomposites. In this study, molecular dynamics and crystallization behaviors of polyethylene (PE) composited with three types of silica (SiO₂) nanoparticles, namely unmodified SiO₂, hydrophobically modified SiO₂, SiO₂‐APTES (3‐aminopropyltriethoxysilane) and SiO₂‐PTES (n‐propyltriethoxysilane), were systematically investigated via a combination of DSC, XRD and ¹H solid‐state NMR measurements. The suppressions in crystallization and chain mobilities of PE rank in the order of unmodified SiO₂ < SiO₂‐APTES < SiO₂‐PTES due to the increasing interfacial interactions between PE and SiO₂ nanoparticles. Additionally, independent of polymer–nanoparticle interactions, a silica network forms for all three kinds of nanocomposites when SiO₂ content reaches 83 wt %. The mobilities of polymer chains are severely restricted by such a percolated network structure, leading to a turning point in the crystallization ability of nanocomposites and a new crystallization peak at 45 °C lower than that of pure PE. The synergetic effects of interfacial interactions and filler network on polymer crystallization have been thoroughly studied in this work, which will provide guidance on modifying and designing nanocomposites with controlled properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 498–505     

Synthesis of a stationary phase based on silica modified with branched octadecyl groups by Michael addition and photoinduced thiol–yne click chemistry for the separation of basic compounds

A novel silica‐based stationary phase with branched octadecyl groups was prepared by the sequential employment of the Michael addition reaction and photoinduced thiol–yne click chemistry with 3‐aminopropyl‐functionalized silica microspheres as the initial material. The resulting stationary phase denoted as SiO₂‐N(C18)₄ was characterized by elemental analysis, FTIR spectroscopy and Raman spectroscopy, demonstrating the existence of branched octadecyl groups in silica microspheres. The separations of benzene homologous compounds, acid compounds and amine analogues were conducted, demonstrating mixed‐mode separation mechanism on SiO₂‐N(C18)₄. Baseline separation of basic drugs mixture was acquired with the mobile phase of acetonitrile/H₂O (5%, v/v). SiO₂‐N(C18)₄ was further applied to separate Corydalis yanhusuo Wang water extracts, and more baseline separation peaks were obtained for SiO₂‐N(C18)₄ than those on Atlantis dC18 column. It can be expected that this new silica‐based stationary phase will exhibit great potential in the analysis of basic compounds.     

Unconventional Assembly of Bimetallic Au–Ni Janus Nanoparticles on Chemically Modified Silica Spheres

This paper reports that Janus Au?Ni nanoparticles (JANNPs) can self‐assemble onto silica spheres in a novel way, which is different from that of single‐component isotropic nanoparticles. JANNPs modified with octadecylamine (ODA) assemble onto catechol‐modified silica spheres (SiO₂?OH) to form a very special core–loop complex structure and finally the core–loop assemblies link each other to form large assemblies through capillary force and the hydrophobic interaction of the alkyl chains of ODA. The nanocomposites disassemble in the presence of vanillin and oleic acid because of the breakage of the catechol–metal link. Vanillin‐induced disassembly enables the JANNPs to reassemble into a core–loop structure upon ODA addition. The assembly of SiO₂?OH and isotropic Ni or Fe₃O₄ particles generates traditional core–satellite structures. This unconventional self‐assembly can be attributed to the synergistic effect of Janus specificity and capillary force, which is also confirmed by the assembly of thiol‐terminated silica spheres (SH?SiO₂) with anisotropic JANNPs, isotropic Au, and Ni nanoparticles. These results can guide the development of novel composite materials using Janus nanoparticles as the primary building blocks.     

可控纳米银胶体的稳定性

纳米银胶体(AgNPs)长期储存不稳定性问题是本研究的中心,着重考察了不同前驱体对纳米银胶体的稳定性影响。分别以银氨([Ag(NH3)2]OH)溶液和Ag NO3溶液为前驱体制备了多份纳米银胶体样品并通过UV-Vis、FE-SEM、EDS、ZETA电位仪等现代分析测试手段研究了纳米银胶的形貌、粒径大小以及稳定性。对比分析发现,以[Ag(NH3)2]OH溶液为前驱体,制备的纳米银胶体具有粒径可控,尺寸均一,分散性良好等特点;而且经过一个月的常温储存,表现出比用Ag NO3溶液为前驱体制备的纳米银胶体具有更高的储存稳定性。     

可控纳米银胶体的稳定性研究

纳米银胶体(AgNPs)长期储存不稳定性问题是本研究的中心,着重考察了不同前驱体对纳米银胶体的稳定性影响.分别以银氨([Ag(NH₃)₂]OH)溶液和AgNO₃溶液为前驱体制备了多份纳米银胶体样品并通过UV-Vis、FE-SEM、EDS、ZETA电位仪等现代分析测试手段研究了纳米银胶的形貌、粒径大小以及稳定性.对比分析发现,以[Ag(NH₃)₂]OH溶液为前驱体,制备的纳米银胶体具有粒径可控,尺寸均一,分散性良好等特点;而且经过一个月的常温储存,表现出比用AgNO₃溶液为前驱体制备的纳米银胶体具有更高的储存稳定性.     

Preparation of Disperse Silver Particles by Chemical Reduction

Mastery over the microscopic shape and size of a nanoparticle enables accurate control of its properties for some strict application. The mechanism of shape-controlled synthesis was discussed by investigating the formation of silver nanospheres prepared by chemical reduction method using Ag(NH₃)₂⁺ as metal source, ascorbic acid as reducing agent and polyvinylpyrrolidone (K-30) as dispersant. The effects of temperature, PVP/AgNO₃ mass ratio, pH value and the interaction between PVP and silver on the shape and particle size were studied by XRD and SEM. The results show that the morphology of silver particles could transform from branched to spherical and the particle size gradually decrease with the increase of PVP/AgNO₃ mass ratio. The particles size can also be significantly influenced by pH value and temperature. The key point for preparing high dispersity spherical silver powder is that the growth rate of each plane of the particle must be uniform and synchronous. Silver powders with spherical particles with mean size of 0.2 μm were synthesized under the optimum conditions (PVP/AgNO₃ mass ratio 0.6, pH 7, reaction temperature of 40°C).     

Comparative Structural,Optical, and Photoluminescence Studies of YF3:Pr,YF3:Pr@LaF3, and YF3:Pr@LaF3@SiO2 Core–Shell Nanocrystals

Praseodymium (Pr³⁺)‐doped YF₃ (core) and LaF₃ ‐covered YF₃ :Pr (core–shell) nanocrystals (NCs ) were prepared successfully by an ecofriendly, polyol‐based, co‐precipitation process, which were then coated with a silica shell by using a sol–gel‐based Stober method. X‐ray diffraction (XRD), transmission electron microscopy (TEM ), thermal analysis, Fourier transform infrared (FTIR) , UV /vis, energy bandgap, and photoluminescence studies were used to analyze the crystal structure, morphology, and optical properties of the nanomaterial. XRD and TEM results show that the grain size increases after sequential growth of crystalline LaF₃ and the silica shell. The silica surface modification enhances the solubility and colloidal stability of the core–shell‐SiO₂ NCs . The results indicate that the surface coating affects the optical properties because of the alteration in crystalline size of the materials. The emission intensity of silica‐modified NCs was significantly enhanced compared to that of core and core–shell NCs . These results are attributed to the formation of chemical bonds between core–shell and noncrystalline SiO₂ shell via La–O–Si bridges, which activate the “dormant” Pr³⁺ ions on the surfaces of the nanoparticles. The luminescence efficiency of the as‐prepared core, core–shell, and core–shell‐SiO₂ NCs are comparatively analyzed, and the observed differences are justified on the basis of the surface modification surrounding the luminescent seed core NCs .     

A Novel Electrogenerated Chemiluminescence Reaction Scheme Using Core-Shell LuminoI-Based SiO2 Nanoparticles as a Regulator and Its Analytical Application

A novel core-shell luminol-based SiO2 nanoparticle While these nanoparticles were used as electrogenerated was synthesized by two step micro-emulsion method. chemiluminescence （ECL） reagent, the electrochemical （EC） reaction as well as the subsequent chemiluminescence （CL） reaction not only could be separated spatially, but also presented high efficiency for analytical purpose. In this case, the core-shell luminol-based SiO2 nanoparticles offered more potential to avoid the contradiction between the EC and the CL reaction conditions. A new ECL method based on the nanoparticle was developed, and isoniazid was selected as a model analyte to illustrate the characteristics of this new ECL method. Under the selected conditions, the proposed ECL response to isoniazid concentration was linear in the range of 1.0 ×10^-10 to 1.0 × 10^-6 g/mL with 2 × 10^-11g/mL detection limit.     

Preparation and enhanced properties of poly(propylene)/ silica‐grafted‐hyperbranched polyester nanocomposites

A series of poly(propylene) silica‐grafted‐hyperbranched polyester nanocomposites by grafting the modified hyperbranched polyester (Boltorn? H20), possessing theoretically 50% end carboxylic groups and 50% end hydroxyl groups, which endcapped with octadecyl isocyanate (C19), onto the surface of SiO₂ particles (30 nm) through 3‐glycidoxy‐propyltrimethoxysilane (GPTS) was prepared. The effect of silica‐grafted‐modified Boltorn? H20 on the mechanical properties of polypropylene (PP) was investigated by tensile and impact tests. The morphological structure of impact fracture surface and thermal behavior of the composites were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The melt viscosity of composites was investigated by melt flow index (MFI). The obtained results showed that: (1) the modified Boltorn? H20 was successfully grafted onto the SiO₂ surface confirmed by FT‐IR and X‐ray photoelectron spectroscopy (XPS) analysis; (2) the incorporation of silica‐grafted‐modified Boltorn? H20 (3–5 wt% SiO₂) greatly enhanced the notched impact strength as well the tensile strength of the composites; (3) the incorporation of silica‐grafted‐modified Boltorn? H20 had no influence on the melting temperature and crystallinity of PP phase; (4) the MFI of PP composites increased when the silica‐grafted‐modified Boltorn? H20 particles were added compared with PP/SiO₂ or PP/SiO₂‐GPTS composites. Copyright © 2004 John Wiley & Sons, Ltd.     

Mn Oxide‐Silver Composite Nanowires for Improved Thermal Stability,SERS and Electrical Conductivity

Redox transformation reaction between aqueous AgNO₃ and Mn(CH₃COO)₂ at low temperature (～80 °C) has been adopted for industrial‐scale production of uniform Ag–MnOOH composite nanowires for the first time. Varying amounts of incorporated Ag in the composite retain the 1D morphology of the composite. Nanowires upon annealing evolve Ag–MnO₂ nanocomposites, once again with the retention of the parental morphology. Just 4 % of silver incorporation in the composite demonstrates metal‐like conducting performance from the corresponding semiconducting material. Transition of MnO₂ to Mn₂O₃ to Mn₃O₄ takes place upon heat treatment in relation to successive increase in Ag concentrations in the nanowires. The composites offer resistance to the observed oxide transformation. This is evidenced from the progressive increase in transition temperature. In situ Raman, ex situ thermal and XRD analysis corroborate the fact. The composite with 12 % Ag offers resistance to the transformation of MnO₂, which is also verified from laser heating. Importantly, Ag nanoparticle incorporation is proved to offer a thermally stable and better surface enhanced Raman scattering (SERS) platform than the individual components. Both the Ag–MnOOH and Ag–MnO₂ nanocomposites with 8 atomic % Ag show the best SERS enhancement (enhancement factor ～10¹⁰). The observed enhancement relates to charge transfer as well as electromagnetic effects.     

A Silica Bilayer Supported on Ru(0001): Following the Crystalline-to Vitreous Transformation in Real Time with Spectro-microscopy

The crystalline-to-vitreous phase transformation of a SiO₂ bilayer supported on Ru(0001) was studied by time-dependent LEED, local XPS, and DFT calculations. The silica bilayer system has parallels to 3D silica glass and can be used to understand the mechanism of the disorder transition. DFT simulations show that the formation of a Stone–Wales-type of defect follows a complex mechanism, where the two layers show decoupled behavior in terms of chemical bond rearrangements. The calculated activation energy of the rate-determining step for the formation of a Stone—Wales-type of defect (4.3 eV) agrees with the experimental value. Charge transfer between SiO₂ bilayer and Ru(0001) support lowers the activation energy for breaking the Si−O bond compared to the unsupported film. Pre-exponential factors obtained in UHV and in O₂ atmospheres differ significantly, suggesting that the interfacial ORu underneath the SiO₂ bilayer plays a role on how the disordering propagates within the film.     

Green synthesis and physical properties of crystalline silica engineering nanomaterial from rice husk (agriculture waste) at different annealing temperatures for its varied applications

Crystalline nano silica (SiO₂) was synthesized using a cost-effective eco-friendly method from agricultural waste material like rice husk. Polymer nanocomposite has been prepared using the sol-gel technique from crystalline nano silica using PVA as a polymer binder. Thermal analysis measurement is employed to investigate thermal stability. The XRD analysis shows the crystalline nature of silica is revealed to have characteristic peaks of SiO₂. The particle size was evaluated using Schererr's formula and found to be in the range of 21–31 nm. FTIR measurement shows the presence of O–Si–O (silane) bond formation. The PL measurement shows broad excitation prominently in the visible region. In the XRD pattern, a major peak of the Nanocomposite is observed at an angular position of 19.5° degree, which is more prominent than that of the PVA with the addition of 0.2 wt percent Nano silica to the PVA composite. SEM provides information on homogeneous distribution. This could be beneficial in terms of higher mechanical qualities as well as multifunctional properties. By hydrogen bonding, the PVA molecules are strongly linked to each SiO₂ nanoparticle as measured by FTIR. The stability of materials is confirmed by Zeta Potential and DLS. In the photoluminescence property of SiO₂-PVA crystalline Nano silica composite is excited using a radiation wavelength of 200 nm. The indirect bandgap was determined to be 4.28 eV which could be attributed to the 1100 °C annealing temperature. Such materials may be used as a semiconductor material obtained from a direct natural source, rice husk. Thus, in the present research structural, physical, and optical properties of crystalline nano silica and its polymer composite are explored, which leads us to prepare technological grads material from agricultural waste for varied applications including Agriculture to medical science.     

A Stable Monomeric SiO2 Complex with Donor–Acceptor Ligands

Isolation of a monomeric SiO₂ compound 3 as a stable donor–acceptor complex with two different ligands —a σ‐donating ligand (pyridine, dimethylaminopyridine, N ‐heterocyclic carbene) and a donor–acceptor ligand (iminophosphorane)—is presented. The SiO₂ complex 3 is soluble in ordinary organic solvents and is stable at room temperature in solution and in the solid state. Of particular interest, 3 remains reactive and can be used as a stable and soluble unimolecular SiO₂ reagent.     

Performance of the Cr[CH(SiMe3)2]3/SiO2 catalyst for ethylene polymerization compared with the performance of the Phillips catalyst

The catalysis of a silica‐supported chromium system {Cr[CH(SiMe₃)₂]₃/SiO₂} was compared with a silica‐supported chromium oxide catalyst, the Phillips catalyst (CrO₃/SiO₂). This catalyst was prepared by the calcining of the typical silica support used for the Phillips catalyst at 600 °C and by the support of tris[bis(trimethylsilyl)methyl]chromium(III) {Cr[CH(SiMe₃)₂]₃} on the silica. In the slurry‐phase polymerization, this catalyst conducted the polymerization of ethylene at a high activity without organoaluminum compounds as cocatalysts or scavengers. The activity per Cr was about 6–7 times higher than that of the Phillips catalyst. Upon the introduction of hydrogen to the system, the molecular weight of polyethylene did not change with the Phillips catalyst, but it decreased with the Cr[CH(SiMe₃)₂]₃/SiO₂ catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 413–419, 2003     

A novel shape memory poly(ε‐caprolactone) network via UV‐triggered thiol‐ene reaction

A facile method to prepare shape memory polymers crosslinked by SiO₂ is described. A series of biodegradable shape memory networks were obtained through thiol‐ene reaction triggered by UV irradiation between surface‐thiol‐modified SiO₂ nanoparticles and end‐acrylate poly (ε‐caprolactone) (PCL). The highly selective thiol‐ene reaction ensured a uniform distribution of PCL chains between crosslinkers, contributing well‐defined network architecture with enhanced mechanical and shape‐memory properties. Thiol‐functionalized silica nanoparticle was characterized by using FTIR and XPS analysis, and ¹H NMR spectra was used to confirm the successful modification of terminal hydroxyl group of PCL diol. Surface‐modified silica particles were found well dispersible in acrylate‐capped PCL supported by SEM. Thermal and crystalline behaviors of the obtained polymers were analyzed by DSC and XRD, and DMA measurement proved good mechanical property. The shape memory behavior and tensile strength was somewhat tunable by the length of PCL. Acceptably, sample SiO₂‐SMP2k presented 99% recovery ratio and 97% shape fixity, and its relatively high tensile strength showed an attractive potential for biomedical application. Finally, a possible molecular mechanism accounting for the shape memory property was illustrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 692–701     

An investigation on the assembling of WO3 particles on the matrix of silica solution

A facile way to prepare modified WO₃ structure by silica support through sol–gel method is reported. The WO₃/SiO₂ complex film was synthesized from a two steps process and dip-coating method. The films were characterized with laser particle analyzer, IR, Raman. The studies of gelation time and particle size distribution of WO₃/SiO₂ sol indicate that the silica addition could largely reduce the polycondensation of WO₃ clusters. The reaction between WO₃ and SiO₂ were further systematically investigated using IR spectra, and an insight of this reaction was illuminated. Results reveal that Si–OH in SiO₂ sols tended to crosslink with WO₃ at the corner-sharing W–O sites, by which only edge-sharing WO_x clusters could be detected. This modified the WO₃ structure was also approved by the Raman spectra, TEM and AFM images. Moreover, gas sensing properties of the WO₃/SiO₂ films were tested. The assembled WO₃ films exhibited more stable gas sensing stability than pure WO₃ films.     

Thermal stability and flammability performance of polypropylene composites with silica pillared montmorillonites

In present work, silica pillared montmorillonite material (C‐SiO₂‐OMT) was prepared via the sol–gel method, and the influence of the powder on thermal stability and flammability performance of polypropylene (PP) composites was investigated. Characterization of C‐SiO₂‐OMT, elucidated with X‐ray diffraction, transmission electron microscopy, and N₂ adsorption–desorption, suggested that the powder had a mesoporous lamellar structure with high specific surface area and mesoporous volume. The formation of porous structure of C‐SiO₂‐OMT was more conducive than organically modified montmorillonite (OMT) to slowing the volatilization of pyrolytic products generated during thermal degradation process, which led to PP/C‐SiO₂‐OMT microcomposite show better thermal stability than PP/OMT nanocomposite at high temperature range. Flammability properties of these polymer materials evaluated by microscale combustion calorimetry, and cone calorimetry showed a contrary tendency, but C‐SiO₂‐OMT holds high promise to reduce the smoke yield. Copyright © 2013 John Wiley & Sons, Ltd.