Profile Prediction and Fabrication of Wet-Etched Gold Nanostructures for Localized Surface Plasmon Resonance

Dispersed nanosphere lithography can be employed to fabricate gold nanostructures for localized surface plasmon resonance, in which the gold film evaporated on the nanospheres is anisotropically dry etched to obtain gold nanostructures. This paper reports that by wet etching of the gold film, various kinds of gold nanostructures can be fabricated in a cost-effective way. The shape of the nanostructures is predicted by profile simulation, and the localized surface plasmon resonance spectrum is observed to be shifting its extinction peak with the etching time.     

Fundamental research on the label-free detection of protein adsorption using near-infrared light-responsive plasmonic metal nanoshell arrays with controlled nanogap

In this work, we focused on the label-free detection of simple protein binding using near-infrared light-responsive plasmonic nanoshell arrays with a controlled interparticle distance. The nanoshell arrays were fabricated by a combination of colloidal self-assembly and subsequent isotropic helium plasma etching under atmospheric pressure. The diameter, interparticle distance, and shape of nanoshells can be tuned with nanometric accuracy by changing the experimental conditions. The Au, Ag, and Cu nanoshell arrays, having a 240-nm diameter (inner, 200-nm polystyrene (PS) core; outer, 20-nm metal shell) and an 80-nm gap distance, exhibited a well-defined localized surface plasmon resonance (LSPR) peak at the near-infrared region. PS@Au nanoshell arrays showed a 55-nm red shift of the maximum LSPR wavelength of 885 nm after being exposed to a solution of bovine serum albumin (BSA) proteins for 18 h. On the other hand, in the case of Cu nanoshell arrays before/after incubation to the BSA solution, we found a 30-nm peak shifting. We could evaluate the difference in LSPR sensing performance by changing the metal materials.     

Ag纳米粒子生长动力学的局域表面等离子体共振研究

采用Meisel方法利用氧化还原反应制各Ag纳米粒子溶胶,通过对Ag纳米粒子局域表面等离子体共振(SPR)吸收光谱的实时观测,研究了Ag纳米粒子形成的动力学过程,并着重探讨了温度对Ag纳米粒子生长过程的影响.实验发现,SPR吸收峰的移动与实验条件有密切关系.采用恒温磁力搅拌直接加热的方式,Ag纳米粒子的SPR吸收峰在整个反应过程中主要体现为红移,其反应动力学主要表现为零级反应,反应速率与温度符合Arrhenius关系,并粗略估算了一定反应条件下的反应活化能;而采用恒温磁力搅拌水浴加热方式,SPR吸收峰则呈现红移→蓝移→红移交替移动现象.初步探讨了SPR吸收峰的红、蓝移影响因素及其移动机理,得出SPR峰的移动方向是粒径大小与电荷转移相互竞争的结果.     

Nanosilver Colloids-Filled Photonic Crystal Arrays for Photoluminescence Enhancement

For the improved surface plasmon-coupled photoluminescence emission, a more accessible fabrication method of a controlled nanosilver pattern array was developed by effectively filling the predefined hole array with nanosilver colloid in a UV-curable resin via direct nanoimprinting. When applied to a glass substrate for light emittance with an oxide spacer layer on top of the nanosilver pattern, hybrid emission enhancements were produced from both the localized surface plasmon resonance-coupled emission enhancement and the guided light extraction from the photonic crystal array. When CdSe/ZnS nanocrystal quantum dots were deposited as an active emitter, a total photoluminescence intensity improvement of 84% was observed. This was attributed to contributions from both the silver nanoparticle filling and the nanoimprinted photonic crystal array.     

Epitope‐Resolved Detection of Peanut‐Specific IgE Antibodies by Surface Plasmon Resonance Imaging

Peanut allergy can be life‐threatening and is mediated by allergen‐specific immunoglobulin E (IgE) antibodies. Investigation of IgE antibody binding to allergenic epitopes can identify specific interactions underlying the allergic response. Here, we report a surface plasmon resonance imaging (SPRi) immunoassay for differentiating IgE antibodies by epitope‐resolved detection. IgE antibodies were first captured by magnetic beads bearing IgE ?‐chain‐specific antibodies and then introduced into an SPRi array immobilized with epitopes from the major peanut allergen glycoprotein Arachis hypogaea h2 (Ara h2). Differential epitope responses were achieved by establishing a binding environment that minimized cross‐reactivity while maximizing analytical sensitivity. IgE antibody binding to each Ara h2 epitope was distinguished and quantified from patient serum samples (10 μL each) in a 45 min assay. Excellent correlation of Ara h2‐specific IgE values was found between ImmunoCAP assays and the new SPRi method.     

Site‐Specific Immobilization of the Peptidoglycan Synthase PBP1B on a Surface Plasmon Resonance Chip Surface

Surface plasmon resonance (SPR) is one of the most powerful label‐free methods to determine the kinetic parameters of molecular interactions in real time and in a highly sensitive way. Penicillin‐binding proteins (PBPs) are peptidoglycan synthesis enzymes present in most bacteria. Established protocols to analyze interactions of PBPs by SPR involve immobilization to an ampicillin‐coated chip surface (a β‐lactam antibiotic mimicking its substrate), thereby forming a covalent complex with the PBPs transpeptidase (TP) active site. However, PBP interactions measured with a substrate‐bound TP domain potentially affect interactions near the TPase active site. Furthermore, in vivo PBPs are anchored in the inner membrane by an N‐terminal transmembrane helix, and hence immobilization at the C‐terminal TPase domain gives an orientation contrary to the in vivo situation. We designed a new procedure: immobilization of PBP by copper‐free click chemistry at an azide incorporated in the N terminus. In a proof‐of‐principle study, we immobilized Escherichia coli PBP1B on an SPR chip surface and used this for the analysis of the well‐characterized interaction of PBP1B with LpoB. The site‐specific incorporation of the azide affords control over protein orientation, thereby resulting in a homogeneous immobilization on the chip surface. This method can be used to study topology‐dependent interactions of any (membrane) protein.     

Greatly improved NIR shielding performance of CuS nanocrystals by gallium doping for energy efficient window

In this work, gallium doped copper sulfide (Ga-doped CuS) nanocrystals were prepared using a solvothermal method. The effects of Ga doping on the crystal structures, chemical composition, morphology, optical properties and thermal performance of copper sulfide (CuS) were investigated. The Ga-doped CuS nanocrystals had a hexagonal structure comparable to that of pure CuS. The Cu⁺/Cu²⁺ ratio first decreased and then increased with increasing Ga³⁺ doping. Both CuS and Ga-doped CuS exhibited nanoplate and nanorod morphologies. The visible transmittance of the Ga-doped CuS films was in the range of 61–77.1%. Importantly, the near-infrared (NIR) shielding performance of the films can be tuned by adjusting the concentration of the Ga dopant. The NIR shielding value of the optimal Ga-doped CuS film was 72.4%, which was approximately 1.5 times as high as that of the pure CuS film. This can be ascribed to the enhanced plasmonic NIR absorption that resulted from an increase in the hole concentration after doping with Ga³⁺ ions. In the thermal performance test, the Ga-doped CuS film lowered the interior temperature of the heat box by 9.1 °C. Therefore, the integration of good visible transmittance and high NIR shielding performance make the Ga-doped CuS nanocrystals a promising candidate for energy-efficient window coatings.     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

Molecular recognition of arginine by supramolecular complexation with calixarene crown ether based on surface plasmon resonance

Arginine plays an important role in cell division and the functioning of the immune system. We describe a novel method by which arginine can be identified using an artificial monolayer based on surface plasmon resonance (SPR). The affinity of arginine binding its recognition molecular was compared to that of lysine. In fabrication of an arginine sensing interface, a calix[4]crown ether monolayer was anchored onto a gold surface and then characterized by Fourier Transform infrared reflection absorption spectroscopy, atomic force microscopy, and cyclic voltammetry. The interaction between arginine and its host compound was investigated by SPR. The calix[4]crown ether was found to assemble as a monolayer on the gold surface. Recognition of calix[4]crown monolayer was assessed by the selective binding of arginine. Modification of the SPR chip with the calix[4]crown monolayer provides a reliable and simple experimental platform for investigation of arginine under aqueous conditions.     

Adsorption of CO2 on Zeolite 13X and Activated Carbon with Higher Surface Area

In this work, adsorption isotherms and adsorption kinetics of CO₂ on zeolite 13X and activated carbon with high surface area (AC-h) were studied. The adsorption isotherms and kinetic curves of CO₂ on the adsorbents were separately measured at 328 K, 318 K, 308 K, and 298 K and with a pressure range of 0–30 bar by means of the gravimetric adsorption method. The mass transfer constants and adsorption activation energy E_a of CO₂ on the adsorbents were estimated separately. Results showed that at very low pressure the amounts adsorbed of CO₂ on the zeolite 13X was higher than that on the AC-h, while at higher pressure, the amounts adsorbed of CO₂ on the AC-h was higher than that on the zeolite 13X since the AC-h has a larger surface area and a larger total pore volume compared to the zeolite 13X. The adsorption kinetics of CO₂ can be well described by the linear driving force (LDF) model. With the increase of temperature, the mass transfer constants of CO₂ adsorption on both samples increased. The adsorption activation energy E_a for CO₂ on the two adsorbents decreased with the increase of pressure. Furthermore, at low pressure the E_a for CO₂ adsorption on the zeolite 13X was slightly lower than that on the AC-h, while at higher pressure the E_a for CO₂ adsorption on the zeolite 13X was higher than that on the AC-h.     

响应曲面法分析零价铁对普施安蓝H-5R脱色的影响因素

该文分别从零价铁（zVI）投加量、粒径、pH值、盐浓度、摇床摇速对偶氮染料普施安蓝H-5R进行脱色速率研究,并通过响应曲面进行试验优化。结果表明在初始染料溶液浓度为200mg／L时,最适投加量为1．5g／L,脱色速率随着粒径和摇床摇速增大而升高,中性和偏酸条件下pH影响不大,高浓度盐可以增加染料的脱色。响应曲面法（RSM）结果还表明不同影响因素之间存在相互作用,从而影响染料脱色。     

Surface structures and adhesion enhancement of poly(tetrafluoroethylene) films after modification by graft copolymerization with glycidyl methacrylate

Surface modifications of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film were carried out via near-UV light-induced graft copolymerization with glycidyl methacrylate (GMA). The structure and chemical composition of the copolymer surface and interface were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). For PTFE substrate with a substantial amount of grafting, the grafted GMA polymer penetrates or becomes partially submerged beneath a thin surface layer of dense substrate chains to form a stratified surface microstructure. The concentration of the surface-grafted GMA polymer increases with the plasma pretreatment time, the near-UV light illumination time, and the monomer concentration. The GMA graft copolymerized PTFE surfaces adhere strongly to one another when brought into direct contact and cured (i) in the presence of a diamine alone or (ii) in the presence of an epoxy adhesive (epoxy resin plus diamine curing agent). In the presence of diamine alone, failure occurs in the interfacial region. For epoxy adhesive-promoted adhesion, the failure mode is cohesive, i.e. it takes place in the bulk of one of the delaminated PTFE films. The lap shear strengths in both cases increase with the amount of surface-grafted epoxide polymer. The development of the adhesion strength depends on the concentration of the surface graft, the microstructure of the graft copolymerized PTFE surface, the interfacial reactions, and the nature of the bonding agent.     

Controlled accommodation of metal nanostructures within the matrices of polymer architectures through solution-based synthetic strategies

Controlled accommodation of metal nanostructures (MNSs) into the matrix of a well-defined polymer architecture offers an effective approach to achieve hierarchically structured nanocomposites with tunable synergistic properties to broaden application potentials in the emerging fields of energy, environmental science, and medicine. This review focuses on the recently developed zero-dimensional and one-dimensional MNSs@polymer hybrid nanostructures obtained by solution-based synthetic strategies. Progress in the controlled synthesis of those hybrid nanostructures in terms of the number (e.g., monomer, dimer and trimer), organization manner (e.g., linear alignment or confined assembly in certain domains), and spatial arrangement (e.g., in the core and shell) of the MNSs within the distinct polymer matrices are detailed. The synergistic properties and potential applications of those MNSs@polymer hybrids associated with their compositions and morphologies are also reviewed.