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.     

表面等离子体共振技术对过氧化氢的检测

表面等离子体激元共振技术是一种通过观察芯片金属薄膜表面厚度变化产生信号的光学技术,具有实时、灵敏度高、免标记等优点,本文通过辣根过氧化物酶的酶催化作用对过氧化氢进行实时快速检测。信号强度与过氧化氢浓度呈线性关系,辣根过氧化物酶共价结合至金膜表面保持了酶的活性。和其它方法相比较,该方法为过氧化氢的检测提供了一种选择。     

On the Use of Surface Plasmon Resonance Biosensing to Understand IgG-FcγR Interactions

Surface plasmon resonance (SPR)-based optical biosensors offer real-time and label-free analysis of protein interactions, which has extensively contributed to the discovery and development of therapeutic monoclonal antibodies (mAbs). As the biopharmaceutical market for these biologics and their biosimilars is rapidly growing, the role of SPR biosensors in drug discovery and quality assessment is becoming increasingly prominent. One of the critical quality attributes of mAbs is the N-glycosylation of their Fc region. Other than providing stability to the antibody, the Fc N-glycosylation influences immunoglobulin G (IgG) interactions with the Fcγ receptors (FcγRs), modulating the immune response. Over the past two decades, several studies have relied on SPR-based assays to characterize the influence of N-glycosylation upon the IgG-FcγR interactions. While these studies have unveiled key information, many conclusions are still debated in the literature. These discrepancies can be, in part, attributed to the design of the reported SPR-based assays as well as the methodology applied to SPR data analysis. In fact, the SPR biosensor best practices have evolved over the years, and several biases have been pointed out in the development of experimental SPR protocols. In parallel, newly developed algorithms and data analysis methods now allow taking into consideration complex biomolecular kinetics. In this review, we detail the use of different SPR biosensing approaches for characterizing the IgG-FcγR interactions, highlighting their merit and inherent experimental complexity. Furthermore, we review the latest SPR-derived conclusions on the influence of the N-glycosylation upon the IgG-FcγR interactions and underline the differences and similarities across the literature. Finally, we explore new avenues taking advantage of novel computational analysis of SPR results as well as the latest strategies to control the glycoprofile of mAbs during production, which could lead to a better understanding and modelling of the IgG-FcγRs interactions.     

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.     

Experimental Evaluation of Quantum Dots and Antibodies Conjugation by Surface Plasmon Resonance Spectroscopy

The application of antibody-functionalized quantum dots (QDs) in different areas has been widely described in the literature. However, a standard routine method for obtaining information on the conjugation efficiency of QDs with antibodies in terms of the interaction of the functionalized QDs with a specific antigen is still lacking. Herein, surface plasmon resonance (SPR) spectroscopy is proposed for this purpose. Gold-coated SPR sensor disks were modified with a self-assembled monolayer of 11-mercaptoundecanoic acid, and carbodiimide cross-linker chemistry was used to covalently immobilize the CD44 biomarker on the premodified surface (Au/CD44). Meanwhile, QDs functionalized with amine-derivatized polyethylene glycol (PEG) (QDs-NH₂) were chosen for conjugation with antibodies because of their low non-specific adsorption on the Au/CD44 surface. Prior to conjugation, the surface binding capacity (B_max) and equilibrium dissociation constant (K_D) of the specific antibodies against CD44 (anti-CD44) were found to be 263.32 ± 2.44 m° and 1.00 × 10⁻⁷ ± 2.29 × 10⁻⁹ M, respectively. QDs-NH₂ and anti-CD44 were conjugated at their initial molar ratios of 1:3, 1:5, 1:10 and 1:12. SPR measurements showed that the conjugates (QDs-anti-CD44) prepared using 1:10 and 1:12 molar ratios interacted comparably with immobilized CD44 biomarkers. The equilibrium angles in the case of 10- and 12-fold concentrations of anti-CD44 were calculated to be 60.43 ± 4.51 and 61.36 ± 4.40 m°, respectively. This could be explained by the QDs-NH₂ and anti-CD44 having a similar surface loading (about four molecules per QDs-NH₂) and similar hydrodynamic diameters, which were 46.63 ± 3.86 and 42.42 ± 0.80 nm for the 1:10 and 1:12 ratios, respectively. An initial QDs-NH₂: anti-CD44 molar ratio of 1:10 was chosen as being optimal. SPR spectroscopy proved to be the right choice for QDs-anti-CD44 conjugation optimization, and can be used for the evaluation of conjugation efficiency for other nanostructures with various bio-recognition molecules.     

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.     

Studies on the Interactions of Copper and Zinc Ions with ��-Amyloid Peptides by a Surface Plasmon Resonance Biosensor

The aggregation of β-amyloid peptide (Aβ) into fibrils plays an important role in the pathogenesis of Alzheimer’s disease (AD). Metal ions including copper and zinc are closely connected to the precipitation and toxicity of Aβ. In this study, a surface plasmon resonance (SPR) biosensor was constructed to investigate the interactions between Aβ and metal ions. Aβ peptide was immobilized on the SPR chip surface through a preformed alkanethiol self-assembled monolayer (SAM). Our observations indicate that the immobilized Aβ undergoes a conformational change upon exposure to the metal ions. A difference in metal binding affinity between Aβ_1–28 and Aβ_1–42 was also detected. The results suggest that SPR is an effective method to characterize the interactions between Aβ and metal ions.     

Novel energy-saving window coating based on F doped TiO2 nanocrystals with enhanced NIR shielding performance

To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR shielding materials for buildings is of great value. In this report, monodispersed F doped TiO₂ nanocrystals with an average size of 8.6 nm were synthesized as novel solar shielding materials for energy-saving windows. All the products adopted an anatase TiO₂ structure. After doping of F ions, the morphology of TiO₂ was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F⁻ ions into the lattice oxygen sites in the TiO₂ structure. The introduction of F⁻ ions generated free electrons and bulk Ti³⁺ in TiO₂ crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO₂ films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO₂ films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO₂ films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO₂ nanocrystals show a great potential to be used for energy-saving windows.     

Surface Plasmon Resonance from Bimetallic Interface in Au–Ag Core–Shell Structure Nanowires

Transverse surface plasmon resonances (SPR) in Au–Ag and Ag–Au core–shell structure nanowires have been investigated by means of quasi-static theory. There are two kinds of SPR bands resulting from the outer surface of wall metal and the interface between core and wall metals, respectively. The SPR corresponding to the interface, which is similar to that of alloy particle, decreases and shifts obviously with increasing the wall thickness. However, the SPR corresponding to the outer surface, which is similar to that of pure metal particle, increases and shifts slightly with increasing the wall thickness. A mechanism based on oscillatory surface electrons under coulombic attraction is developed to illuminate the shift fashion of SPR from bimetallic core–shell interface. The net charges and extra coulombic force in metallic wall affect the SPR energy and the shift fashion.     

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.     

高比表面积的镁铝复合氧化物纳米薄片的制备及其吸附性能

m2/g提高到224.3 m2/g,这些变化均提高了复合氧化物的吸附性能.     

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。     

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.