Carbohydrate-protein interactions at interfaces: comparison of the binding of Ricinus communis lectin to two series of synthetic glycolipids using surface plasmon resonance studies

Two C-lactosyl lipids and the related C-galactosyl lipids have been synthesised and their binding to RCA120 plant lectin was compared with a second series of thiolactosylethoxyalkanes. The interactions were measured quantitatively in real time by surface plasmon resonance (BIAcore) at a range of concentrations and temperatures from 5 to 30 degrees C. The C-galactosyl lipid (1,3-dimethyl-5-[beta-D-galactopyranosyl]-5-(4-octadecyloxybenzyl)pyrimidine-2,4,6-trione) bound much more weakly with a K(A) = 8.86 x 10(5) than the corresponding C-lactosyl lipid (1,3-dimethyl-5-[beta-D-galactopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-5-(4-octadecyloxybenzyl)pyrimidine-2,4,6-trione) (K(A) = 2.31 x 10(7)). The influence of the linker region of the two different series of lactosyl lipids was clearly demonstrated by the differences in the binding to RCA120 lectin. The changes in kinetic values and in the enthalpic and entropic contribution to the free energy of binding reflected the importance of the linker and the hydrocarbon anchor holding the synthetic glycolipids in the neomembrane.     

Recent developments and applications of hybrid surface plasmon resonance interfaces in optical sensing

Nanostructured noble metals exhibit an intense optical near field due to surface plasmon resonance, therefore promising widespread applications and being of interest to a broad spectrum of scientists, ranging from physicists, chemists, and materials scientists to biologists. A wealth of research is available discussing the synthesis, characterization, and application of noble metal nanoparticles in optical sensing. However, with respect to the sensitivity of the frequency and width of these surface plasmon resonance modes to the particle’s shape, size, and environment, in nearly every case, success strongly depends on the availability of highly stable, adhesive, and sensitive nanoparticles. This undoubtedly presents a challenging task to nanofabrication. The past decade has witnessed fascinating advances in this field, in particular, the construction of oxide-based hybrid plasmonic interfaces to overcome the problem addressed above by (1) coating the metallic nanostructures with thin overlayers to form sandwiched structures or (2) embedding metallic nanostructures in a dielectric matrix to obtain metal/dielectric matrix nanocomposite films. In this critical review, we focus on recent work related to this field, beginning with a presentation of hybrid films with enhanced structural and optical stability, readily and selectively designed using chemical and physical techniques. We then illustrate their interesting optical properties and demonstrate exciting evidence for the postulated application in surface plasmon sensing fields. Finally, we survey the work remaining to be done for that potential to be realized.     

Protein interactions with self-assembled monolayers presenting multimodal ligands: a surface plasmon resonance study

This paper describes the use of surface plasmon resonance (SPR) spectroscopy and self-assembled monolayers (SAMs) to understand the characteristics of surfaces that promote the adsorption of proteins at high ionic strengths (high-salt conditions). We synthesized SAMs presenting different multimodal ligands and determined the influence of surface composition, solution composition, and the nature of the protein on the extent of protein adsorption onto the SAMs. Our results confirm that hydrophobic interactions can contribute significantly to protein adsorption under high-salt conditions. In particular, the extent of protein adsorption under high-salt conditions increased with increasing surface hydrophobicity. The extent of protein adsorption was also influenced by the solution composition and decreased with an increase in the chaotropicity of the anion. The combination of SPR and SAMs is well-suited for studying the interaction of proteins with complex surfaces of relevance to chromatography.     

Non-linear plasmon response to protein binding at a nanostructured gold particle plasmon resonance surface

Rapid adsorption kinetics have been observed for protein binding to a 800 nm aggregated nanoparticle, showing extreme sensitivity resulting from a non-linear particle plasmon response.     

Detection of carbohydrate-binding proteins by oligosaccharide-modified polypyrrole interfaces using electrochemical surface plasmon resonance

This paper reports on the use of electrochemical surface plasmon resonance (E-SPR) for the detection of carbohydrate-binding proteins. The generation of an SPR sensor specific to lectins Arachis hypogaea (PNA) and Maackia amurensis (MAA) is based on the electrochemical polymerization of oligosaccharide derivatives functionalized by pyrrole groups. The resulting thin conducting polymer films were characterized using E-SPR and atomic force microscopy (AFM). The specific binding of PNA to polypyrrole-lactosyl and of MAA to polypyrrole-3'-sialyllactosyl films was investigated using SPR. The detection limit was 41 nM for PNA and 83 nM for MAA. Through Scatchard analysis and linear transformation of the SPR sensorgram data, association (k(ass)) and dissociation rate constants (k(diss)) could be determined.     

Real-time monitoring of biomolecular interactions in blood plasma using a surface plasmon resonance biosensor

We report a novel approach to biosensor-based observations of biomolecular interactions which enables real-time monitoring of biomolecular interactions in complex media. This approach is demonstrated by investigating the interaction between the human chorionic gonadotropin (hCG) and its antibody in blood plasma using a surface plasmon resonance biosensor and a dispersionless microfluidics system. The real-time binding data obtained in blood plasma are compared with those obtained in buffer and blood plasma using a conventional method. It is also demonstrated that the proposed approach can enhance the capability of the biosensor to detect biomolecules in complex samples in terms of detection time and sensitivity. In the model experiment, this approach is shown to enable direct detection of hCG in blood plasma at levels which are five times lower than those detected using the conventional detection approach.     

Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy

Surface plasmon resonance (SPR) is a label-free spectroscopic technique that is highly sensitive to various surface reactions. Incorporating SPR into electrochemical measurements has emerged as a powerful method to study both faradaic and non-faradaic processes. SPR microscopy (SPRM) integrates an optical microscope into SPR detection, which further offers high throughput detection and spatially resolved information at an electrode surface and thus, has attracted attention especially in single entity electrochemical studies. In this review, the progress in the studies of electrochemical interfaces by SPR and SPRM during the past two years will be discussed.     

Recent advances in the development of graphene-based surface plasmon resonance (SPR) interfaces

Surface plasmon resonance (SPR) is a powerful technique for measurement of biomolecular interactions in real-time in a label-free environment. One of the most common techniques for plasmon excitation is the Kretschmann configuration, and numerous studies of ligand–analyte interactions have been performed on surfaces functionalized with a variety of biomolecules, for example DNA, RNA, glycans, proteins, and peptides. A significant limitation of SPR is that the substrate must be a thin metal film. Post-coating of the metal thin film with a thin dielectric top layer has been reported to enhance the performance of the SPR sensor, but is highly dependent on the thickness of the upper layer and its dielectric constant. Graphene is a single-atom thin planar sheet of sp2 carbon atoms perfectly arranged in a honeycomb lattice. Graphene and graphene oxide are good supports for biomolecules because of their large surface area and rich π conjugation structure, making them suitable dielectric top layers for SPR sensing. In this paper, we review some of the key issues in the development of graphene-based SPR chips. The actual challenges of using these interfaces for studying biomolecular interactions will be discussed and the first examples of the use of graphene-on-metal SPR interfaces for biological sensing will be presented.     

Inhibition binding studies of glycodendrimer/lectin interactions using surface plasmon resonance

Understanding protein/carbohydrate interactions is essential for elucidating biological pathways and cellular mechanisms but is often difficult due to the prevalence of multivalent interactions. Here, we evaluate the multivalent glycodendrimer framework as a means to describe the inhibition potency of multivalent mannose-functionalized dendrimers using surface plasmon resonance (SPR). Using highly robust, mannose-functionalized dithiol self-assembled monolayers on gold surfaces, we found that glycodendrimers were efficient inhibitors of protein/carbohydrate interactions. IC₅₀ values ranging from 260 nM to 13 nM were obtained for mannose-functionalized dendrimers with Concanavalin A.     

Detection of transglucosidase-catalyzed polysaccharide synthesis on a surface in real time using surface plasmon resonance spectroscopy

Biological systems that involve enzyme catalysis at surfaces, particularly strategically important ones that involve insoluble substrates/products such as the cell wall and the starch granule, require analyses beyond classical solution state enzymology. Using a model system, we have demonstrated the real-time measurement of transglucosidase activity on a surface using surface plasmon resonance (SPR) spectroscopy. We monitored the extension of a (partially carboxymethylated) dextran surface with alternansucrase and sucrose as a glycosyl donor. Conditions were used where surface polymer synthesis rates were a function of enzyme concentration and proportional to the extent of enzyme binding to the surface. A method to determine the turnover number of the enzyme on the surface was also developed. The presence of a new amorphous polysaccharide was observed optically, detected by lectin binding and imaged by atomic force microscopy. This surface method will have utility in a wide range of carbohydrate enzyme systems including screens.     

Maneuvering the surface plasmon resonance of silver nanostructures through shape-controlled synthesis

Silver nanostructures are containers for surface plasmons - the collective oscillation of conduction electrons in phase with incident light. By controlling the shape of the container, one can control the ways in which electrons oscillate, and in turn how the nanostructure scatters light, absorbs light, and enhances local electric fields. With a series of discrete dipole approximation (DDA) calculations, each of a distinctive morphology, we illustrate how shape control can tune the optical properties of silver nanostructures. Calculated predictions are validated by experimental measurements performed on nanocubes with controllable corner truncation, right bipyramids, and pentagonal nanowires. Control of nanostructure shape allows optimization of plasmon resonance for molecular detection and spectroscopy.     

Electrochemical impedance spectroscopy and surface plasmon resonance studies of DNA hybridization on gold/SiOx interfaces

The use of Au/SiO(x) interfaces for the investigation of DNA hybridization using electrochemical impedance spectroscopy (EIS) and surface plasmon resonance (SPR) simultaneously is demonstrated. Standard glass chemistry was used to link single-stranded DNA (ss-DNA) on aldehyde-terminated Au/SiO(x) interfaces. The layer thickness and amount of grafted oligonucleotides (ODNs) were calculated from SPR on the basis of a multilayer system of glass/Ti/Au/SiO(x)/grafted molecule. Capacitance and resistance values of the modified interface before and after hybridization were calculated from EIS data using an equivalent circuit and allowed the affinity rate constant, K(A) = 4.07 x 10(5) M(-1), to be determined. The EIS results were comparable to those obtained by SPR hybridization kinetics recorded in parallel.     

Janus particles with a functional gold surface for control of surface plasmon resonance

We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper.     

Molten salt synthesis and localized surface plasmon resonance study of vanadium dioxide nanopowders

Rutile-type vanadium dioxide nanopowders with four different sizes were successfully synthesized by carbothermal reducing V₂O₅ in KCl-LiCl molten salt. XRD and TEM characterizations suggested that vanadium dioxide particles formed by a broken and reunited process of vanadium oxide. Molten salt and organic carbon sources are crucial to the size of final particles. In the presence of the molten salt, the organic carbon with a shorter chain length would induce smaller particles. The UV-VIS-IR spectral measurements for as-prepared vanadium dioxide announced an obvious localized surface plasmon resonance band in the near infrared region at 90 °C.     

Colloidal synthesis of new silver-based nanostructures with tailored localized surface plasmon resonance

Silver-based nanostructures with tailored localized surface plasmon resonance are of interest for a number of practical applications. They can conventionally be divided into three main groups: (1) anisotropic silver particles, (2) particles of alloys of silver with other metals, and (3) composite particles with dielectric or magnetic cores and silver shells. Fine “tuning” of plasmon resonance of these particles is ensured by changes in their shapes, composition, and/or structure. Procedures for the colloidal synthesis of nanostructures of all these groups and some fields of their application are described, with the main attention focused on core/shell composite particles.     

Antigen-antibody interactions: binding studies with fluorescence and surface plasmon resonance exemplified by acid-traseolide as antigen

The interaction between the musk fragrance acid-traseolide and monoclonal antibodies (mAB) generated against this odorant has been investigated with two different techniques. Fluorescence spectroscopy was used to study the quenching of tryptophan fluorescence of the antibody upon binding acid-traseolide. This spectroscopic approach is based on measurements under equilibrium conditions. The second technique exploited the surface plasmon resonance (SPR) phenomenon. The acid-traseolide was immobilized in the surface matrix and upon presenting mAB changes in SPR were recorded in real time during the association reaction. The SPR approach can be considered as a kinetic method. Although having a different origin, both methods lead to comparable equilibrium dissociation constants (Kd). However, the results obtained with fluorescence spectroscopy were more accurate and reproducible. Not only the association of acid-traseolide with antibody was evaluated, also Fab fragment and peptide (H3-peptide) mimicking the heavy chain CDR3 of this antibody were included in this study. The Kd-values, determined by both methods, increase in the order mAB < Fab < H3-peptide because of diminishing recognition.     

Multichannel surface plasmon resonance imaging and analysis of micropatterned self-assembled monolayers and protein affinity interactions

Multichannel images of 11-mercaptoundecanoic acid and 11-mercapto-1-undecanol self-assembled monolayers together with a biospecific interferon-gamma (IFN-gamma)/anti-IFN-gamma antibody immunoaffinity interaction were observed by the two-dimensional surface plasmon resonance (2D-SPR) imaging system. With the fabricated 2D-SPR imaging system, adopting a white light source in combination with a narrow band-pass filter, sharp images were resolved, minimizing the diffraction patterns on the resulting images. Micropatterning of self-assembled monolayers was acheived by exploiting the UV photolysis of thiol bonding, instead of conventional photolithography. The line profile calibration of the image contrast with ellipsometric analysis enabled us to discriminate the change in monolayer thickness within a sub-nanometer scale. For the protein interactions on the surface, the biospecific affinity recognition reaction of IFN-gamma antigen with surface-immobilized antibody was analyzed. Through the signal amplification strategy based on the enzyme-catalyzed precipitation reaction in a sandwich-type immunoassay, biospecific antigen binding was found detectable down to a concentration of 1 ng/mL.     

A model for describing the thermodynamics of multivalent host-guest interactions at interfaces

A model has been described for interpreting the binding of multivalent molecules to interface-immobilized monovalent receptors through multiple, independent interactions. It is based on the concept of effective concentration, C(eff), which has been developed before for multivalent binding in solution and which incorporates effects of lengths and flexibilities of linkers between interacting sites. The model assumes: (i). the interactions are independent, (ii). the maximum number of interactions, p(max), is known, (iii). C(eff) is estimated from (simple) molecular models. Simulations of the thermodynamics and kinetics of multivalent host-guest binding to interfaces have been discussed, and competition with a monovalent competitor in solution has been incorporated as well. The model was successfully used to describe the binding of a divalent guest to self-assembled monolayers of a cyclodextrin host. The adsorption data of more complex guest-functionalized dendrimers, for which p(max) was not known beforehand, was interpreted as well. Finally, it has been shown that the model can aid to deconvolute contributions of multivalency and cooperativity to stability enhancements observed for the adsorption of multivalent molecules to interfaces.