Hydrophobic and hydrophilic au and ag nanoparticles. Breakthroughs and perspectives

This review provides a broad look on the recent investigations on the synthesis, characterization and physico-chemical properties of noble metal nanoparticles, mainly gold and silver nanoparticles, stabilized with ligands of different chemical nature. A comprehensive review of the available literature in this field may be far too large and only some selected representative examples will be reported here, together with some recent achievements from our group, that will be discussed in more detail. Many efforts in finding synthetic routes have been performed so far to achieve metal nanoparticles with well-defined size, morphology and stability in different environments, to match the large variety of applications that can be foreseen for these materials. In particular, the synthesis and stabilization of gold and silver nanoparticles together with their properties in different emerging fields of nanomedicine, optics and sensors are reviewed and briefly commented

Surface plasmon resonance: a versatile technique for biosensor applications

Surface plasmon resonance (SPR) is a label-free detection method which has emerged during the last two decades as a suitable and reliable platform in clinical analysis for biomolecular interactions. The technique makes it possible to measure interactions in real-time with high sensitivity and without the need of labels. This review article discusses a wide range of applications in optical-based sensors using either surface plasmon resonance (SPR) or surface plasmon resonance imaging (SPRI). Here we summarize the principles, provide examples, and illustrate the utility of SPR and SPRI through example applications from the biomedical, proteomics, genomics and bioengineering fields. In addition, SPR signal amplification strategies and surface functionalization are covered in the review.open1

Development of Nanofiber and Surface Plasmon Resonance Sensors for VOCs, Biochemical, and Bacterial Analysis

It is important to monitor potential exposure to various chemicals and toxicants that may adversely affect both human and environmental health. Biosensors have been developed to identify and quantify these analytes of interest in early warning systems and diagnosis devices. This dissertation implements nanomaterials, such as nanofibers and nanoparticles, into the biological recognition element of a biosensor for selectively and sensitively to detect trace analytes in either gas, liquid, or solid phases.This dissertation is an agglomeration of several different projects that investigates the novel applications of nanomaterials into biosensor designs with two major application focuses: nanofibers and surface plasmon resonance (SPR) The first half of this dissertation focuses on the application of nanofiber surfaces for sensor developments. The nanofibers were fabricated through electrospinning and incorporated into various sensor designs. The first project develops polyaniline nanofibers into a chemiresistor sensor for sensitive detection of VOCs (small chain alcohols) by employing variants of reduced graphene oxides. The second project applies the nanofiber property of high surface area to volume ratio to maximize surface adsorption of EDTA-functionalized silver nanoparticles (AgNPs) as the biorecognition element of this sensor. The EDTA-AgNPs formulates a nickel ion bridge for selective capture and release of NTA and His tagged proteins that can be detected through fluorescent spectroscopy. The second half of this dissertation transitions into the application of surface plasmon resonance for the development of biosensor signal transducers. The third project focused on combining the potential of 3D printing with gold nanoparticles (AuNPs) to create a novel integrated localized SPR (LSPR) sensor surface capable of sensitive protein detection. The synthesis of gold nanoparticles in-situ on a 3D printed prism surface enables the fabrication of a biosensor device for the disposable field of site usage with qualities comparable performances with sensors using commercial optical prisms. The last project focuses on developing an SPR experimental model of a double lipid bilayer membrane. This model mimics the unique structure of the double lipid bilayer membrane system found in the chloroplast, mitochondria, and gram-negative bacteria. This novel experimental model combined with SPR analysis creates a biosensor platform that enables the interrogation of chemical and protein interactions at interfaces such as the gram-negative bacteria cell wall and membrane system

Development of a highly specific amine-terminated aptamer functionalized surface plasmon resonance biosensor for blood protein detection

This paper presents a generally applicable approach for the highly specific detection of blood proteins. Thrombin and thrombin-binding aptamers are chosen for demonstration purposes. The sensor was prepared by immobilizing amine-terminated aptamers onto a gold modified surface using a two-step self-assembled monolayer (SAM) immobilization technique and the physical detection is performed using Surface Plasmon Resonance (SPR). The developed sensor has an optimal detectable range of 5–1000 nM and the results show the sensor has good reversibility, sensitivity and selectivity. Furthermore, the sensor shows the potential of being improved and standardized for direct detection of other blood proteins for clinical applications

Smart and Functional Interfaces for Sensitive SPR Biosensing Towards Biomedical Applications

The aim of this thesis is to develop Surface Plasmon Resonance (SPR) methods that improve biosensing performance, in particular the sensitivity and selectivity of the analysis and their adaptation for biomedical applications to samples with complex background. This is of significant importance in translating the biosensor technologies to deliver the same results as the conventional methods but in a more accessible, efficient, and economical manner. The first study exploited SPR as a DNA biosensor for the detection of Malaria Plasmodium falciparum parasite with the hybridization chain reaction (HCR), which resulted in the formation of self-assembled target DNA nanostructures for signal enhancement. The sensitivity was further improved by using gold nanoparticles (AuNPs) for additional signal amplification. Tests with human blood plasma indicated the results were comparable to analyses in buffer, despite noticeable non-specific binding from the plasma. The concern of non-specific binding was systematically investigated in the second study where an antifouling surface consists of supported lipid bilayer membranes (SLBs) and protein A was developed for detection of trace amount of proteins in undiluted human serum. Specifically, cholera toxin (CT) spiked into the serum was used as the target, and advanced interface was further extended to immunosensing of immunoglobulin G (IgG). In the third study, SPR biosensor was employed in combination of bright field microscopy to characterize cellular apoptosis. HeLa cells undergoing apoptosis induced by hydrogen peroxide (H2O2) were monitored by SPR and the signals were compared to microscopic analysis of the morphological changes. SPR study revealed a decreased signal as cell confluency decreases, with the rates increasing as H2O2 concentration increases. An abnormality was found at high concentrations when both apoptosis and necrosis were induced. A mathematical model was proposed to explain SPR response where a non- uniform adsorbed layer was partially responsible. The significance of this thesis is that a number of high performing biosensing approaches have been developed and demonstrated. In addition to the advantages of SPR (e.g. label-free, real-time biomolecules binding, and portability), these methods have paved the way towards realizing effective sensing in biomedical research, especially in the early detection of infectious diseases and in the treatment of cancers

Interaction of Solid Lipid Nanoparticles and Specific Proteins of the Corona Studied by Surface Plasmon Resonance

The applications of pharmaceutical and medical nanosystems are among the most intensively investigated fields in nanotechnology. A relevant point to be considered in the design and development of nanovehicles intended for medical use is the formation of the "protein corona" around the nanoparticle, that is, a complex biomolecular layer formed when the nanovehicle is exposed to biological fluids. The chemical nature of the protein corona determines the biological identity of the nanoparticle and influences, among others, the recognition of the nanocarrier by the mononuclear phagocytic system and, thus, its clearance from the blood. Recent works suggest that Surface Plasmon Resonance (SPR), extensively employed for the analysis of biomolecular interactions, can shed light on the formation of the protein corona and its interaction with the surroundings. The synthesis and characterization of solid lipid nanoparticles (SLN) coated with polymers of different chemical nature (e.g., polyvinyl alcohol, chitosans) are reported. The proof-of-concept for the use of SPR technique in characterizing protein-nanoparticle interactions of surface-immobilized proteins (immunoglobulin G and bovine serum albumin, both involved in the formation of the corona) subjected to flowing SLN is demonstrated for non-chitosan-coated nanoparticles. All assayed nanosystems show more preference for IgG than for BSA, such preference being more pronounced in the case of polyvinyl-alcohol-coated SLN.Facultad de Ciencias ExactasCentro de Investigación y Desarrollo en Fermentaciones IndustrialesInstituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Creation of novel gold-nanorod-based localized surface plasmon resonance biosensors

Starting with a comprehensive review of both surface plasmon resonance (SPR) based and localized surface plasmon resonance (LSPR) based sensors, this thesis reports the studies on the development of a novel sensitive gold nanorod (GNR) based label-free LSPR optical fibre biosensor, and the development of a novel robust method for effectively modifying the surface of cetyl-trimethyl ammonium bromide (CTAB) capped GNRs and their LSPR biosensing applications. A novel GNR-based LSPR optical fibre sensor was fabricated and evaluated in this work. The sensor probe was prepared by covalently immobilizing GNRs, synthesized using a seed-mediated growth method, on the decladed surface of a piece of multimode optical fibre. In order to operate the LSPR sensor as a reflective sensor, a silver mirror was also coated at one distal end of the sensor probe by a dip coating method. In the refractive index sensitivity test, it was found that the longitudinal plasmon band (LPB) of GNRs is highly sensitive to the refractive index change close to the GNRs surface, and the sensitivity of the LSPR optical fibre sensor increases with the increase of the aspect ratio of GNRs. The results showed that the GNR-based LSPR optical fibre sensors prepared in this work have linear and high refract index sensitivities. For sensors based on GNRs with aspect ratios of 2.6, 3.1, 3.7 and 4.3, their refractive index sensitivities were found to be 269, 401, 506 and 766 nm/RIU (RIU = refractive index unit), respectively, in the refractive index range from 1.34 to 1.41. In order to evaluate the biosensing performance, the GNR-based LSPR optical fibre sensor with aspect ratio of 4.1 and a 2 cm sensing length was further functionalized with human IgG to detect the specific target — anti-human IgG, and a detection limit of 1.6 nM was observed using a wavelength-based interrogation approach. In another study, in order to overcome the drawbacks of the CTAB-capped GNRs found in biosensing and biomedical applications, a simple yet robust pH-mediated method for effectively modifying the surface of CTAB-capped GNRs synthesized by the seed-mediated growth method was developed. This method allows the complete replacement of the CTAB molecules attached on the GNRs surface with the 11-mercaptoundecaonic acid (MUA) molecules to take place in a total aqueous environment by controlling the pH of the MUA aqueous solution, thus avoiding the irreversible aggregation of GNRs during the complex surface modification process observed in the previous reported methods. The success of the complete replacement of CTAB with MUA was confirmed by the surface elemental analysis using an X-ray photoelectron spectroscopy (XPS), and the MUA-modified GNRs created in this work demonstrated a high stability up to 4 months at least when stored in a buffer solution at pH 9 at 4°C. The MUA-modified GNRs with an aspect ratio of 3.9 were furthered developed as a solution-phase-based label-free LSPR biosensor by functionalizing the GNRs with human IgG. A detection limit as low as 0.4 nM for detecting anti-human IgG was achieved by this sensor. The achievements of this work are concluded and the directions of future work are also pointed out

Magnetic and Plasmonic Contrast Agents in Optical Coherence Tomography

Optical coherence tomography (OCT) has gained widespread application for many biomedical applications, yet the traditional array of contrast agents used in incoherent imaging modalities do not provide contrast in OCT. Owing to the high biocompatibility of iron oxides and noble metals, magnetic and plasmonic nanoparticles, respectively, have been developed as OCT contrast agents to enable a range of biological and pre-clinical studies. Here we provide a review of these developments within the past decade, including an overview of the physical contrast mechanisms and classes of OCT system hardware addons needed for magnetic and plasmonic nanoparticle contrast. A comparison of the wide variety of nanoparticle systems is also presented, where the figures of merit depend strongly upon the choice of biological application