An interlaboratory comparison of mid-infrared spectra acquisition: Instruments and procedures matter

Diffuse reflectance spectroscopy has been extensively employed to deliver timely and cost-effective predictions of a number of soil properties. However, although several soil spectral laboratories have been established worldwide, the distinct characteristics of instruments and operations still hamper further integration and interoperability across mid-infrared (MIR) soil spectral libraries. In this study, we conducted a large-scale ring trial experiment to understand the lab-to-lab variability of multiple MIR instruments. By developing a systematic evaluation of different mathematical treatments with modeling algorithms, including regular preprocessing and spectral standardization, we quantified and evaluated instruments' dissimilarity and how this impacts internal and shared model performance. We found that all instruments delivered good predictions when calibrated internally using the same instruments' characteristics and standard operating procedures by solely relying on regular spectral preprocessing that accounts for light scattering and multiplicative/additive effects, e.g., using standard normal variate (SNV). When performing model transfer from a large public library (the USDA NSSC-KSSL MIR library) to secondary instruments, good performance was also achieved by regular preprocessing (e.g., SNV) if both instruments shared the same manufacturer. However, significant differences between the KSSL MIR library and contrasting ring trial instruments responses were evident and confirmed by a semi-unsupervised spectral clustering. For heavily contrasting setups, spectral standardization was necessary before transferring prediction models. Non-linear model types like Cubist and memory-based learning delivered more precise estimates because they seemed to be less sensitive to spectral variations than global partial least square regression. In summary, the results from this study can assist new laboratories in building spectroscopy capacity utilizing existing MIR spectral libraries and support the recent global efforts to make soil spectroscopy universally accessible with centralized or shared operating procedures

Electrochemical polychlorinated biphenyls immunosensor based on functionalized polyaniline nanocomposite

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2015.Immunosensors are analytical devices comprising antibody (Ab) molecules intimately integrated with electronic physicochemical transducers. Abs are responsible for specific recognition of an analyte so called antigen (Ag) while transducers are responsible for the conversion of chemical changes brought about by Ab-Ag interactions into measurable and processable signal. Amongst the many analytical tools, immunosensors have shown outstanding performance in applications in fields such as clinical diagnostics, agricultural purposes and environmental monitoring. They have come in place of the many conventional analytical methods which showed a number of disadvantages; high cost and longer time of operation, and requirement of highly knowledgeable personnel. On the other hand, immunosensors have shown potential to overcome these constraints. Their advantages include possibilities of portability, miniaturization, and simplified procedures. Of the possible fields of immunosensor applications, this study focussed on the environmental aspect. The safety of the environment is good for the well-being even though there are still some environmental threats that exist. Polychlorinated biphenyls (PCBs) have reportedly been found to be some of the potential substances to pose such threats due to their toxic and persistent behaviour. In this study, we have developed an electrochemical immunosensor as an analytical tool for the analysis and monitoring of PCBs. The development was based on the use of silver nanoparticles-doped polyaniline (PANI/Ag NPs) for modification of an electrode as a process for fabrication of the transducer. The PANI/Ag NPs composite was deposited on the glassy carbon (GC) and platinum (Pt) electrodes by oxidative electropolymerization of aniline in the presence of Ag NPs in 1 M HCl using cyclic voltammetry (CV) by ramping the potential from -0.1 to 1.4 V at 50 mV/s. The composite was then characterized and evaluated as a potential material for electrochemical transduction. Evaluation was on electroactivity, which is the main property of interest for materials used in the fabrication of electrochemical devices. The PANI composites were characterized using spectroscopic (FTIR), microscopic (TEM) and electrochemical CV techniques. Results confirmed the formation of PANI in its emeraldine form and the presence of Ag NPs. Characteristic functional groups and peaks of PANI were observed in FTIR and CV respectively. TEM micrograms showed one dimensional nanofibric tubes and crystalline-like structure of the composite. The incorporation of Ag NPs was indicated by the transition from the amorphous (PANI) to crystalline (PANI/Ag NPs) structure accompanied by increase in size as well as smoothness of the tubes. EDS-TEM counts increase of the chlorine (Cl) peaks is due to the closeness of these peaks to those of Ag, thus confirming incorporation of Ag NPs

Development of a silver functionalised polyaniline electrochemical immunosensor for polychlorinated biphenyls

An electrochemical immunosensor based on a silver nanoparticles (Ag NPs)-doped polyaniline (PANI) modified glassy carbon electrode (GCE) transducer, wherein polyclonal anti-polychlorinated biphenyl (PCB) antibody (Ab) was immobilized by a covalent linkage with glutaraldehyde (GA), was developed. The optimum conditions for the fabrication of the immunosensor were immersion, 30 min incubation in 1.0% GA. Electrochemical measurements of PCB 28 were done using the square wave voltammetry (SWV) technique. The optimum methodology conditions were a 20 mV s−1 scan rate, sweep potential range of −1 to 1 V and PCB incubation period of 2 h. The electrochemical response obtained under these optimum conditions was linear within 0.2 and 1.2 ng mL−1 with limit of detection (LOD) and limit of quantitation (LOQ) values of 0.063 ng mL−1 and 0.209 ng mL−1, respectively. The specificity of the developed sensor towards PCB 28 against benzyl chloride (BnCl) and PCB 180 was poor due to structural similarities. However, the PCB 180 results correspond to total PCB, thus indicating the sensor's applicability to regular total PCB determination. Cations and anions tested had a minimum effect on the sensor. Recoveries in water and guava juice ranged from 90% to 102%. Thus, proving the immunosensor's selectivity to PCBs and its possible application in the detection and monitoring of PCBs in food, water bodies and general environmental samples

Potential of silver nanoparticles functionalized polyaniline as an electrochemical transducer

Modification of commercial platinum (Pt) and glassy carbon (GC) electrodes with polyaniline (PANI) and silver nanoparticles doped polyaniline (PANI/Ag NPs) through electropolymerization of aniline in the absence and presence of Ag NPs in 1 M hydrochloric acid (HCl) was interrogated. Fourier transform infrared (FTIR) and transmission electron microscope (TEM) techniques were used for structural, compositional and morphological elucidation. FTIR spectra for PANI and PANI/Ag NPs had the characteristic PANI functional groups as well as desired bands for the conducting emeraldine (EM) form. The predominance of the PANI pattern in the spectra is indicative of the intact PANI structure in the presence of Ag NPs while the slight band shifts are signify interfacial interactions between PANI and Ag NPs. TEM micrograms depicts different size one dimensional nanofibric tubes of the supramolecular structures of PANI. Ag NPs functionalized PANI had larger smoother tubes, suggesting organized morphology arrangement. An increased energy dispersive spectroscopy (EDS)-TEM count from 256 to 277 confirms incorporation of Ag NPs in PANI. GC/PANI/Ag NPs exhibited outstanding electroactivity (higher conductivity and rate of electron transfer).This might be a result of the large surface coverage, film thickness and diffusion coefficient as a result of the large GC surface area. Possibly, the improvement might be due to the GC electrode properties. The electroactivity of the electrodes increased in the order: Pt < GC < Pt/PANI < Pt/PANI/Ag NPs < GC/PANI < GC/PANI/Ag NPs. The effect of Ag NPs in the polymer was demonstrated by ultimate band gap reduction of PANI and enhanced magnitudes of current response per electrode

An interlaboratory comparison of mid-infrared spectra acquisition: Instruments and procedures matter

Diffuse reflectance spectroscopy has been extensively employed to deliver timely and cost-effective predictions of a number of soil properties. However, although several soil spectral laboratories have been established worldwide, the distinct characteristics of instruments and operations still hamper further integration and interoperability across mid-infrared (MIR) soil spectral libraries. In this study, we conducted a large-scale ring trial experiment to understand the lab-to-lab variability of multiple MIR instruments. By developing a systematic evaluation of different mathematical treatments with modeling algorithms, including regular preprocessing and spectral standardization, we quantified and evaluated instruments' dissimilarity and how this impacts internal and shared model performance. We found that all instruments delivered good predictions when calibrated internally using the same instruments' characteristics and standard operating procedures by solely relying on regular spectral preprocessing that accounts for light scattering and multiplicative/additive effects, e.g., using standard normal variate (SNV). When performing model transfer from a large public library (the USDA NSSC-KSSL MIR library) to secondary instruments, good performance was also achieved by regular preprocessing (e.g., SNV) if both instruments shared the same manufacturer. However, significant differences between the KSSL MIR library and contrasting ring trial instruments responses were evident and confirmed by a semi-unsupervised spectral clustering. For heavily contrasting setups, spectral standardization was necessary before transferring prediction models. Non-linear model types like Cubist and memory-based learning delivered more precise estimates because they seemed to be less sensitive to spectral variations than global partial least square regression. In summary, the results from this study can assist new laboratories in building spectroscopy capacity utilizing existing MIR spectral libraries and support the recent global efforts to make soil spectroscopy universally accessible with centralized or shared operating procedures

Advances in electrochemical immunosensors

Immunosensors are compact tools on which antibody and antigen interactions are formed. The specific interaction between antibody and antigen is detected by using a transducer and an electrical signal is measured. This specific interaction between these molecules makes immunosensor very attractive for several applications in different fields. Electrochemical immunosensors are successful devices in selective and sensitive detection of several analytes. Electrochemical transducing methods such as voltammetric, potentiometric, conductometric or impedimetric have been utilized in different applications due to their excellent properties such as being low-cost, sensitivity and simplicity. In this chapter, the fundamentals of electrochemical immunosensors are summarized and different applications in food, environmental and clinical analyses are investigated and discussed

Advances in immunosensor technology

In recent years, advances in immunosensor device fabrication have significantly expanded the use of this technology in a broad range of applications including clinical diagnosis, food analysis, quality control, environmental studies and industrial monitoring. The most important aspect in fabrication is to obtain a design that provides a low detection limit. The utilization of nanomaterials as a label, catalyst and biosensing transducer is, perhaps, the most popular approach in ultrasensitive devices. This chapter reviews recent advances in immunosensor fabrication and summarizes the most recent studies. Strategies employed to significantly improve sensitivity and specificity of immunosensor technology and the advantages and limitations thereof are explored. © 2021 Elsevier Inc