Redundant chemical sensors for calibration-impossible applications

Multiple chemical sensors are used to measure the same analyte simultaneously to determine whether the redundant signals can improve the long-term accuracy and circumvent the need for periodic calibrations. A specific marine chemistry application was investigated where six glass pH electrodes were placed in a synthetic seawater solution for nearly 2 months without recalibration. The pH accuracy was evaluated by comparison with spectrophotometric pH measurements. The standard deviation, t-test and principal-component analysis were used to evaluate the redundant signals. The average signal standard deviation was useful for determining the onset of drift, whereas, the principal-component analysis readily identified specific sensors that were drifting. The sensor signals, shown through t-tests to be outliers, were eliminated from the data set, resulting in a significant improvement in measurement accuracy. After 56 days, the signals from non-drifting and drifting sensors resulted in a pH accuracy of +/-0.012 and +/-0.040, respectively, over a threefold improvement. The residual +/-0.012 inaccuracy was limited by the performance of the remaining sensors, which appeared to drift with similar magnitude and could therefore not be statistically separated. These results indicate that redundant sensors coupled with a principal-component analysis are a potential alternative for situations where calibrations are not feasible.     

Nanomaterials and nanotechnologies in chemical and biochemical sensors: Capabilities and applications

The publications reporting on the use of nanomaterials and nanotechnologies in chemical and biochemical sensor designing were reviewed for the recent decade. The capabilities and applications were discussed for nanoparticles based on gold, silver, magnetic and semiconductor materials (quantum dots), lanthanides, and silica compounds, as well as for nanotubes and nanolayers (Langmuir-Blodgett films, selfassembled monolayers) used in optical (absorbance, luminescence, surface enhanced Raman spectroscopy, surface plasmon resonance), electrochemical, and mass-sensitive sensors. It was shown that the unique capabilities of nanosensors might hold the key to improve the analysis of liquids, gases, and especially biochemical and biological objects in the near future.     

Supramolecular complexes based on calixarenes: force field calculations and applications for chemical sensors

The inclusion of organic molecules to different calixarenes was investigated both experimentally and theoretically. Experimental data were obtained for various calixarenes of different thicknesses interacting with perchloroethylene, chloroform, benzene and toluene at different partial pressures and temperatures. The amount of included molecules was monitored by frequency responses of mass-sensitive bulk acoustic wave devices. To estimate ‘key-lock’ binding energies, the activation energy of desorption was determined experimentally from thermodesorption spectroscopy. The host/guest interaction energies were calculated theoretically with the TRIPOS force field approach which, in contrast to current quantum chemical approaches (MOPAC/AM1, MOPAC/PM3), gave satisfactory distance-dependent energy minima. Experimentally observed changes in the binding energies for the inclusion of C₂Cl₄, CHCl₃, CH₃C₅H₆ and C₆H₆ molecules in calixarenes agree surprisingly well with results with theoretical calculations.     

Rational materials design of sorbent coatings for explosives: applications with chemical sensors

A series of chemoselective polymers had been designed and synthesized to enhance the sorption properties of polymer coated chemical sensors for polynitroaromatic analytes. To evaluate the effectiveness of the chemoselective coatings, a polynitroaromatic vapor test bed was utilized to challenge polymer coated surface acoustic wave (SAW) devices with different explosive vapors. Dinitrotoluene detection limits were determined to be in the <100 parts per trillion ranges. ATR-FTIR studies were used to determine the nature of the polymer-polynitroaromatic analyte interactions, and confirm the presence of hydrogen-bonding between polymer pendant groups and the nitro functional groups of polynitroaromatic explosive materials.     

Optical waveguide sensors in analytical chemistry: today’s instrumentation, applications and trends for future development

Current concepts for chemical and biochemical sensing based on detection with optical waveguides are reviewed. The goals are to provide a framework for classifying such sensors and to assist a designer in selecting the most suitable detection techniques and waveguide arrangements. Sensor designs are categorized on the basis of the five parameters that completely describe a light wave: its amplitude, wavelength, phase, polarization state and time-dependent waveform. In the fabrication of a successful sensor, the physical or chemical property of the determined species and the particular light wave parameter to detect it should be selected with care since they jointly dictate the sensitivity, stability, selectivity and accuracy of the eventual measurement. The principle of operation, the nature or the detected optical signal, instrumental requirements for practical applications, and associated problems are analyzed for each category of sensors. Two sorts of sensors are considered: those based on direct spectroscopic detection of the analyte, and those in which the analyte is determined indirectly through use of an analyte-sensitive reagent. Key areas of recent study, useful practical applications, and trends in future development of optical waveguide chemical and biochemical sensors are considered.     

Optical waveguide sensors in analytical chemistry: today’s instrumentation, applications and trends for future development

Current concepts for chemical and biochemical sensing based on detection with optical waveguides are reviewed. The goals are to provide a framework for classifying such sensors and to assist a designer in selecting the most suitable detection techniques and waveguide arrangements. Sensor designs are categorized on the basis of the five parameters that completely describe a light wave: its amplitude, wavelength, phase, polarization state and time-dependent waveform. In the fabrication of a successful sensor, the physical or chemical property of the determined species and the particular light wave parameter to detect it should be selected with care since they jointly dictate the sensitivity, stability, selectivity and accuracy of the eventual measurement. The principle of operation, the nature or the detected optical signal, instrumental requirements for practical applications, and associated problems are analyzed for each category of sensors. Two sorts of sensors are considered: those based on direct spectroscopic detection of the analyte, and those in which the analyte is determined indirectly through use of an analyte-sensitive reagent. Key areas of recent study, useful practical applications, and trends in future development of optical waveguide chemical and biochemical sensors are considered. Received: 19 January 1998 / Revised: 15 May 1998 / Accepted: 21 May 1998     

Non-selective chemical sensors in analytical chemistry: from “electronic nose” to “electronic tongue”

Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the “electronic tongue” based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider “electronic tongue” as a perspective analytical tool.     

Non-selective chemical sensors in analytical chemistry: from “electronic nose” to “electronic tongue”

Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the “electronic tongue” based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider “electronic tongue” as a perspective analytical tool. Received: 17 July 1997 / Revised: 19 February 1998 / Accepted: 24 February 1998     

Conjugated steroids: analytical approaches and applications

An introduction to conjugated steroids and the justification for their analysis is provided covering both environmental and biological samples. Determining conjugated steroids or indeed any organic chemical which is conjugated upon excretion from the body has relevance in diagnostic monitoring, forensic screening and environmental analysis (from the endocrine disrupter perspective). The various analytical approaches and the accompanying issues are application-dependent. There are numerous options at each stage of analysis, from extraction, hydrolysis, derivatisation, and detection, and advances can be confined to the specific application for which it was developed. Emphasis is placed on the choice of separation and how gas or liquid chromatography necessitates different preparative stages to enable conjugated steroid determination. Possible future directions and research for conjugated steroid analysis are discussed.     

Direct optical sensors: principles and selected applications

In the field of bio and chemosensors a large number of detection principles has been published within the last decade. These detection principles are based either on the observation of fluorescence-labelled systems or on direct optical detection in the heterogeneous phase. Direct optical detection can be measured by remission (absorption of reflected radiation, opt(r)odes), by measuring micro-refractivity, or measuring interference. In the last case either Mach–Zehnder interferometers or measurement of changes in the physical thickness of the layer (measuring micro-reflectivity) caused, e.g., by swelling effects in polymers (due to interaction with analytes) or in bioassays (due to affinity reactions) also play an important role. Here, an overview of methods of microrefractometric and microreflectometric principles is given and benefits and drawbacks of the various approaches are demonstrated using samples from the chemo and biosensor field. The quality of sensors does not just depend on transduction principles but on the total sensor system defined by this transduction, the sensitive layer, data acquisition electronics, and evaluation software. The intention of this article is, therefore, to demonstrate the essentials of the interaction of these parts within the system, and the focus is on optical sensing using planar transducers, because fibre optical sensors have been reviewed in this journal only recently. Lack of selectivity of chemosensors can be compensated either by the use of sensor arrays or by evaluating time-resolved measurements of analyte/sensitive layer interaction. In both cases chemometrics enables the quantification of analyte mixtures. These data-processing methods have also been successfully applied to antibody/antigen interactions even using cross-reactive antibodies. Because miniaturisation and parallelisation are essential approaches in recent years, some aspects and current trends, especially for bio-applications, will be discussed. Miniaturisation is especially well covered in the literature.     

Photochemically relevant DNA-based molecular systems enabling chemical and signal transductions and their analytical applications

In biology, DNA is the central molecule that stores the genetic information. DNA also has attractive physicochemical features for use as materials in molecular assemblies. DNA is chemically stable and can be prepared in nearly any length and sequence by chemical and enzymatic syntheses. Auxiliary functional groups can be built into the backbone as amidite reagents using automated DNA synthesizers. In addition, we can choose an appropriate method from abundant chemistries for post-modifications. The structures of DNA complexes can be rationally designed by bottom-up self-assembly. Therefore, functional groups can be positioned on the DNA scaffold in distinct distance and spatial arrangements.In the last decade, a number of DNA-based allosteric molecular systems have been reported. Some of the systems function as signal transducers, amplifiers, and chemical catalysts. These systems are rather exciting as fundamental achievements of the studies for nanomachines or nanodevices. They should also be useful as robust molecular sensors for sensitive bioassays. In this review, we will cover the photochemically relevant DNA-based molecular systems. They are classified into three groups: (i) DNA-templated molecular/ion assemblies; (ii) DNA-directed complexation; and (iii) chemical transformations accelerated on DNA.     

Polyaniline nanofibers: facile synthesis and chemical sensors

Polyaniline nanofibers with uniform diameters between 30 and 50 nm can be made in bulk quantities through a facile aqueous/organic interfacial polymerization method at ambient conditions. The nanofibers have lengths varying from 500 nm to several micrometers and form interconnected networks. Thin films made of the nanofibers have superior performance in both sensitivity and time response to vapors of acid (HCl) and base (NH3).     

Fluorescence optical sensors in analytical chemistry

Recent advances in fluorescence spectroscopy, optical fiber technology, and opto-electronics have led to an exciting new analytical technique called fiber-optical fluorosensing. Optical sensors offer some interesting advantages over other sensor types in that they are not subject to electrical interferences, do not require a reference signal, and can be quite small. Remote sensing over wide distances is another attractive feature of the method. Working principles and typical fluorosensor representatives will be described here in some detail.     

Optical fibre chemical sensors

Summary Optical fibre chemical sensors permit the determination of a wide range of anions, cations, gases and organic compounds in solution or gas phases. For in-line operation in complex or aggressive mixtures the requirements of selectivity, sensitivity, longevity and reproducible response impose great demands on the sensor reagents and protective membrane system. These demands will be alleviated by preceding the sensors with sample pretreatment and separation procedures and permit the best exploitation of their characteristics. For simpler analytical matrices, or those which are largely unchanging, tailored sensors provide a very useful means of specific determination. There is a clear need for high sensitivity and high selectivity of the reagent over as wide a range of conditions as possible — a demanding requirement.

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Faseroptische chemische Sensoren

Zusammenfassung Faseroptische chemische Sensoren erlauben die Bestimmung einer großen Zahl von Anionen, Kationen, Gasen und organischen Verbindungen in Lösung oder Gasphasen. Für den direkten Einsatz in Komplexen oder aggressiven Mischungen stellen die Ansprüche hinsichtlich Selektivität, Empfindlichkeit, Langlebigkeit und Reproduzierbarkeit hohe Anforderungen an die Sensorreagentien und das schützende Membransystem. Diese Anforderungen werden dadurch gemildert, daß Probenvorbereitung und Trennverfahren vorausgeschickt werden, was die beste Ausnutzung der Sensoreigenschaften ermöglicht. Für einfachere Matrices oder solche, die im wesentlichen unveränderlich bleiben, stellen maßgeschneiderte Sensoren ein nützliches Mittel für die spezifische Bestimmung dar.Die Notwendigkeit liegt auf der Hand, daß die Reagentien über einen möglichst großen Bereich von Einsatzbedingungen hohe Empfindlichkeit und hohe Selektivität aufweisen — eine wichtige Anforderung.

     

ZnO-thin film chemical sensors

The properties of reactively sputtered ZnO thin films used as chemical sensors are investigated in N₂, synthetic air, 10 ppm of NO₂, 30 ppm of CO and in the presence of humidity. The behaviour is correlated to a grain boundary determined conduction model. Using the resistance ratio of twin sensors, one of which is coated with a thin Au catalytic layer, allows the sensor response to CO to be increased and the output signal to be stabilized against sensor drift; the response time is also reduced.