Optical multiple chemical sensing: status and current challenges

Multiple optical sensors for chemical species are sensitive, non-toxic and non-invasive and enable spatially and temporally resolved multianalyte detection. Recent advances are highlighted with a focus on fluorescence-based methods and the biologically and clinically important analytes oxygen, pH, carbon dioxide and temperature. Indicator chemistries such as permeation-selective microbeads and nanoparticles allow the production of microscopically homogeneous sensor layers. The use of combinations of spectral discrimations along with time-resolved monitoring schemes based on luminescence lifetime or intensity-lifetime ratios enables all-optical real-time multianalyte determination.     

Carbon dioxide versus xenon as a mobile phase for flow cell packed column SFC/FT-IR

Xenon is compared to carbon dioxide as a mobile phase for super critical fluid chromatography/Fourier transform infrared spectrometry. The study showed xenon to be comparable to carbon dioxide in terms of resulting chromatography for non-polar analytes. Xenon was confirmed to be a very poor mobile phase, however, for polar analytes. It was determined that small wavenumber shifts in the infrared spectra of probe analytes occurred as either the density or temperature of the mobile phase was increased. The degree of these shifts was often similar for xenon and carbon dioxide. Analyte spectra for five different compounds were produced in both super critical xenon and carbon dioxide and compared to condensed phase and vapor phase library spectra. In all cases, carbon dioxide spectra were readily matched to their corresponding vapor phase spectra, despite having blanked portions of the spectrum due to carbon dioxide infrared absorption. Xenon produced technically superior spectra without such blanked regions, but at a much higher economical cost than carbon dioxide and with no real improvement in terms of library matching.     

Supramolecular optical chemosensors for organic analytes

Supramolecular optical chemosensors are abiotic molecular devices that bind analytes by noncovalent interactions, producing a change in light absorption or fluorescence. This review summarizes recent progress in the development of such chemosensors for organic analytes based on artificial receptors. Important design considerations, such as analyte affinity, choice of chromophore or fluorophore, binding selectivity, and optical signaling mechanism are briefly discussed. Chemists have fashioned chemosensors from a wide range of molecular structures, including polyalcohols, crown ethers, calixarenes, helicenes, sterically geared tripods, metal complexes, pinwheels, porphyrins, and fused-ring heterocycles. Analytes of interest include amines, carboxylic acids, amino acids, hydroquinones, alkaloids, carbohydrates, peptides, urea and creatinine.     

Thermal analysis of binding of iodinated contrast agents to TiO2

Iodinated contrast agents such as iohexol and diatrizoate are pharmaceutical compounds of emerging concern in sewage and drinking water. These are resistant to removal through conventional water treatment processes. Photocatalytic degradation (PD) of these compounds over titanium dioxide has been suggested as a possible technique for the removal of iohexol and diatrizoate from sewage water. Several studies have evaluated these compounds, finding that the two do not respond in the same way to the presence of photocatalyst, which could imply that direct oxidation by surface electron holes is a major route for one compound but not the other. It is necessary that analytes adsorb to the photocatalyst for this oxidation to occur. We employ thermogravimetric analysis to characterize desorption of these analytes from two different forms of titanium dioxide. Compared to pure analyte and pure photocatalyst, additional peaks are seen near 700 °C when the contrast agents are adsorbed to titanium dioxide. This implies that direct oxidation by electron holes is not a primary factor in the PD of iodinated contrast agents. We evaluate the effects of analyte concentration and titanium dioxide crystal structure on these results to address the general applicability of our approach.     

Filter-free integrated sensor array based on luminescence and absorbance measurements using ring-shaped organic photodiodes

An optical waveguiding sensor array featuring monolithically integrated organic photodiodes as integrated photo-detector, which simplifies the readout system by minimizing the required parts, is presented. The necessity of any optical filters becomes redundant due to the proposed platform geometry, which discriminates between excitation light and sensing signal. The sensor array is capable of measuring luminescence or absorption, and both sensing geometries are based on the identical substrate. It is demonstrated that background light is virtually non-existent. All sensing and waveguide layers, as well as in- and out-coupling elements are assembled by conventional screen-printing techniques. Organic photodiodes are integrated by layer-by-layer vacuum deposition onto glass or common polymer foils. The universal and simple applicability of this sensor chip is demonstrated by sensing schemes for four different analytes. Relative humidity, oxygen, and carbon dioxide are measured in gas phase using luminescence-based sensor schemes; the latter two analytes are also measured by absorbance-based sensor schemes. Furthermore, oxygen and pH in aqueous media were enabled. The consistency of calibration characteristics extending over different sensor chips is verified.

Optical colorimetric sensor arrays for chemical and biological analysis

In recent years, the sensor array has attracted much attention in the field of complex system analysis on the basis of its good selectivity and easy operation. Many optical colorimetric sensor arrays are designed to analyze multi-target analytes due to the good sensitivity of optical signal. In this review, we introduce the targeting analytes, sensing mechanisms and data processing methods of the optical colorimetric sensor array based on optical probes (including organic molecular probes, polymer materials and nanomaterials). The research progress in the detection of metal ions, anions, toxic gases, organic compounds, biomolecules and living organisms (such as DNA, amino acids, proteins, microbes and cells) and actual sample mixtures are summarized here. The review illustrates the types, application advantages and development prospects of the optical colorimetric sensor array to help broad readers to understand the research progress in the application of chemical sensor array.     

Recent progress in graphene-material-based optical sensors

Graphene material has been widely used for optical sensors owing to its excellent properties, including high-energy transfer efficiency, large surface area, and great biocompatibility. Different analytes such as nucleic acids, proteins, and small molecules can be detected by graphene-material-based optical sensors. This review provides a comprehensive discussion of graphene-material-based optical sensors focusing on detection mechanisms and biosensor designs. Challenges and future perspectives for graphene-material-based optical sensors are also presented.     

Effervescence-assisted dispersive micro-solid phase extraction

Extraction techniques are surface dependent processes since their kinetic directly depends on the contact area between the sample and the extractant phase. The dispersion of the extractant (liquid or solid) increases this area improving the extraction efficiency. In this article, the dispersion of the sorbent at the very low milligram level is achieved by effervescence thanks to the in situ generation of carbon dioxide. For this purpose a special tablet containing the effervescence precursors (sodium carbonate as carbon dioxide source and sodium dihydrogen phosphate as proton donor) and the sorbent (OASIS-HLB) is fabricated. All the microextraction process takes place in a 10 mL-glass syringe and the solid, enriched with the extracted analytes, is recovered by filtration. Acetonitrile was selected to elute the retained analytes. The extraction mode is characterized and optimized using the determination of five nitroaromatic compounds in water. The absolute recoveries of the analytes were in the range 61-85% while relative recoveries close to 100% in all cases, which demonstrates the absence of matrix effect on the extraction. These values permit the determination of these analytes at the microgram per liter range with good precision (relative standard deviations lower than 6.1%) using ultra performance liquid chromatography (UPLC) combined with ultraviolet (UV) detection as instrumental technique.     

Effervescence-assisted carbon nanotubes dispersion for the micro-solid-phase extraction of triazine herbicides from environmental waters

Extraction techniques are surface-dependent processes since their kinetic directly depends on the contact area between the sample and the extractant phase. The dispersion of the extractant (liquid or solid) increases this area improving the extraction efficiency. In this article, the dispersion of a nanostructured sorbent at the very low milligram level is achieved by effervescence thanks to the in situ generation of carbon dioxide. For this purpose, a special tablet containing the effervescence precursors (sodium carbonate as carbon dioxide source and sodium dihydrogen phosphate as proton donor) and the sorbent [multiwalled carbon nanotubes (MWCNTs)] is prepared. All the microextraction steps take place in a glass beaker containing 100 mL of the sample. After the extraction, the MWCNTs, enriched with the extracted analytes, are recovered by vacuum filtration. Methanol was selected to elute the retained analytes. The extraction mode is optimized and characterized using the determination of nine herbicides in water samples as model analytical problem. The absolute recoveries of the analytes were in the range 48–76 %, while relative recoveries were close to 100 % in all cases. These values permit the determination of these analytes at the low microgram per liter range with good precision (relative standard deviations lower than 9.3 %) using ultra performance liquid chromatography (UPLC) combined with ultraviolet detection (UV).     

Simultaneous determination of carbon dioxide and sulphur dioxide in wine by gas-diffusion/flow-injection analysis

A method is proposed for the simultaneous determiantion of carbon dioxide and sulphur dioxide in complex matrices. The method involves preseparation of the analysis with a flow-through gas-diffusion unit. The analytes are sensed by two detectors in series, a potentiometric detector responsive to both analytes and a photometric detector for SO₂ (p-rosaniline—formadehyde method). The usefulness of the method was tested by applying it to samples of fruity wines and the results were compared with those obtained with the standard EEC recommended method. The reproducibility was generally 7% or better, with a sampling frequency of about 25 h^-1.     

Oxygen indicators and intelligent inks for packaging food

The detection of oxygen using optical sensors is of increasing interest, especially in modified atmosphere food packaging (MAP), in which the package, usually containing food, is flushed with a gas, such as carbon dioxide or nitrogen. This tutorial review examines the ideal properties of an oxygen optical sensor for MAP and compares them with those developed to date, including the most recent advances. The basic technologies underpinning the different indicator types are described, examples given and their potential for application in MAP assessed. This tutorial review should be of interest to the MAP industry and researchers in optical sensors and oxygen sensing.     

On-line preconcentration methods for capillary electrophoresis

The limits of detection (LOD) for capillary electrophoresis (CE) are constrained by the dimensions of the capillary. For example, the small volume of the capillary limits the total volume of sample that can be injected into the capillary. In addition, the reduced pathlength hinders common optical detection methods such as UV detection. Many different techniques have been developed to improve the LOD for CE. In general these techniques are designed to compress analyte bands within the capillary, thereby increasing the volume of sample that can be injected without loss of CE efficiency. This on-line sample preconcentration, generally referred to as stacking, is based on either the manipulation of differences in the electrophoretic mobility of analytes at the boundary of two buffers with differing resistivities or the partitioning of analytes into a stationary or pseudostationary phase. This article will discuss a number of different techniques, including field-amplified sample stacking, large-volume sample stacking, pH-mediated sample stacking, on-column isotachophoresis, chromatographic preconcentration, sample stacking for micellar electrokinetic chromatography, and sweeping.     

Precipitation as a simple and versatile method for preparation of optical nanochemosensors

Optical nanosensors for such important analytes as oxygen, pH, temperature, etc. are manufactured in a simple way via precipitation. Lipophilic indicators are entrapped into nanobeads based on poly(methyl methacrylate), polystyrene, polyurethanes, ethylcellulose, and other polymers. Charged groups greatly facilitate formation of the small beads and increase their stability. Sensing properties of the beads can be tuned by choosing the appropriate indicator. Nanosensors for carbon dioxide and ammonia are found to be cross-sensitive to pH if dispersed in aqueous media. These nanobeads are successfully employed to design bulk optodes. Nanochemosensors with enhanced brightness via light-harvesting and multi-functional magnetic nanosensors also are prepared.     

Responsive Inverse Opal Hydrogels for the Sensing of Macromolecules

Dual responsive inverse opal hydrogels were designed as autonomous sensor systems for (bio)macromolecules, exploiting the analyte‐induced modulation of the opal’s structural color. The systems that are based on oligo(ethylene glycol) macromonomers additionally incorporate comonomers with various recognition units. They combine a coil‐to‐globule collapse transition of the LCST type with sensitivity of the transition temperature toward molecular recognition processes. This enables the specific detection of macromolecular analytes, such as glycopolymers and proteins, by simple optical methods. While the inverse opal structure assists the effective diffusion even of large analytes into the photonic crystal, the stimulus responsiveness gives rise to strong shifts of the optical Bragg peak of more than 100 nm upon analyte binding at a given temperature. The systems’ design provides a versatile platform for the development of easy‐to‐use, fast, and low‐cost sensors for pathogens.     

Characterization of thin polymer and biopolymer layers by ellipsometry and evanescent field technology

The characterization of sensitive layers is the prerequisite for the optimization of chemical and biochemical sensors. The application of SE (Spectral Ellipsometry) and SPR (Surface Plasmon Resonance) as methods of characterization of such sensitive layers is discussed. In combination with infrared spectroscopy, the properties of polymer networks, micro-porous polymers, liquid crystals, and biomimetic polymers can be examined regarding their applicability for optical sensing. Apart from the basic principles regarding the characterization approaches, applications in the area of environmental sensing, optimization of hydrogel layers for antigen/antibody interaction, and discrimination of analytes in homologous series of alcohols are discussed. The effects of analytes on the phase transition in combination with disordering of liquid crystals are given.     

On-line pervaporation-capillary electrophoresis for the determination of volatile acidity and free sulfur dioxide in wines

Pervaporation has been coupled on-line to capillary electrophoresis (CE) by a simple interface consisting of a modified CE vial. The approach allows volatile analytes to be removed and injected into the capillary meanwhile the sample matrix remains in the pervaporator. By this approach volatile acidity and free sulfur dioxide have been simultaneously determined in wines. The detection limits (LODs) are 1.25 and 5.00 microg/mL, the quantification limits 4.12 and 16.50 microg/mL, and the linear dynamic ranges between LOD and 50 microg/mL and between 0.1 and 0.9 g/L for free sulfur dioxide and volatile acidity, respectively. The repeatability and within laboratory reproducibility, expressed as relative standard deviation (RSD), are 1.61% and 3.00% for free sulfur, and 3.35% and 4.58% for volatile acidity, respectively. The optimal pervaporation time and the time necessary for the individual separation-detection of the target analytes are 6 and 5 min, respectively. The analysis frequency is 7 h(-1) and the sample amount necessary is less than 7 mL. The proposed method and official methods for the analytes were applied to 32 wine samples. A two-tailed t-test was used to compare the methods, which yielded similar results. The errors, expressed as RSD for the two parameters, ranged between 1.3 and 4.1%.     

New chromogenic and fluorogenic reagents and sensors for neutral and ionic analytes based on covalent bond formation–a review of recent developments

To date, hydrogen bonding and Coulomb, van der Waals and hydrophobic interactions are the major contributors to non-covalent analyte recognition using ionophores, ligands, aptamers and chemosensors. However, this article describes recent developments in the use of (reversible) covalent bond formation to detect analyte molecules, with special focus on optical signal transduction. Several new indicator dyes for analytes such as amines and diamines, amino acids, cyanide, formaldehyde, hydrogen peroxide, organophosphates, nitrogen oxide and nitrite, peptides and proteins, as well as saccharides have become available. New means of converting analyte recognition into optical signals have also been introduced, such as colour changes of chiral nematic layers. This article gives an overview of recent developments and discusses response mechanisms, selectivity and sensitivity.     

Cloud point extraction utilizable for separation and preconcentration of (ultra)trace elements in biological fluids before their determination by spectrometric methods: a brief review

This review summarizes and discusses applications related to the determination of (ultra)trace elements in biological fluids using cloud point extraction as sample pretreatment technique. Biological fluids, such as urine, whole blood, serum or plasma, are the most often analyzed biological materials in these applications. Spectrometric methods, such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry, are commonly used for quantification of elements preconcentrated by the extraction technique. Optimized extraction procedures lead to the high extraction recoveries of the target analytes. High enrichment factors achieved lead to the lowering of quantification limits. All these achievements illustrate the great potential of extractions for reliable quantification of (ultra)trace elements in complex biological matrix what is documented in this review of a number of works published on this topic.     

Indicator–displacement assays

Indicator displacement assays (IDAs) are now a popular method for converting most any synthetic receptor into an optical sensor. In this review many such assays are highlighted, along with biological counterparts. The focus is upon colorimetric, fluorescent, and metal containing IDAs. The power of the method can be readily appreciated by the large diversity of analytes that have been targeted with this technique. It is clear that the method is now well accepted and will continue to be one of many methods used to create optical detection methods from synthetic receptors.