Anal. Chem.

2008, 80, 4269–4283

Fiber-Optic Chemical Sensors and Biosensors
Otto S. Wolfbeis Institute of Analytical Chemistry, Chemo- and Biosensors, University of Regensburg, D-93040 Regensburg, Germany
Review Contents Books and Reviews Sensors for Gases, Vapors, and Humidity Hydrogen Hydrocarbons Oxygen Other Gases Vapors Humidity Sensors for pH and Ions Sensors for Organic Chemicals Organics Biosensors Enzymatic Biosensors Immunosensors DNA Biosensors Bacterial Biosensors Applications Sensing Schemes and Spectroscopies Fiber Optics Capillary Waveguides Microsystems and Microstructures Refractive Index Spectroscopies Literature Cited 4269 4271 4271 4271 4272 4272 4274 4274 4275 4276 4276 4276 4276 4277 4278 4278 4279 4279 4279 4280 4280 4280 4280 4281

This review covers the time period from January 2006 to January 2008 and is written in continuation of previous reviews (1–3). Data were electronically searched in SciFinder and MedLine. Additionally, references from (sensor) journals were collected by the author over the past 2 years. The number of citations in this review is limited, and a stringent selection had to be made therefore. Priority was given to fiber-optic sensors (FOS) of defined chemical, environmental, or biochemical significance and to new schemes. The review does not include the following: (a) FOS that obviously have been rediscovered; (b) FOS for nonchemical species such as temperature, current and voltage, stress, strain, displacement, structural integrity (e.g., of constructions), liquid level, and radiation; and (c) FOS for monitoring purely technical processes such as injection molding, extrusion, or oil drilling, even though these are important applications of optical fiber technology. Unfortunately, certain journals publish articles that represent marginal modifications of prior art, and it is mentioned here explicitly that the (nonpeer-reviewed) Proceedings of the SPIE are particularly uncritical in that respect. Fiber optics serve analytical sciences in several ways. First, they enable optical spectroscopy to be performed at sites inaccessible to conventional spectroscopy, over large distances, or even at several spots along the fiber. Second, in being optical waveguides, fiber optics enable less common methods of interrogation, in particular evanescent wave spectroscopy. Fibers are
10.1021/ac800473b CCC: $40.75  2008 American Chemical Society Published on Web 05/08/2008

available now with transmissions over a wide spectral range. Current limitations are not so much in the transmissivity but in the (usually shortwave) background fluorescence of most of the materials fibers are made from, in particular plastic. There is an obvious trend toward longwave sensing where background signals are weaker. Major fields of applications are in sensing gases and vapors, in medical and chemical analysis, molecular biotechnology, marine and environmental analysis, industrial production monitoring, bioprocess control, and the automotive industry. Note: In this article, sensing refers to a continuous process, while probing refers to single-shot testing. Both have their fields of applications. FOS are based on either direct or indirect (indicator-based) sensing schemes. In the first, the intrinsic optical properties of the analyte are measured, for example its refractive index, absorption, or emission. In the second, the color or fluorescence of an immobilized indicator, label, or any other optically detectable bioprobe is monitored. Aside from the design of label and probes, active areas of research include advanced methods of interrogation such as time-resolved or spatially-resolved spectroscopy, evanescent wave and laser-assisted spectroscopy, surface plasmon resonance (SPR), and multidimensional data acquisition. In recent years, fiber bundles also have been employed for purposes of imaging, for biosensor arrays (along with encoding), or as arrays of nonspecific sensors whose individual signals may be processed via artificial neural networks. The success of SPR in general, and in the form of FOS in particular, is impressive. Following the recent sensor hype of (mainly organic) chemists that tend to refer to optical molecular probes as “sensors”, the literature has become more difficult to sort. This review covers literature on methods that enable sensing of (bio)chemical species as opposed to conventional types of optical assays. Unfortunately, there is a tendency to even refer to conventional indicators (such as for pH or calcium) as biosensors if only used in vivo. Similarly, optical analysis of a solution by adding an appropriate indicator probe is now referred to as “sensing” (to the surprise of the sensor community). I have outlined the situation in more detail in my previous review (3). BOOKS AND REVIEWS It is obvious that fiber optic chemical sensors (FOCS) have had a particular success in areas related to sensing gases and vapors. Many of the systems implemented are based on direct spectroscopies that range from UV to IR, and from absorbance to fluorescence and surface plasmon resonance. Optical chemical sensors have been comprehensively reviewed by McDonagh et al. quite recently (4). The article covers sensing platforms, direct (spectroscopic) sensors, reagent-mediated sensors and discusses trends and future perspectives. Fiber-optic UV systems for gas
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a kind of holy grail in FOBS. surface plasmon resonance. Vol. reduction. Flowers et al. while optical nanobiosensors and nanoprobes were reviewed by Vo-Dinh (24) with respect to the principles. and light-addressable potentiometry). DNAzymes can selectively identify charged organic and inorganic compounds at ultratrace levels in waste and emissions. e. lightweight. complexation. a liquid multibatch pipeline and a gas pipeline. It is stated (somewhat overoptimistically) that chemical sensing can “simply” be achieved by transporting light to and from a measurement site with a plain fiber light guide for spectrophotometry. passive and can be multiplexed. cyanide. Applications range from the use of fibers acting as plain light pipes to complex chemical sensors. the tapered fiber-optic biosensors (TFOBS) were reviewed (25). Such sensors are minimally invasive. A more general review covers recent developments in FOBS (26).. bitumen analysis. sensitivity. Buchanan has reviewed recent advances in the use of near-IR (NIR) spectroscopy in the petrochemical industry (6) and points out NIR is particularly attractive in this field because it measures the overtone and combination bands predominately of the C-H stretches. June 15. Raman spectroscopy. The state of the art in continuous glucose sensing. One specific class of FOBS. and environmental analysis. new concepts for sensing based on the use of plasmonic metal nanoparticles. and catalytic rates of DNAzymes. The devices were classified according to their mechanism of operation and in terms of sensing materials. part of the fiber is tapered so that the evanescent field of the lightwave can interact with samples. The trend toward miniaturization is obvious. specifically with respect to achievements in employing nanosensors and biochips (e. One focus is on fiber-optic probes for UV resonance Raman spectroscopy that offer several advantages over conventional excitation/collection methods. dynamic range. formaldehyde. gene chips) in cellular analyses ranging from medical diagnostics to genomics. by preconcentration. and applications of fiber-optic nanobiosensor systems using antibodybased probes.g.. has been summarized in a book (21). fiber-optic systems.and vapor analysis have been reviewed (5). fluorescence. and spectroscopies have been reviewe (12). Applications of optical fiber (bio)sensors (FOBS) also include areas such as high-throughput screening of drugs (18). resonant mirrors. fluorometry. (8). sensitivity. materials. Practical examples include sensing schemes for oxygenates in fuels. Applicability is demonstrated for two examples. Tools for life science research based on fiber-optic-linked Raman and resonance Raman spectroscopy were also reviewed (7). for application in the gas industry. while interferometry is said to be most suitable for low-molecular weight chemical liquids and vapors if selectivity is not a critical issue. FOCS for volatile organic compounds have been reviewed by Elosua et al. and new means (such as color changes of chiral nematic layers) of converting analyte recognition into optical signals are described. and optical nanowires are discussed. The strong absorbance of vapors and gases in the UV region is advantageous and resulted in a compact detection system of good accuracy.g. Additionally. photonic crystal fibers. and robustness. and luminescence as biosensors and chemosensors have been critically compared (16). and (fiber) optical methods based on the use of glucose oxidase and transduction via oxygen consumption are reviewed in one chapter (22). Mohr (11) has reviewed recent developments in chromogenic and fluorogenic reagents and sensors for neutral and ionic analytes based on covalent bond formation. absorption. and in environmental sensing by making use of DNAzymes (20). accuracy. Theoretical sensitivities of interferometry and SPR are detailed along with parameters affecting these sensitivities. determination of octane numbers. and resolution were calculated and compared from a range of data from the literature. discussed aspects of fiber-optic spectro-electrochemical sensing for in situ determination of metal ions. SPR (which is label-free) possibly can sense proteins with a resolution similar to that of luminescence. The term 4270 Analytical Chemistry. Significant strides have been made in terms of selectivity. New indicator dyes for amines and diamines. Luminescence is said to offer the best resolutions for sensing of protein and DNA. In these. DNAzymes enable accurate quantification of such compounds and thus represent an attractive alternative to stateof-the-art affinity sensors. 80. and for environmental monitoring using nanoporous thin-film Fabry-Perot transducer elements or intrinsic fiber Bragg grating sensor networks for structural health monitoring. Selected examples of advanced optical fiber sensor systems based on subwavelength structured components are presented. TFOBS are often used with transduction mechanisms such as changes in refractive index. Nanostructure-based optical fiber sensor systems and examples of their application have been reviewed by Willsch et al. Femtoliter wells can be loaded with individual beads to create such arrays for multiplexed screening and bioanalysis. Challenges remain in the development of efficient signal transduction technology for in situ applications. The state of the art in leak detection and localization and respective legal regulations have been reviewed by Geiger (9). the composition of fuels. the detection of food-borne pathogens (19) (based on either SPR. (10). mainly copper(II) (15). These include sensor for humidity and hydrocarbons. Borisov and Wolfbeis (17) have presented what appears to be the most comprehensive review on optical biosensors so far. 12.” The performances of interferometry. No. 2008 spectro-electrochemical sensing does not relate to electroluminescence but to electrochemical conversion of an analyte prior to its spectroscopic detection. oxidation. summarize their research on plastic microparticles and nanoparticles for fluorescent chemical sensing and encoding (13). Borisov et al. or SPR. In combination with laser based detection. amino acids. organophosphates. hydrogen peroxide. peptides and proteins. nitrogen oxide and nitrite. as well as for saccharides also are described. it does not come as a surprise that the authors point to “the need for further refinement of the sensor’s design and the experimental protocol to improve the method’s sensitivity. and SPR. Adherent cells may be attached to the fiber substrate to provide a method for observing cell migration and for screening antimigratory . A rather wide and shallow review covers advances in fiberoptic sensing in medicine and biology (14). Specific aspects include sensor reliability. Aspects of multiple optical chemical sensing with respect to parameters. Sensitivity. development. and optical detection. Given its complexity. whereas Walt (27) describes fiberoptic biosensor arrays for creating high-density sensing arrays. another on novel probes based on hollow-core photonic band gap fibers that virtually eliminate the generation of silica Raman scattering within the excitation optical fiber. Nanoscale optical biosensors and biochips for cellular diagnostics have been reviewed by Cullum (23). arrays.

Jeronimo et al. Comparing Mg-Ni and Mg-Ti based alloys. The review highlights promising microarray techniques either making use of labels or label-free. as well as biosensors. Rather than miniaturizing the optical fiber. The sensitivity of the LPG sensor is better by a factor of ∼500.2 dB (32%) with a risetime of 100 s. One major research focus is on hydrogen and methane because both are highly explosive when mixed with air and may be sensed more safely with FOS than with electrical devices. These. Luna-Moreno et al. The use of FOCS for on-site monitoring and analysis of industrial pollutants with respect to detecting the identity. in turn. A gasochromic TiO2based sensing film was used for hydrogen detection by means of a fiber-optic Fabry-Perot interferometric sensor (44). Concepts include fluorescence spectrophotometer design geometry and the correlation of color with emission wavelength. Hydrogen interacts strongly with metallic palladium and platinum films and with tungsten oxide. It was applied to monitor hydrogen gas in air below the lower explosion limit. No. lecture demonstrations can be made of various concepts in molecular fluorescence spectroscopy. deposited via the Langmuir-Blodgett and electrostatic self-assembly techniques. along with flammable alkanes. and regenerates quickly (at room temperature). Active and passive coatings. AND HUMIDITY This section covers all room-temperature gaseous species including their solutions in liquids. SWCNTs were deposited by the Langmuir-Blodgett technique at the distal end of the fibers. it is always detected indirectly. With the use of this instrument. and extent of toxic chemical contamination was overviewed (31). and LPG sensors are mainly based on the coupling between the cladding modes and evanescent or surface plasmon waves. Aspects of process monitoring of fiber reinforced composites using optical fiber sensors were summarized (32). The same material was used to design a hydrogen sensor based on core diameter mismatch and annealed Pd-Au thin films (42). Hydrocarbons. The nanomorphology of the surface considerably improves the gasochromic properties. While such sensor elements are mainly aimed for use in telecommunications systems. with a focus on thermosetting resins and on spectroscopy-based techniques that can be used to monitor the processing of these materials A classroom demonstration was described for a portable fiberoptic probe multichannel spectrophotometer (33). 2008 4271 . and even individual enzyme molecules can be loaded into the wells. both coated with Pd nanolayers. The Pd-Au film can detect 4% hydrogen with a response time of 15 s. have reported on the effect of hydrogen on a thick film Pd-Au alloy (41). may be utilized to affect the transmission of optical fibers. June 15. in contrast to hydrogen or oxygen. Palladium-capped magnesium hydride was used as an alternative sensing material in a fiber-optic hydrogen detector (43). typically caused by 1% hydrogen in argon gas (38). and the initial response velocity in the range from -30 to 80 °C. were investigated. Fiber Bragg gratings (FBG) and long period gratings (LPG). 40). thus enabling single molecule detection via enzymecatalyzed signal amplification. Heating the palladium layer with an auxiliary laser diode improves the response time at low temperatures. the time-response. Two rather similar articles have been published by this group (39. these may be covered with nanostructured coatings (29). Since hydrogen gas does not display intrinsic absorptions/ emissions that could be used for purposes of simple optical sensing. If exposed to hydrogen. has a short response time. A drop in the reflectance of this material by a factor of 10 is demonstrated at hydrogen levels as low as 15% of the lower explosion limit. the latter has superior optical and switching properties. a 10 ppm sensitivity for hydrogen was reported (along with cross sensitivity to environmental conditions) (46). The resulting sensor consists of a multimode fiber in which a short section of single mode fiber is coated with the Pd-Au film. the optimal change output power obtained in this experiment was 1. concentrations. 80. provide a powerful tool for the simultaneous analyses of thousands of parameters. the refractive index of the Pd-Au layer becomes smaller and causes attenuation on the transmitted light. Hydrogen. Experiments carried out at 113 K revealed the potential of sensing <5% of gaseous hydrogen with good reversibility and fast response time. Vol. The FBG sensors appear to be pure strain sensors. One more fiber-optic Raman sensor was reported for sensing ethanol and methanol in gasoline (48). remains to be the analyte where safety considerations have led to a substantial amount of research in terms of fiber-optic sensing. The sensor is capable of monitoring methanol and ethanol in water and gasoline Analytical Chemistry. The gasochromic properties of nanostructured tungsten oxide films coated with a palladium catalyst were used to sense hydrogen gas via the change in the optical transmittance at 645 nm. The response occurs within a few seconds. ionic species and solvents. (30) review optical sensors and biosensors based on sol-gel films. In another type of FBG sensor. Fiber gratings coated with Pd metal were reported to enable sensing of hydrogen gas (45). gases. Optical microarray biosensing techniques (28). The sensor was used to monitor the aging of certain materials. be they DNA or proteins. The authors have studied the transmission. 12. a hydrogen sensor was reported based on palladium coated side-polished single mode fiber (35). When exposed to 4% hydrogen gas. Methane and other hydrocarbons are almost exclusively sensed via their intrinsic absorption in the near-infrared (NIR). It employs a frequency doubled 532 nm Nd:YAG laser and a specially designed fiber-optic Raman probe and enables online determination of sample constituents without employing an expensive IR fiber. it is very likely that chemical sensor and biosensor development may benefit from such research. Optical fibers coated with single-walled carbon nanotubes (SWCNTs) were shown to enable determination of hydrogen at cryogenic temperatures (47). VAPORS. can be detected via their intrinsic absorption in the (near) infrared-albeit cross sections (molar absorbances) remains small or via Raman scatter. excitation. SENSORS FOR GASES. Hydrogen. The interactions result in both spectral changes (an effect sometimes called gasochromism) and in an expansion of the materials. and emission spectra. The history of research on FOCS and FOBS has been summarized (34). Thus.compounds. Applications include sensors for pH. Improved response times were reported for a similar sensor based on the same scheme (36). Palladium also was incorporated into silica nano- composites of the sol-gel type and used in a reversible hydrogen FOCS (37).

or both. Both the UV absorption at 254 nm and the visible absorption at 600 nm were studied. 12. A composite fluorescent material was described that enables simultaneous sensing and imaging of oxygen and carbon dioxide (66).007 vol. The sensing dye. 80. was immobilized in the cladding using a sol-gel process. or the intensity of their luminescence. (67). and this can be described by the socalled two-site model assuming two quenching constants. 2008 quenching of the long-lived delayed fluorescence of fullerene C70 incorporated in thin films of ethyl cellulose or organosilica (59). Arain et al. reduces the risk of fluorescence energy transfer between indicator dyes. Fiber optic microsensors with a tip diameter of ∼140 µm were reported for simultaneous sensing of oxygen and pH and of oxygen and temperature (62). Oxygen. Rather similar materials resulted in even faster responses as reported in a second paper by this group (53). have lifetimes on the order of 8-13 µs in the unquenched state. coli and Pseudomonas putida. It has been shown that an artificial network also may be applied to model the dynamic quenching of the fluorescence of a ruthenium-derived probe (54). Their surfaces were modified by xerogel layers. was copolymerized with a polymerizable monomer. Most oxygen sensors display nonlinear Stern-Volmer relationship. methylene blue. It did not leach out due to its high hydrophobicity. and toxicological assays. where temperature can be measured optically and used to calculate temperature-corrected data for pO2.0. Molecular recognition is accomplished by functionalization of the silver nanoparticles with appropriate host molecules.solutions. and the spectral width of their luminescence. the peak wavelength. and polyphenoloxidase. The most sensitive sensor for oxygen known so far exploits the efficient 4272 Analytical Chemistry. Unlike in electrochemical techniques. Highperformance fiber-optic oxygen sensors based on fluorinated xerogels doped with quenchable Pt(II) complexes were reported by Chu et al. and response times range from 4 to 7 s. The method is based on kinetic measurements of the oxygen partial pressure inside a chamber sealed by the sample contact lens. Quantum dots undergo temperature-dependent changes of the intensity. Activity screening was demonstrated for glucose oxidase and for monitoring the growth of E. The same group has presented new and ultrabright fluorescent probes for oxygen that are based on cyclometalated iridium(III) coumarin complexes (61). mid-IR. Oxygen sensors were used to transduce the activity of catalase (57). Three kinds of microstructure fibers (MSFs) for sensing gaseous hydrocarbons were reported (51) that enable the quantitation of aromatic hydrocarbons. Oxygen and carbon dioxide are clinically highly significant blood gases. It relies on the measurement of the phase shift of the luminescence decay time of a material composed of microbeadcontained indicators (with well-separated excitation and emission wavelengths) and polymers with excellent permeation selectivities as well as favorable optical and adhesive properties. The sensors yield linear Stern-Volmer plots.3 and 1. Sensing in the UV region . but are less photostable than ruthenium-based probes for oxygen. The luminescent indicator. A porous plastic sensor was developed for the determination of dissolved oxygen in seawater (55). The sensor is said to respond logarithmically linear between 0. have quantum yields between 0. where a thin luminescent O2-sensitive film is being placed. Benzene was quantified down to 500 ppm using a PVC polymer coating. a ruthenium(II)diimine complex. The response of the sensors to toluene in nitrogen gas results from spectral changes of the output light from the fibers at 1600-1800 nm. (63) have characterized microtiterplates (MTPs) with integrated optical sensors for oxygen and pH and have applied them to enzyme activity screening. Borisov et al. The use of microbeads enables the ratio of the signals to be easily varied. No. A detection limit of 0. Thin hydrophilic sensing films consisting of an analyte-sensitive indicator and a reference fluorophore were deposited on the bottom of the MTPs. The tip of the fiber was covered with sensor chemistries based on luminescent microbeads that respond to the respective parameters by a change in the decay time. The probes are less cross-sensitive to temperature.6% and 20. Oxygen sensing remains another area where FOCS are quite successful. Other Gases. they can be used as probes to compensate for effects of temperature in FOCS (65). (52). and a porogen. Oxygen almost exclusively is sensed by virtue of the quenching effect it exerts on certain fluorophores. Molecular oxygen in concentrations as low as 200-800 ng/L can be determined by this method either at single sensor spots or spatially resolved over a temperature range of more than 100 °C. A toxicological assay also is reported that enables monitoring the respiratory activity of P. June 15. Capillary silica fibers were also fabricated. The permeability of contact lenses for oxygen can be determined with a fiber-optic luminescent sensor system (56). The MSFs with 10-50 µm air holes were arranged to one sensor. respirometry.% of toluene was achieved. evanescent wave fiber-optic sensor for the detection of hydrocarbon pollutants in water was constructed and tested (50). A luminescent dual sensor for time-resolved imaging of pCO2 and pO2 in aquatic systems was reported by Schroeder et al.3 °C was achieved. putida. peroxidase. The assay allows for the screening of green coffee samples for CAT activities. The beads contain Fe3O4 and can be magnetically fixed at the bottom of a microbioreactor and enable contactless monitoring of oxygen in cultures of Escherichia coli using fiber optics. An evanescent wave fiber sensor was used to determine oxygen deficiency (58). the optical sensor is unaffected by the thickness of the contact lens and other effects. and reduces the adverse effect of singlet oxygen that is produced in the oxygen-sensitive beads. The group of Klimant (60) has presented magnetically separable optical sensor beads for oxygen. Sensing is based on dynamic quenching of the fluorescence of the ruthenium indicator. Vol.9% oxygen. This is of interest to characterize the oxidative metabolism in coffee cherries during maturation as it appears to be regulated by the timely expression of redox enzymes such as catalase (CAT). A resolution of 0. Effects are almost linear and fully reversible. A modular. Hence. a cross-linking reagent. Ozone gas was sensed via its UV and visible absorption (68). The setup uses a broadband light source with backreflecting optics coupled to a fiber-optic sensing element coated with an analyte-enriching polymer that preconcentrates the analyte. Surface-enhanced Raman spectroscopy and surfaceenhanced IR spectroscopy were applied to selective determination of polycyclic aromatic hydrocarbons (49). In order to compensate for the rather strong effects of temperature on oxygen sensors based on dynamic quenching of luminescence. (64) have developed a composite luminescent material for dual sensing of oxygen and temperature.

Ammonia in the gas phase may be sensed either via its NIR absorption or (in being a weak base) via the weak pH changes it can induce in immobilized pH indicators. The microsensors were used to establish ammonia microprofiles of high spatial resolution. A new sensing scheme for ammonia is based on monitoring the optical changes of the Q-band of tetrakis(4sulfophenyl)-porphine (TSPP) at 700 nm. Most ammonia sensors reported so far make use of its effect on appropriate pH probes. Oberg et al. Dissolved CO2 usually is sensed via the effect it exerts on the pH of a buffer immobilized in a matrix. The visible region has a significantly lower absorption coefficient but enables monitoring high ozone levels. (79) have designed a simple optical sensor for vapors of organic amines based on silica microspheres dyed with pH indicators such as bromocresol green (a probe reported to be useful for sensing ammonia by others several times before). a low-cost sensor employing compact mid-IR components is presented that was used to measure CO2 in the exhaust of a commercial diesel engine. As conventional automotive pollution sensors fail to meet monitoring requirements as specified by the European Community. Signal generation is based on the spectroscopic changes of a reagent contained in the nanopores of a sol-gel element that undergoes an irreversible chromogenic reaction. The microsphere sensor is said to be more sensitive than other optical amine sensor described in the literature but heavily interfered by ammonia. Nanoporous matrixes also may be used to host pH-sensitive phenolic dyes and an alkaline phase transfer agent. A sulfonated hydroxypyrene named HPTS has been widely used as a pH probe in such CO2 sensors in the past two decades. (69). This is also true for one more sensor that makes use of a sol-gel matrix (76). Two fiber-optic designs are described. The group of Mohr reports (80) that functional liquid crystal films can selectively recognize amine vapors and thereby undergo a change in their color. The UV based sensor can detect 0-1 mg/L of ozone and the longwave sensor 25-126 mg/L. 80. The indicator was immobilized in porous SiO2 which then was deposited on the surface of a bent optical fiber core. A fluorescent pH indicator placed in a cellulose ester matrix at the tip of an optical microfiber is deprotonated by ammonia. The first approach uses a fiberoptic spectrometer. Note: sensors for amines in fluid phases are treated in section D on sensors for organic molecules. One more fiber-optic probe was reported for the selective determination of NO2 in air samples (81). (70). Ammonia also was sensed with the help of silica nanocomposites doped with silver nanoparticles and deposited on an optical fiber waveguide (78). as induced by ammonia in the electrostatic interaction between TSPP and poly(diallyldimethylammonium) chloride (75). A novel kind of optical sensor for carbon dioxide makes use of silicone encapsulated ionic liquids (72). The second approach uses narrow bandwidth optical filters to detect the emission intensity. It can detect organic amine vapors down to 1-2 ppb levels. A respective FOCS to monitor the concentration ratio of nitrogen and oxygen in a cryogenic mixture was reported by Tiwari et al. Exposure to gas containing ammonia enhances the attenuation of light power guided through the fiber probe. The resulting ammonium ion is stabilized by a cation trap. A practical sensor for online sensing of atomic nitrogen in direct current glow discharges was reported by Popovic et al. thereby undergoing a large change in fluorescence intensity. and one more type of organically modified sol-gel was used to develop one more modification of this kind of sensor (73). Cross-sensitivities toward protons and alkali ions were prevented by coating the sensor with a layer of Teflon. The material was deposited onto the surface of a bent silica fiber by the dip-coating technique. Both NH3 vapor and trace NH3 dissolved in water can be detected. Another FOCS for NO2 makes use of poly(3-octylthiophene) as a sensing material (82). In combination with a silicone protection coating. to record the desired spectral lines. all showing a linear sensitivity to NH3 in the 0-100 ppm range and a response time of around 30 s. The limit of detection is 13 ppb in gas samples and 5 ppb in water samples. Because the gel is partially fluorinated. for various reasons. Sub-ppm levels of NH3 can be continuously monitored by this technique. The sensor is not very stable Analytical Chemistry. The SiO2 nanocomposite was prepared by the sol-gel technique in the presence of (3-mercaptopropyl)trimethoxysilane) and doped with 25 µm silver nanoparticles.5 µg/L. This is comparable to previously reported probes exploiting the same effect. Sensing is accomplished by monitoring the intensities of the atomic nitrogen spectral line at 822 nm and the bandhead at 337 nm. Nitrogen is a species not easily sensed by optical means except by Raman spectroscopy. while the ionic liquid contains a pH probe (in its base form) that undergoes a distinct color change after its (reversible) reaction with CO2. The detection limit is reported to be 0. ammonia remain another active area of research. Vol. The Raman peak intensity ratios for mixtures of liquid nitrogen and liquid oxygen were analyzed for their applicability to impurity sensing using different excitation light sources. Measurements were performed using two methods. The scheme was extended to sensing ammonia via fiber-optic microsensors at 2-100 µg/L levels that are known to be highly toxic to fish and other organisms (77). reagents typically employed in sensors for CO2 (74). 12. The silicone matrix acts as a permeation-selective material for CO2. Interference by trimethylamine was minimized using an 18-crown-6 ether as a cation trap and by the permeability properties of the polymer matrix. Molecular recognition is accomplished by cholesteric liquid crystals combined with molecules carrying a trifluoroacetyl group. It also is the prefered one in that it is applicable to aqueous solutions (unless extractive phases are employed in IR sensing schemes). The sensor was regenerated by rinsing with water. This material undergoes large spectral changes at 543 nm if exposed to NO2. calibrated with a standard source. No. Sensors for carbon dioxide and. to a lesser extent. Spontaneous Raman scattering was used to monitor of the purity of liquid oxygen in the oxidizer feed line during ground testing of rocket engines. Three thin film samples with different thicknesses were prepared layer-by-layer. and a miniaturized sensing system was developed that responds within a few seconds. The latter approach is more sensitive. June 15. relative to the oxygen line at 845 nm. The response to aliphatic amines is linear up to 2 ppm. the response is faster. 2008 4273 . Optical data are collected for a range of experimental conditions in a flowing glow discharge of N2-O2 mixtures.allows for highly sensitive detectors due to its high absorptivity in that region. ammonia can be sensed in watery samples. Carbon dioxide emissions from a diesel engine can be monitored with the help of a midinfrared optical fiber sensor (71).

If exposed to a gas sample at high temperatures. The pathological threshold is 200 ppb. The maximum of the peak is shifted on exposure to oxidizing or reducing gases. The polymers are patterned on glass substrates and undergo color changes that can be interrogated at different wavelengths.2 min). Certain cross interferences observed can be eliminated by applying a signal processing algorithm that also reduces false alarms. The sensor was applied to measure RH in food and in a weather station. and CO were found not to interfere. No.5 years of discontinuous measurement. An irreversible active core fiber-optic probe was developed for determination of trace H2S at high temperature using a cadmium oxide doped porous silica fiber as a transducer (85). CH4. The CdS formed also emits strong fluorescence. Also see ref 91. highly selective. but this signal is quenched at 450 °C. The Langmuir-Blodgett technique was applied to deposit the CNTs directly onto the optical and acoustic sensors substrates. with a peak emission at around 500 nm. An FOCS for VOCs was reported 4274 Analytical Chemistry. Humidity. and this effect was used in a respective fiber-optic sensor (87). Single-walled CNT multilayer coatings were used that cause a response toward toluene and xylene vapors. The process is fully reversible. Linear responses up to 50 and 150 mg/L were obtained for free and total SO2. carbon monoxide. The sensors have response times (t90) of less than 20 s. In another kind of RH sensor. Ru(II) complexes were employed since their luminescence decay time depends on RH. Response times are <4 s. It exhibits long-term stability and a linear response over the humidity range from 0 to 4000 ppm. Numerous materials including Nafion films doped with crystal violet responding to humidity by a change in their reflectance (97). It can detect iodine with a rather high concentration detection limit of 6 µM. Optical humidity sensors are a kind of evergreen given their highly different applications. Another fiber-optic RH sensor reported (100) is based on large-core . The authors have used the same material in a Fabry-Perot interferometer with a nanosized cavity along with a optical fiber pigtail system (93).018% RH (equal to ∼4 ppm). 12. and sensitive. The optical effects resulting from exposure to various VOCs are reversible and may result from adsorption of VOCs with attendant reduction of anisotropy. (92). It is based on a new vapochromic red powder consisting of a silver metal organic compound. exerts a quenching effect on a derivative of aminobenzanthrone. The toxic industrial chemicals hydrogen cyanide. Miniature waveguide channels result in enhanced sensitivity owing to the increased path length. The results demonstrate ppm to ppb sensitivity. Activated carbon is used as a prefilter. Vol.25% can be determined with the respective sensor. Reversal times depend on exposure time and % RH. and hydrogen (all in dry air) was observed for a layer of a metal oxide multilayer of the type InxOyNz covered with gold nanoclusters (84). The output of the sniffer was amplified by substrate regeneration via reduction with ascorbic acid. and any breakthrough of the VOC through the carbon results a large change in the reflectivity of the porous silica. and changes up to 3 dB in the reflected optical power were registered. Both free and total SO2 can be determined. NO. MM levels between 9 and 11 000 ppb were detectable. Fuel gases such as H2. The sensor can make use of ambient light as a light source and the eye as a detector to register the resulting color changes and thus is capable of real time monitoring of VOCs. (96) report on a microsensor for VOCs where a photonic crystal of porous silicone is attached to the distal end of an optical fiber. often referred to as volatile organic compounds (VOCs). Relative humidity (RH) between 0 and 0. This forms the basis of a novel type of fiberoptic RH sensor (99). An optical biosniffer for methyl mercaptan. The sensing scheme is based on the detection of the oxygen consumed as a result of enzymatic oxidation of methyl mercaptan (MM) by MAO. The sensor consists of a nanometer-scale Fizeau interferometer doped with the vapochromic material and placed at the cleaved end of a multimode fiber-optic pigtail. 2 ppm for SO2.in that the response decreases after each exposure to NO2 but is rapid. and this is detected at around 370 nm with a fiber-optic spectrometer. Elemental iodine. with lower limits of detection of 2 ppm for NO2. with a detection limit as low as 0. 2008 (90) that uses birefringent porous glass oriented between two crossed polarizers and serving as the basis for this broad-spectrum sensor. A rather complex method for optical sensing of sulfur dioxide in wines (89) employs a dinuclear palladium ligand complex immobilized in a PVC membrane plasticized with o-nitrophenyloctylether (o-NPOE). and high repeatability. the limits of human perception are on the order of 10 ppb. Signal stability was verified for >2. The incorporation of the gold nanoclusters leads to a broad absorption peak in the visible (purple) due to the excitation of localized surface plasmons. It is used to simultaneously measure their concentrations. emission peaking at 600 nm). Its color and refractive index change when exposed to vapors of VOCs. In a related paper. SO2 were detected using an ultraviolet optical fiber based sensor (83). The analytical information is obtained via phase-sensitive determination of the decay time (98). so that fluorescence can only be used for probing trace H2S at low temperature. trace H2S in the sample diffuses into the porous fiber and reacts with cadmium oxide to form cadmium sulfide (CdS). The operational range is from 4 to 100% RH at 20 °C. respectively. Vehicle exhaust emissions such as NO2. Certain porphyrins deposited in Nafion films undergo waterinduced tautomerism. The response is fully reversible (with some hysteresis) in dry nitrogen. The sensor can detect moisture in process gases such as nitrogen and HCl. The performance of a carbon nanotube (CNT) based thin films fiber-optic for VOCs was described (94). Vapors. often are sensed by optical means in order to reduce the risk of explosion. VOCs such as acetonitrile vapors can be detected at concentrations of >50 ppm. and 20 ppm for NO. June 15. The ruthenium probe was immobilized on a Teflon support. Vapors. and chlorine can be sensed with waveguides coated with doped polymer materials in the form of arrays (86). The response of the material toward different alcohols was measured at 850 nm. 80. A fiber-optic nanosensor for volatile alcoholic compounds has been described by Elosua et al. Its response time is shorter than 2 min (recovery time <1. the incorporation of CNTs into hollow core fiber optics is reported (95). hydrogen sulfide.37 and 0.70 mg L-1. fast response. unlike chlorine. one of the smelling principles in halitosis. Monoamine oxidase (MAO) was immobilized at the tip of a fiber-optic oxygen sensor with a luminescent oxygen probe (excitation at 470 nm. with detection limits of 0. was reported (88). King et al. Optical sensitivity to NO2.

sensing of pH values below 1 and above 12 still represents a substantial challenge in terms of material sciences. In other words: it is not specific for RH. Absorption and emission spectra. A scheme for measurement of very high pH values as they occur in chemical processing was presented by Gotou et al. (110) have obtained wide-range pH optical sensor by immobilizing three indicators in a sol-gel matrix that was deposited in a fiber optic waveguide and optically interrogated by evanescent wave absorptiometry. The sensors have a dynamic range from pH 4.5 to 13. intensity. microsensors were described for simultaneous sensing of pH and oxygen (114). and that authors often do not properly cite previous work on the subject. A novel wide pH range sensing system was described that is based on a sol-gel encapsulated amino-functionalized corrole (109). Congo red and neutral red on a cellulose acetate support have been reinvented as a material for sensing the 4. Seki et al. The sensor displays a 27 times better sensitivity to RH than a comparable overlay. respectively. A complex algorithm enables precise calculation of pH even if the spectra of the indicator dyes (for pH and oxygen) overlap. respectively.0-12. SENSORS FOR pH AND IONS This section covers sensors for all kinds of inorganic ions including the proton (i. An amino modified fluorescent aminophenylcorrole immobilized in a sol-gel SiO2 matrix undergoes large changes in fluorescence intensity owing to multiple steps of protonation and deprotonation. The Schiff bases can be photoexcited at 556 and 570 nm. Indicator loaded microbeads that are permeation selective for either protons or dissolved oxygen were used in a respective dually sensing membrane and a single fiber-optic sensor (113).. and acidity constants were determined in organic solvents and in PVC. viz. The number of articles on pH sensors is decreasing.0 and 7. thereby allowing larger pH ranges (1-11) to be covered than via respective tetraphenylporphyrins. It also needs to be stated that many pH sensors presented in the past few years are modifications only of existing sensing schemes and materials. The resulting sol-gel (TiO2) is said to be more resistant and to have a longer lifetime than SiO2 films. Data are evaluated by a modified dual luminophore referencing method which relates the phase shift (as measured at two different frequencies) to pH and to O partial pressure. Two aromatic Schiff bases were studied for their suitability in terms of sensing alkaline pH values (108). The same group also has developed sol-gel matrixes by controlled hydrolysis of a titanium tetraalkoxide (106). and anions. fluores- cence lifetimes. or both.quartz/polymer optical fiber pairs.0 pH range.e. photostabilities. It is noted at this point by the author of this review that sol-gels and other condensates of that kind are known not to provide a temporally stable matrix but rather to change their microstructure over periods of typically a few months. Dong et al. The matrix was doped with various pH indicator dyes. The applicability of this sensor was tested for its performance in pH analysis in tap and bottled mineral water (105). cations. On the other side.0-12. respectively (107). (111). In related work but using different materials (for optoelectronic reasons). The ratio between the two signals is proportional to pH but independent of excitation light intensity. report (102) that a thermoplastic polyimide when deposited on a fiber-optic Bragg grating can act as a material sensitive to RH in that it undergoes reversible expansion and shrinkage. The sensitivity of a tapered optical fiber relative humidity (RH) sensor was optimized by means of tuning the thickness of nanostructured sensitive coatings (101). The sensing scheme relies on the measurement of the fluorescence intensity of the pH indicator that is related to the intensity of the blue excitation light reflected by the sensing phase. which does not come as a surprise in view of the state of the art and the fact that certain pH FOS are commercially available. The pH probe (a carboxyfluorescein) and the oxygen probe (a ruthenium complex) were incorporated into two kinds of microparticles. this enabling monitoring human breathing. pH). Huang et al. pH changes were detected by measuring the loss spectra at 575 and 545 nm. though. This is important in clinical chemistry and if minute sample volumes are only available. It is used to establish a health monitoring method for chemically exposed fiber reinforced plastic structures in that it can detect the penetration of corrosive solutions into plastics. describe a pH sensor based on a heterocore structured fiber optic (112). and respond to pH in the range from 8. Optical pH sensors respond over a limited range of pH only (in most cases).1-9. Analytical Chemistry. Both kinds of beads were then dispersed into a hydrogel matrix and placed at the distal end of an optical fiber waveguide for optical interrogation. The pH indicator phenol red was immobilized in a sol-gel matrix at the surface of the heterocore portion. Vol. sensors are presented that are inferior to others described before. The sensor is constructed from low cost fiber optic and optoelectronic components including a blue light emitting diode and a photodiode. It consists of multimode fibers and a short piece of single mode fiber which was inserted into the multimode fibers. A single mode tapered fiber was coated with a specific nanostructured polymer whose thickness was controlled so to optimize sensitivity to RH. A phase-modulated blue-green LED served as the light source for exciting luminescence whose average decay times or phase shifts served as the analytical information. an amino-modified poly(hydroxyethyl methacrylate) and an organically modified sol-gel. 12. Optical sensing of pH remains to be of greatest interest even though all optical sensors suffer from cross sensitivity to ionic strength. pH is calculated by chemometric means from selected data points of the fluorescence spectra of aminofluorescein at high concentration so that a strong inner filter is operative.0. The microsensors with a tip diameter of ∼140 µm make use of luminescent microbeads that respond to the respective parameters by a change in the decay time. This is rarely addressed by authors of respective work. A high-pH indicator is used along with an optical fiber connected to a spectrophotometer. 2008 4275 . Martin et al. quantum yields. describe a new organic pH indicator dye (mercurochrome) that was immobilized in a sol-gel matrix placed at the end of a fiber optic and enables measurement of pH in the pH 4-8 range (104). respectively.3 and 4. In the worst case. The group of Scheper has introduced a scheme for referenced sensing of pH that is based on spectral analysis of fluorescence (103). 80. Such sensors are not treated here. Examples of vapors that interfere (or may be sensed with this device) include those of acetone and ethanol.0.2-6. No. respectively. June 15. each being sensitive to different pH ranges.

(131). dynamic range. and can be used at near neutral pHs. Concentrations as low as 0. Methanol. It makes use of single-walled carbon nanotubes whose reflectivity changes in the presence of toluene. (124) describe fluoro-reactands for the enzymeless determination of saccharides. Binding constants of the various amines depend on the kind of solvent and are highly different. e. and rapid response.. Unlike in the case of electrochemical schemes where direct electron shuttle from the substrate to the electrode has become possible as a result of enzyme wiring. The detection limit is reported to be 30 µg/L. The cladding layer ensures the ability of the capillary to guide light. and interferences were studied.1 mg/mL were detectable. Limits of detection are as small as 30 nM. A Fabry-Perot interferometric system was developed containing a thin layer of nanoporous zeolite synthesized on the cleaved end face of a single mode fiber. Polymer membranes containing a chromogenic functional azo dye undergo color changes on (reversible) interactions with amines in organic solvents (127). Traces of vanadium(V) ion can been determined by using an irreversible chromogenic reaction between vanadium ion and a hydroxamic acid immobilized in a poly(vinyl chloride) (PVC) membrane (117). The dynamic range at pH 5 is linear up to 0. Both methods have the potential to be utilized in small fiber sensors that may be inserted into subcutaneous tissue. and other common substances. 80. June 15. limits of detection (poor).2 µM. Cu(II) and Zn(II) interfere to some extent. A fluorescent dosimeter for formaldehyde determination in water utilizes the Nash reagent incorporated into silica gel beads (129). 2-hydroxyethyl methacrylate. 2008 a covalent bond between their boronic acid moiety and the diol moiety of saccharides. For a review. PVC and ethyl cellulose acted as sensor matrixes. Like similar sensors described before. drugs and pharmaceuticals. the sensor is based on the intrinsic evanescent wave absorption by chromate ions in a water sample inside the capillary. On reaction with formaldehyde. Ruthenium(II)tris(bipyridine) on Nafion was immobilized on a carbon electrode. The MIP was synthesized from acrylamide. 2-propanol. The capillary has a cladding layer and a protective polymer coating on its outside surface. antibodies. The same group has synthesized a fluorescent semicarbazone and demonstrated its applicability as a selective probe in an FOCS for copper(II) (119). the limit of detection is 4 µM. a fluorescent product is formed that can be detected instrumentally or visually. Stable ormosil layers were obtained using various fractions of organically modified sol-gel precursors. At pH 5. these still rely on (a) . sensitivity. Aqueous solutions of glucose were analyzed by fiber based attenuated total reflection spectroscopy and by transmission spectroscopy. and rather high detection limits (0. and toluene were detected with high sensitivity. emits with a peak at 600 nm. this resulting in strongly varying limits of detection. (121). and miscellaneous other organics. Dissolved amines also can be sensed by incorporating an aminecarrying chromoionophore into a sol-gel matrix (128). The MIP was prepared with Al(III) ion acting as the template. agrochemicals. They are based on hemicyanine dyes containing a boronic acid receptor and are capable of forming 4276 Analytical Chemistry. Base-catalyzed sensor layers underwent large signal changes. No. while the protective coating increases its mechanical strength. BIOSENSORS This section covers biosensors based on the use of enzymes. Both acidand base-catalyzed sol-gel processes were studied. and whole cells. The probe can be photoexcited at around 460 nm. Vol. Enzymatic Biosensors. The dye (covalently linked to the polymer matrix) recognizes the analyte via covalent binding. reversibility. Response time. Organics. This causes their fluorescence to increase. Aluminum ion in aqueous media can be probed with a regenerable sensor that uses a molecularly imprinted polymer (MIP) as the recognition receptor (120). with response times of around 1-2 min. but the former were found not to respond at all. SENSORS FOR ORGANIC CHEMICALS This chapter covers sensors for organic species (mainly saccharides). no such approach is possible in optical sensors. Sensing glucose remains to be an evergreen. It should be noted that some of the biosensors can be found in other chapters if this was deemed to be more appropriate. System features include good stability of the steady-state signal. A fluorescence-based calcium nanosensor was described (116) that exploits silica nanoparticles (prepared by inverse microemulsion polymerization) doped with the calcium(II) probe calcein as both a recognition and transduction element for optical determination of calcium in blood serum. Biosensors make use of biological components in order to sense a species of interest (which by itself need not be a “biospecies”). Dissolved organics in water samples can be sensed with a nanoporous zeolite thin film-based fiber sensor (130). The dosimeter does not respond to primary alcohols. The sensor is operated by monitoring changes in the thickness of the thin film caused by the adsorption of organic molecules by white light interferometry. A 30 m long capillary has the capability of detecting as little as 31 ppm of chromate. A FOCS for toluene in water was described by Consales et al. A quenchable fluorescent benzofurane derivative in the plasticized PVC matrix served as the indicator dye in an FOCS for ferric ion (118). chemical sensors not using a biological component but placed in a biological matrix are not biosensors by definition. Tri-n-propylamine and the drugs benzhexol and procyclidine were determined via electrochemiluminescence (ECL) in a sensor constructed by the screen-print technique (126). nucleic acids. Hence. On the other side. and ethylene glycol dimethylacrylate as a cross-linker. pollutants. Mid-IR laser spectroscopy was performed by either using cryogenically cooled lead salt lasers or quantum cascade lasers operating at room temperature and applied to reagentless (enzymeless) sensing of glucose (123).An evanescent wave direct spectroscopic sensor for chromate anion reported by Tao & Sarma (115) uses a flexible fused silica light guiding capillary as a transducer. In related work it is reported (122) that Pb(II) ions can be (irreversibly) probed by a similar method but using CdTe quantum dots capped with thiols. They report on a luminescent nanosensor for Hg(II) where the fluorescence of carnitine capped quantum dots made from CdSe/ZnS is quenched by Hg(II) ions with an efficiency that resulted in a detection limit of 0. on probes for saccharides and glycosylated biomolecules see ref 125. and both absorption and emission spectrometry can be applied. The detection limit is virtually the same.1 mM.g. and 8-hydroxyquinoline sulfonate acted as a fluorogenic ligand. and its ECL resulting from the interaction with the analytes was measured. Mohr et al. Mercury(II) ions were optically probed by Li et al. methyl triethoxysilane. nerve agents. ketones.1 mM). 12.

and does not require a secondary antibody.transduction via metabolic coreactants (such as oxygen or NAD+). and this is detected via the pH probe fluorescein immobilized at the tip of the FOBS. The gas permeable tubing warrants constant air saturation in the flow cell. Concentrations down to 80 ng/L of the chemicals were detectable. in principle. A tubing as used in microdialysis contains an integrated fiber-optic sensor. Comprehensive reviews have appeared (132). The group of Klimant has designed a fiber-optic flow through sensor for online monitoring of glucose in patients in intensive care units (133). the response time is slow (8-10 min). The sensor was evaluated in a 24 h test on a healthy volunteer. A waveguide based immunosensor for the food toxins aflatoxin B1 and ochratoxin A uses either the competitive or the direct immunoassay format (147). Antibodies against the F1 antigen of Yersinia pestis (the cause for plague and a potential terroristic agent) can be detected by a sandwich immunoassay on the surface of an optical fiber (145). Conjugated to biotin. or failure of the peristaltic pump. This is one of the few reversible optical methods that are based on the transduction of oxidase based reactions via H2O2. A human monoclonal IgM isolated from breast cancer patients targets the GIPC-1 protein and thus can be detected in concentrations down to 30 pg/mL. Luminescent yeast cells were entrapped in hydrogels in order to optically detect estrogenic endocrine disrupting chemicals (137). with a linear response at ∼65 mg/L. for the binding of the protein. Quantitative comparisons were made between the five matrixes and between the binding strategies.e. The sensing area was coated over ∼1 cm length with silver and then with the enzyme naringinase. and this was exploited in a optical glucose assay using the enzyme GOx. The unclad portion of an optical fiber was covered with selfassembled gold colloids whose surface was functionalized with antigens. Antinuclear antibodies can be quantified with an optical fiber biosensor modified with colloidal gold (144). Hydrolysis of organophosphates by OPH causes the pH to fall.. Its sensitivity is higher by at least 1 order of magnitude than that of the ELISA method. it was attached to a polystyrene waveguide along with the fluorescent pH indicator carboxynaphthofluorescein. the buildup of fluorescent products from single enzyme molecules catalysis over the array of reaction vessels can be observed. temperature fluctuations. On the basis of the previous work on sensing H2O2 via the amount of oxygen formed by catalytic decomposition of H2O2. The antibody conjugate was imAnalytical Chemistry. Fiber optic absorbance spectroscopy was compared with surface plasmon optical detection methods for lactamases bound to interfacial structures via biotin-avidin coupling (138). (136) have designed a robust and reversible sensor where ruthenium(IV)dioxide is used as a catalyst. This sensing platform is label-free. Unlike in so-called “ensemble” responses in which many analyte molecules give rise to the measured signal. or NADH). One assay was completed within 3 min. Single molecules of galactosidase were monitored (140) using a 1 mm diameter fiber-optic bundle with individually sealed femtoliter microwell reactors. A good reproducibility was observed 60 times without exchange of the enzyme membrane. Antinuclear antibodies in serum can be determined quantitatively. and asymptomatic controls were tested for the presence of IgM anti-GIPC-1 autoantibodies by the two methods. Mills et al. A reference oxygen sensor is used to detect changes in oxygen supply caused by adverse effects such as bacterial growth. The quantum dots have a rather high specific surface area which enables a relatively large amount of GOx to be immobilized. June 15. Real time activity assays of β-lactamase were performed by a detection scheme that combines an affinity test and a catalytic sensor. Organophosphate pesticides and chemical warfare agents can be sensed with a FOBS that exploits the enzyme organophosphate hydrolase (OPH) as the biorecognition element (139). The calibration curve was linear for glucose in fish plasma. describe a needle-type enzyme sensor system for determining glucose levels in fish blood (134). All matrixes were suited. Autoantibodies to ovarian and breast cancer-associated antigens are detectable with high sensitivity by using a chemiluminescence based optical fiber immunosensor (146). No. The amount of oxygen liberated is determined via the quenching effect it exerts on the luminescence of a ruthenium(II) ligand complex. Sera from 11 ovarian cancer patients. 2008 4277 . which is 50 times lower than the chemiluminescent ELISA and ∼500 times lower than the colorimetric ELISA. enables real-time detection. 12. 22 breast cancer patients. Vol. and this is reported by the pH probe. hydrogen peroxide. The SPR wavelength maximum increases with the concentration of naringin. Endo et al. Haloalkane dehalogenase in whole cells of Xanthobacter autotrophicus immobilized in calcium alginate at the tip of a fiber-optic coverts the haloalkanes into acidic products (i. lowers the pH). The chemicals induce a chemiluminescence to be emitted by the cells. Immunosensors. The dynamic range for determination of paraoxon is from 1 to 800 µmol/L. The protein GIPC-1 was conjugated to the tip of an optical fiber. (b) of coproducts (such as protons. Like most cell-based catalytic biosensors. or (c) on affinity binding (such as to concanavalin A). A fiber-optic enzymatic biosensor was described for determination of 1. 80. Glucose is sensed via oxygen consumption which occurs as a result of the oxidation of glucose catalyzed by immobilized GOx. Rajan et al. report on the fabrication and characterization of a surface plasmon resonance based enzymatic FOBS for detection of the bittering component naringin (143). DCA was quantified at levels as low as 11 mg/L.2-dichloroethane (DCA) (142). This approach should prove useful for single molecule enzymology and ultrasensitive bioassays. The data obtained with this sensor roughly correlated with LC-MS/MS analytical results. and the results agree well with the accepted ELISA method. Results obtained by SPR and optical waveguide measurements correlate excellently. and a digital concentration readout can be obtained by application of statistical analysis. The group of Nann (135) found that the luminescence of silica coated quantum dots is dynamically quenched by hydrogen peroxide (H2O2). Genetically modified Saccharomyces cerevisiae cells containing the estrogen receptor expression of the luc reporter gene were immobilized in hydrogel matrixes. A similar approach (141) was applied to 24 000 individual reaction chambers to sense DNA and antibodies and again is expected to be applicable to assays that utilize an enzyme label to catalyze the generation of a fluorescent signal. A hollow needle was used that also was comprised of an immobilized enzyme membrane and a optic fiber probe with a quenchable ruthenium-based oxygen indicator. The probe was stored for 1 month at -80 °C but full activity was attained again at room temperature.

The flavobacterium contains a hydrolase that hydrolyzes methyl parathion into optically detectable p-nitrophenol. Several pathogens (including hepatitis virus) were detected by this technique. Only 75 µL of sample are needed to detect 0. Dipping the stick into two reagent solutions results in a correlated conversion of a chromogenic substrate by a His6targeted enzyme complex. and macrolide antibiotics in food samples. this approach may be quite powerful. an easily detectable ECL is generated in the presence of the ruthenium complex at +1. and ecosystems.5 and 10 ng/mL. A strain was used that displays low substrate selectivity and responded to mono. The sensor is reusable because the target DNA can be stripped off the grating surface after the assay. The dipstick assay consists of a membrane support strip coated with streptavidin and immobilized biotinylated operator DNA. Bacterial transcriptional regulators are known to be dosedependently released from their operators upon binding of specific classes of antibiotics. specifically oligonucleotides and hybridized oligonucleotides. Another optical fiber biosensor for biochemical oxygen demand (BOD) is based on microorganisms coimmobilized in an ormosil matrix (160). Given the sensitivity of ECL-based methods.5 kb was found to be a suitable sensing nucleic acid. In another approach.3 nmol/L concentrations of methyl parathion.and disaccharides. localized SPR spectroscopy was coupled to interferometry (155). June 15. The multichannel system developed is based on mini-bioreactors containing four kinds of recombinant bioluminescent bacteria and is connected to a luminometer via a fiber-optic cable. The consumption of dissolved oxygen is measured with a fluorescent optical fiber sensor. Hybridization was visualized using fluorescently labeled secondary probes. Antibiotics present in specific samples triggered the dose-dependent release of the capture DNA-biosensor interaction. the electrochemiluminescence (ECL) of the Ru(II) bipyridyl complex (a weak intercalator) is used to generate optical analytical information (156). to fatty acids. which acts as capture DNA to bind hexa-histidine (His6)tagged bacterial biosensors. the assay time being 45 min without a separate amplification step.6 µg/L of Hg(II). In a comparable approach. Microbially available dissolved organic carbon was quantified with a microsensor (159) containing microorganisms in a polyurethane hydrogel. The authors exploit the fact that DNA fragments attached to NPs precipitate them only at locations where cDNA strands exist. An elegant diagnostic device for the detection of the hepatitis B virus was presented (149). The intensity of light reflected by the chip resulted in an optical pattern that was highly sensitive to changes in the effective thickness of the layer on the surface. Genetically engineered bioluminescent bacteria were applied to the detection of toxicants in surface waters (161). In another type of DNA biosensor. Results are in good agreement with those obtained by ELISA. regional economies. The probe DNA was immobilized on the silanized surface of the grating and then hybridized with the complementary (target) DNA. Following fragmentation with restriction enzymes and denaturation. Wang et al. Hence. A fiber-optic DNA microarray for simultaneous determination of multiple harmful algal bloom species was reported by Ahn et al. (148). The indirect method was used to sense toxins in barley and wheat flour samples. antibiotics in seafood were screened for a fiber-optic fluorometric assay based on competitive binding of the analyte and an intercalating dye to double stranded DNA (151). and to amino acids. the interaction of the two strands is found to be specific both with oligonucleotides and with genomic nonamplified DNA.mobilized on a sensor chip and exposed to the analytes in a flow injection analyzer. No. while ss-DNA (which is not intercalated) does not give this effect. 12. Bioavailable mercury and arsenic in soil and sediments were determined with fiber-optic bacterial biosensors (157). Algal blooms are a serious threat to coastal resources. A gold layer was deposited on porous anodic alumina and interrogated by both interferometry and localized SPR. detecting even single-base mismatched DNA targets in concentrations down to 10 pM. The antibiotics affect the binding of the intercalator to the double stranded nucleic acid. The concentration of the analyte is indirectly determined by the decrease in fluorescence intensity. the opacity of the chip surface changes due to the accumulation of NPs and this can be used to detect targeted DNA fragments. 80. A DNA of 48. The usual amplification step is found not to be necessary. DNA Biosensors. The BOD values obtained correlate well with those determined by the conventional BOD5 method for seawater samples. The 90% response time was 1-5 min. If ds-DNA binds to intercalators such as doxorubicin or daunorubicin. A detection limit as low as 5 cells is achieved. Bacterial Biosensors. streptogramin. 141 µg/L of As(V). The approach is very sensitive. Sulfathiazole and chloramphenicol in shrimps were sensed by this method with detection limits from 0. (150) use a generic dipstick-based technology for rapid determination of tetracycline. Link et al. Vol. and 18 µg/L of As(III). The system can be continuously operated due to the separation of the bacteria culture reactor from the test reactor without system shutdown by abrupt inflows of severe pollutants. 4278 Analytical Chemistry.19 V (vs Ag/AgCl). report on a DNA detection protocol utilizing the opacity of self-assembled nanometallic particles (NPs) and the optical response of a CMOS image sensor (153). Alginate-immobilized recombinant luminescent bacteria were immobilized on optical fibers and enabled luminescent quantification of 2. 2008 Surface plasmon resonance (SPR) spectroscopy was used for detecting target sequences in genomic DNA differing in terms of copies in the relative genome (154). causing a variety of impacts on public health. adsorbed on glass fiber filters as a disposable biocomponent (158). thereby changing the fluorescence intensity. The sandwich hybridization assay combines fiber-optic array technology with appropriate oligonucleotide probes immobilized on microspheres. The pesticide methyl parathion was shown to be detectable using Flavobacterium sp. Bioluminescent signatures were delivered from four channels by switching one at once. The system is now being implemented to a drinking water reservoir and river for remote sensing as an early warning system. In a novel kind of DNA biosensor. It has detection limits as low as 1/40 of the licensed threshold. An isothermal amplification method is employed so to detect the viral DNA in a 25 µL reaction volume following several automated handling steps. The detection range of the competitive detection method was between 0.5 to 1 ng/mL. . An optical biosensor for real-time detection of DNA interactions was demonstrated with a long-period fiber-grating biosensor (152).

Na. and moisture in alfalfa (164). Mn. (171). The authors measured chloride ions in a typical concrete sample immersed in salt water solutions in concentrations ranging from 0 to 25%. The sensor exhibited a linear decrease in the transmission loss and resonance wavelength shift when the chloride was increased. Optical fibers are used to connect the interrogating unit to the sensing capillary. while freshly prepared or washed fibers are not. (165). The prediction capacity of the model and the robustness of the method were checked in the external validation in alfalfa samples of unknown compounds. Most regional differences of water content were calculated from the peak height of the 1900 nm water band normalized to the peak height of the 2175 nm amide band. New in-line fiber-optic structures for environmental sensing applications were described (174). it enables inline chemical reaction monitoring (162). oxidized fibers that can release arsenate ions are toxic. The humidity sensors were fabricated using fiber Bragg gratings coated with moisture sensitive polymers and are employed in detecting the movement of moisture through standardized cubes made from samples of different types of structural concrete. Huber et al. thus offering the possibility of detecting a change in chemical concentration. to mention only the more important ones. indicated by a shift in the Bragg wavelength of the sensor. and for distributed sensing. No. (163) reports on the measurement of the ingress of oxygen into PET bottles using oxygen sensor technology. Hence. production. TAS fibers undergo oxidation on air to form a water-soluble nanometer-thin layer that is soluble in water.04%. Sensors based on the interaction of surface plasmons or evanescent waves with the surrounding environment are usually obtained by tapering an optical fiber. One large area of application of FOCS is in monitoring the mechanical and chemical integrity of concrete structures. stable in water over several days. Optical fiber sensors have been used to monitoring the ingress of moisture in structural concrete (170). Glasses displaying less strong interfering vibrations in the 2-5 µm spectral region were prepared from TeO2-BaO-Bi2O3 mixtures (166). Preliminary in vivo tests were carried out in pigs with altered respiratory function.03 pH units and an accuracy of 0. Blood samples were taken from the forearm every minute during each exercise bout. The method allows immediate analysis of alfalfa without prior sample treatment. Sensing is based on quenching of the fluorescence by oxygen of a sensor spot placed on the inner wall of the transparent bottle. In combination with robust and flexible fiber-optics. Thus. Chloride ion in concrete can be sensed with a long-period fiber grating (LPFG) (172). food. Fiber Optics. The data for venous and arterial blood were found to be highly different when exercising. changes in chemical composition are of high interest given the health risk and costs associated with disintegrated structures.07 pH units were obtained. and related applications of FOCS and FOBS. Aside from their use as plain waveguides. and the temperature dependence of the viscosities of the glasses is reported. P. The biocompatibility of Te-As-Se (TAS) glass fibers for use in infrared sensors was studied by Wilhelm et al. The optical fiber sensors reacted to the ingress of water by detecting the moisture migrating through the sample. 80. pH sensors for concrete are needed to detect any (highly adverse) changes in the rather high pH (>11) of concrete. Data obtained can give information on the properties of different types of concrete but also on the migration of dissolved salts. A partial least-squares regression method was employed. pharmaceutical. The current success of (fiber optic) surface plasmon resonance (SPR) is obvious. Graded index optical Analytical Chemistry. such as sodium chloride which is important in view of their deleterious effects on reinforcement bars within concrete. Regional differences in the water content of human skin can be studied by diffuse reflectance near-infrared spectroscopy (169). Gaseous or dissolved oxygen can be detected in the ppm to ppb range. Vol. a newly developed miniaturized diamond ATR probe has been described that displays high chemical and pressure resistance. The pH indicator phenol red is covalently immobilized on the inner wall of the capillary. There was a difference in the ratio of the two water bands centered near 1450 and 1900 nm between the contact and noncontact measurements. The LPFG device is sensitive to the refractive index of the medium around the cladding surface of the sensing grating. Fe. A fiber-optic structure is presented that maintains the structural integrity of the optical fiber.APPLICATIONS This section comprises sensors for environmental. An fiber-optic pH sensor was developed that can be incorporated into concrete and thus is capable of early detection of the danger of corrosion in steel-reinforced concrete structures (173). A fiber-optic sensor was inserted into muscle for continuous measurement of intramuscular data. and quality control applications. in microsensors and nanosensors. Near-infrared reflectance spectroscopy was applied to quantitate Ca. carbon dioxide. 12. however. A resolution of 0. A fiber-optic cable is positioned outside and measures changes in luminescence lifetime. IR and Raman spectroscopic studies were carried out. industrial. A similar approach was introduced by Yeo et al. and oxygen as obtained with fiberoptic sensors on intramuscular and venous blood during rhythmic handgrip exercise were compared (168). biotechnological. Sensitivity was further enhanced by coating a monolayer of colloidal gold nanoparticles as the active material on the grating surface of the LPFG which increase the sensitivity by a factor of 2. K. Aside from sensing mechanical integrity (not treated here). for imaging and sensor array purposes. The glass underneath this layer is. The interstitial sample fluid drawn subcutaneously from adipose tissue flows through a microfluidic circuit formed by a microdialysis catheter in series with a glass capillary. 2008 4279 . protein. A fiber-optic sensor for measurements of interstitial pH was further improved (167). Data on pH. June 15. Permeation rates are obtained without piercing the package or bottle which is ideally suited for assurance. Zn. medical. The fibers are used for IR direct spectroscopy of cultivated mammalian cells. A noninvasive fiber-optic oxygen meter detects oxygen permeability of PET bottles for soft drinks by measuring trace levels of oxygen inside the bottle. fibers have been used for evanescent wave excitation of fluorescence or Raman scatter. Reflectance spectra in the 1250-2500 nm region for the skin of volunteers reveal large regional differences of water content. SENSING SCHEMES AND SPECTROSCOPIES This section reports on improved or novel sensing schemes based on the use of fiber optics and related waveguides. The limit of detection for chloride ions is ∼0.

Almost any optical disk can be employed for deposition and readout of sensor films. A single grating spectrograph with fiber-optic input and photodiodes at three different wavelengths was compared to a system comprising 1-3 fiberoptic splitters and photodiode detectors with integrated interference filters. and it is found that that the systems have similar characteristics. A photonic band gap fiber for measurement of RI was described by Sun and Chan (187). Signals were obtained from optical sensor films deposited on conventional CD and DVD optical disks. there are domains in which the indicator reagents are immobilized and domains where diffusive transport of the analyte occurs. It allows realtime monitoring of the displacement of a chemical substance along a capillary.g. Moreover. 150. The sensor measures the light intensity of the internally reflected light at a fixed wavelength from an optical fiber where the extinction cross-section of self-assembled gold nanoparticles on the unclad portion of the optical fiber changes with the refractive index of a sample near the gold surface. A sub-nanoliter spectroscopic gas sensor was described (180) and compared to existing sensors designs. Specifically. This novel gas sensor has the capability of gas detection with a cell volume in the sub-nanoliter range. The resulting devices were used to measure the concentrations of sugar solutions. These elements are fused by an optical fiber splicer. and peroxides (based on immobilized horseradish peroxidase and a chromogenic substrate). The disk drives also perform the function of reading and writing digital content to optical media. Toluene vapor in nitrogen gas was investigated. connecting the coated FSCap to a light source and a photodetector. Such a sensor platform is quite universal and can be applied to sensing and combinatorial screening. Ink jet printing technology was applied to fabricating microsized optical fiber imaging sensors (183). e. This perturbation leads to a wavelength-splitting in two separate peaks: the peak at lower wavelengths corresponds to the thinned region and is dependent on the outer RI and the local temperature. toluene in water samples and ammonia in a gas sample were fabricated and tested. and a coreless optical fiber acts as the interaction area. Tao et al. Fiber optic (bio)sensors were reported that are based on localized surface plasmon resonance (SPR) (188). The sensor consists of a Bragg grating where the cladding layer is removed along half of the grating length. It causes a change in the refractive index changes of the xerogel fiber cladding at 670 nm. chemical concentrations at high pressure conditions (189). June 15. 4280 Analytical Chemistry. Capillary Waveguides. and delivering a sample through the FSCap were developed. while the peak at longer wavelength responds to thermal changes only. hollow core microstructured polymer optical fibers can be used for sensing chiral species. Various prototypes of sensors were prepared. and quantified in the optical disk drive. They consist of nanosized domains of hydrophilic and hydrophobic polymers (comparable to a polyacrylamide-co-polyacrylonitrile copolymer referred to as Hypan and previously introduced by others). An array of photopolymerizable sensing elements containing a pH sensitive indicator was deposited on the surface of an optical fiber image guide. The fiber is then filled with an aqueous solution of (L)-fructose. Three types of splitters were tested. 80. A study of the capabilities of microstructure fibers for evanescent wave vapor sensing is presented in ref 181. Hence. (184) showed that nanophase-separated amphiphilic networks represent versatile matrixes for optical chemical and biochemical sensors. A distributed fiber-optic polarimetric sensor was reported by Caron et al. Refractive Index. Hence. A FSCap for pH is demonstrated. Evanescent absorbance was linear with the concentration of a nonpolar dye but nonlinear with ionic dyes due to adsorption to the capillary wall. coating the inner surface of the FSCap with a polymer. A light guiding flexible fused silica capillary (FSCap) was used that is similar to a conventional silica fiber in that it can guide light in the wavelength region from UV to near IR. exposed to different concentrations of Ca(II). The inner surface of the FSCap capillary was coated with a reagent doped polymer to design a FOCS. for sensing gaseous chlorine (based on a chromogenic reaction). vapors of acids (based on immobilized bromophenol blue). and the resulting optical rotation is measured. also if used in a colorimetric CO2 sensor. Vol. Hanko et al. single-mode.. (177). the waveguiding properties of a FCSap for chemical sensing applications were investigated by Keller et al. Sensors for Cu(II). 12. Sensing is based on the measurement . and 250 µm inner diameter FSCaps show that greater sensitivity is achieved in thinner walled tubings because of more internal reflections. Because of the spatial separation. Two optical system designs were compared for fiberoptic chemical sensor applications (175). A related reflection based localized SPR fiber-optic probe was developed to determine refractive indexes and. colorimetric calcium-sensitive films were deposited onto a DVD. A self-temperature-referenced sensor based on nonuniform thinned fiber Bragg gratings was described (186). (176) described the application of a light guiding flexible tubular waveguide in evanescent wave absorption based sensing. The sensor is based on evanescent wave polarimetric interferometry and is intended for use in gas chromatography. thus. No. It is demonstrated how the band gaps of such a hollow core polymer optical fiber scale with the refractive index of a liquid introduced into the holes of the microstructure. Techniques were developed for activating the inner surface of an FSCap. and multimode fibers and postsensitized by HF etching treatment (185). Absorbance within the tubing was measured by optically coupling the FSCap to a spectrophotometer. The FSCap operated evanescently or as a liquid core waveguide depending upon the refractive index of the sample solution within the capillary. A liquid-filled hollow core microstructured polymer optical fiber (178) is said to be opening up many possibilities in FOCS. specific changes in absorbance due to C-H overtone absorptions of toluene at 1600-1800 nm were exploited.fiber elements are used as lenses. 2008 Analog signal acquisition from computer optical disk drives was demonstrated to be useful in chemical sensing (182). Microsystems and Microstructures. (179). The reproducibility of the microjet printing process was found to be excellent for micrometer-sized sensor spots. Similarly. Sensing of the Ni(II) ion and label-free detection of streptavidin and staphylococcal enterotoxin B is demonstrated at picomolar levels. the intrinsically insensitive Bragg grating became sensitive to refractive index (RI). Absorbance measurements in 50. High-sensitivity optical chemosensors were implemented by exploiting fiber Bragg grating structures in D-shape. Spectroscopies. The sensor was characterized in terms of thermal and RI sensitivities.

pp 17-44. 108. J. 3rd ed. Rev. C2H2. The Netherlands. D. DC. 2007. 36.of the intensity of internal light reflection at a fixed wavelength from an optical fiber. Wolfbeis. In Optical Chemical Sensors. FL. 32. 2004. D. Opt. James. S. Vol. C. Mayr. and in the design of advanced (nano)materials (including fluorescence upconverters) for use in (bio)chemical sensing. A. F. By measuring at 1. B. R. serves as the analytical information. Int. Klimant. T. 2007. Topics in Fluorescence Spectroscopy. acetylene gas can be detected at limits as low as 19 nTorr(!).. Hung.. Homola. J. Spangenberg. M. 1683–1688. 17/1–17/10. P. Rev. and the instrument can be deployed in-field.. B. H. K. Cavity ringdown (CRD) absorption spectroscopy enables spectroscopic sensing of gases with a high sensitivity and accuracy. Burke. Austria.. 375– 403. Chem.. 2006. Anal. 74. T.1-20. Tatam.4 MPa at 308 K. Fernando. Cullum. P. D. M. 51. D. H2O. 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Practical Spectroscopy..56 µm yield sub-ppb (v/v) sensitivity in the gas phase for CO2. C. He acts on the board of several journals including Angewandte Chemie and is the Editor-in-Chief of Microchimica Acta. 10. W. Vol. Opt. Lakowicz. M.. Schaeferling.. CRC Press: Boca Raton. Acta 2006. 4. Degamber. R. Ojeda.-F. Sens. S.. Grattan. Li.. U. P. W. S430–S444. A. Crit. Biol. Anal. A.. Springer Series in Fluorescence... M. P. SPIE-Int. 2008. (Optical Sensing Technology and Applications) Mohr. S. Since 1995 he is a Full Professor of Analytical and Interface Chemistry at the University of Regensburg. Addison. and has acted as the (co)organizer of several conferences related to fluorescence spectroscopy (MAF) and to chemical sensors and biosensors (Europtrode). 65850B/1–65850B/8. . 2006. Bartelt. J... J. Chem. S. C. Chim. S.. The CRD spectrometer therefore is a high performance sensor in a relatively simple. Jirasek. Analyst 2007. Polymers. M. 72. 18. A. FL. J. MacCraith. Rev. Voros. Chem. 2007. E. A.. Sanchez. L. B. The light attenuation caused by the absorption of self-assembled gold nanoparticles on the unclad portion of the optical fiber changes with a different refractive index of the environment near the gold surface. He has authored around 470 papers and reviews on optical (fiber) chemical sensors. Borisov S. and other hydrocarbons. O. R. Buchanan.. S. C. F. A significant variation of the spectral transmittance of the device is produced as a function of the concentration of the analyte by tuning the plasmon resonance to a wavelength for which the outer medium is absorptive. S. Vol. R. Nagl. Wolfbeis. Two luminescent indicators are needed in this scheme that have overlapping absorption and emission spectra but largely different decay times. Vol. F. A. Opt. Talanta 2007.. Geddes. G. 423–461. Actuators.. low cost. S. Glucose Sensing.. no pages given.51 to 1. This continuous-wave CRD spectrometer uses a rapidly swept cavity of simple design. J. DOI: 10. Springer: Dordrecht. In Fluorescence of Supermolecules... Bosch. Rev. Vol. D. Sci. Springer: New York. 35. Lett.. Rojas.. Response is fast. Bhunia. 193198. 38 (11).. which is an important feature for any kind of FOCS or FOBS. In the frequency domain m-DLR method. K. J. S. 505–519. 13–27. Geng. 2007. J. They are excited by a single light source. S. Duerkop. 80. 8. M. Sheeran. Becker. Shankar. L. S. A fiber-optic prototype was constructed using low-cost optoelectronics including a light emitting diode and a photodiode detector. Elosua. Topics in Fluorescence Spectroscopy. Chem. E.. 2006. The method was demonstrated to work for the case of dually sensing oxygen and carbon dioxide. J. Eds. Schaeferling.) 2008. Conceicao. The method is based on the difference between the lifetimes of the phosphorescence and fluorescence emissions of a dually emitting indicator (an aluminum-ferron complex). 108. Anal. Vol. 76. A. 65–106. Chem.. Educ. 2006. K. With this mechanism. S. B: Chem. No. W. 6 (11). 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Eng. N. O. 2006. Sci... B. A.. Taricska. 7. Anal. 2006.D. T. Chem. Proc. CRC: Boca Raton. S. M. Opt. New Approaches in Biomedical Spectroscopy.. Nagl. 2008. Scopesi. CAN 148:44768. Mutharasan. J. 2007. (Washington. American Chemical Society: Washington. J. Sci. Y... O.. 529531. T. Wolfbeis holds a Ph. Martelucci. Ed. 758–760. Germany. A. 83. 40. The probe demonstrated a stable and repeatable response for sequential operations of pressurization and depressurization at 0.. R. 386. 2007. R. pp 133-155. O. S. G. Anal. S. G. O. 12. Bariain. J.. S. online computer file. A. Flowers. H. Karasyov. H. Environ. C. Matias. Konorov. Borisov. 2008. R. Wolfbeis. 413432. Interface Anal. Soc. has (co)edited several books. 2007. A luminescent ratiometric method in the frequency domain with dual phase-shift measurements was applied to oxygen sensing (193).. Eds. The geometry of a fiber-optic surfaceenhanced Raman scattering (SERS) sensor was optimized with respect to trace detection (192). 2007. 118. G. In Hazardous Industrial Waste Treatment. 3269–3284. Adriaens. M. Med. 85. O. O.. Wang. 11. Blades. 3859–3873. 224. O. F. Narayanaswamy.. Ser. Araujo. B. N... R. 507–511. and compact instrument. P. 1–20. A. After having spent several years at the Max-Planck Institute of Radiation Chemistry in Muelheim and at the University of Technology at Berlin. Opt. Halter. 1442–1458. C. The analytical information is obtained by measurement of the phase shifts at two modulation frequencies. Ojeda.. Geiger..-T. Bosch. M. Chojnacki. T. 118. P. Klein.. A new concept of an SPR fiber-optic sensor was presented (190). R. Eng. Sun. its active surface and the number of internal reflections at the interface between silica and silver is largely increased. Ecke. Bioanal. C. Turner. 2006. Rolfe. 569. Glucose Sensing. Springer: New York. and Nanosystems . Technol. S. in fluorescence-based analytical formats including imaging. Technol. Bally. pp 351-375. O. 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