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Current
Analytical Chemistry
ISSN: 1573-4110

Current Analytical Chemistry
Volume 4, Number 4, October 2008
Contents
Fiber Optic Chemical and Biological Sensors: Perspectives
and Challenges Approaching the Nano-Era
Guest Editor: Andrea Cusano, Antonello Cutolo and Michele
Giordano

Editorial: Pp. 271-272
New Trends in Fiber-Optic Chemical and Biological
Sensors Pp. 273-295
Guillermo Orellana and David Haigh
[Abstract]
Integrated Development of Chemoptical Fiber Nanosensors
Pp. 296-315
Andrea Cusano, Michele Giordano, Antonello
Cutolo, Marco Pisco and Marco Consales
[Abstract]
Molecularly Imprinted Polymers as Selective
Recognition Elements in Optical Sensing Pp.
316-340
María C. Moreno-Bondi, Fernando Navarro-Villoslada,
Elena Benito-Peña and Javier L. Urraca
[Abstract]
Fiber-Optic Chemical Nanosensors by Electrostatic
Molecular Self-Assembly Pp. 241-355
Ignacio Del Villar, Ignacio R. Matias and
Francisco J. Arregui
[Abstract]
Real-Time Monitoring of Siloxane Monolayer
Film Formation on Silica Using a Fiber Bragg Grating Pp.
356-361
Christopher J. Stanford, Mario Dagenais,
Ju-Hee Park and Philip DeShong
[Abstract]
High Coupling Efficiency in 2D Guided-Wave
Photonic Band Gap Extended Microcavities for Sensing Applications
Pp. 362-370
Caterina Ciminelli, Richard M. De La Rue
and Mario N. Armenise
[Abstract]
Scattered Colorimetry and Multivariate
Data Processing as an Objective Tool for Liquid Classification
and Mapping Pp. 371-377
Leonardo Ciaccheri and Anna G.
Magnani
[Abstract]
Fiber Optic Sensors for Biomedical Applications
Pp. 378-390
Francesco Baldini, Ambra Giannetti, Andrea
A. Mencaglia and Cosimo Trono
[Abstract]
Chemical Sensor Networks for Gas Detection
and Environmental Monitoring Pp. 391-402
Kevin Duffin, Walter Johnstone, Andrew McGettrick,
Dave Moodie, George Stewart, Graham Thursby and Brian
Culshaw
[Abstract]
Abstracts

[Back to top]
Editorial:Fiber Optic Chemical and Biological Sensors:
Perspectives and Challenges Approaching the Nano-Era
Fiber optic sensors emerged from the low loss fiber
optic technology developed in the 70’s and incredibly
increased their growth in both research and applications over
the last two decades. Cost effectiveness of fiber optic sensors
comes out from the rapid developments in telecommunications
optics, cost reduction in laser diodes and optical fibers.
Actually primary fiber optic sensors markets are oil wells,
security, smart structures and seismic detection in oil industry
with a market grew of about 90% in 2005 achieving revenue
of about 130 million $. Today, market opportunities for sensors
are developing and expanding due to the increase of environmental
global modifications, homeland security needs and elderly
population. Fiber optic based technology can respond to these
needs due to the inherent networking efficiency, the optimal
cost/performance ratio and the demonstrated ease of integration
of optical fibers with sensitive materials for physical, chemical
and biochemical sensors.
A wide choice of discrete and distributed fiber optic sensors
are commercial available based on well assessed optical transduction
schemes such as Fabry Perot cavities and Fiber Bragg Gratings
or Raman and Brillouin scattering techniques that cover most
of the relevant applications in physical sensing (temperature,
strain, stress, vibration). Moreover applications in chemical,
biological, environmental and medical fields requires a new
generation of devices which principle of operation relies
on the sensing functions added by specific designed coating
materials. In fact fiber optic sensing technology still continues
to be the subject of significant basic research effort not
only investigating novel phenomena that can be utilized in
sensing but also addressing the integration of novel materials
and nano/micro technology in the optical sensor design. In
particular, the ongoing interest is stimulated by an ever
increasing portfolio of technologies through which light may
be caused to interact with chemical or biological conditions
which surround it and, in recent years, materials nano/micro
technology has provided new opportunities for chemical and
biological applications. This issue will contribute toward
encapsulating recent exciting developments in the integration
of new transduction mechanisms and novel materials whilst
in parallel covering the continually expanding world of field
trials and application assessments, with special attention
to explore new perspectives and outline technological challenges.
A novel generation of fiber optic devices for chemical and
biological sensing is approaching based on the concurrent
addressing of the issues related to the different aspects
of their global design, such as: dielectric properties definition
and optical modeling, materials identification, functionalization
and activation, novel optical transduction principle development.
Up to now, great effort has been carried out by the scientific
community to develop photonic devices, however, the weak integration
of competencies required to address this challenge, intrinsically
multidisciplinary, limits the capability to achieve high performances
devices. A highly integrated approach involving continuous
interactions of different backgrounds aimed to optimize each
single aspect with a continuous feed-back, would enable the
definition of an overall and global design concept.
This special issue presents relevant developments in the field
of fiber optic chemical and biological nano/micro sensors
starting from a last five years review presented in chapter
1 including gas optodes (oxygen, hydrogen, carbon dioxide
and ammonia), humidity sensors, monitors for pH, cations and
anions, sensors for organic compounds. Also, biosensors based
on enzymes, antibodies, nucleic acids and whole microorganisms
are described to illustrate the state-of-the-art in this active
area.
Chapter 2 illustrates advanced interdisciplinary approaches
to in-fibre chemical sensing where nano structured materials
(nanocristalline polymers, carbon nanotubes and microstructured
metallic oxides) and innovative optical transducers schemes
(near field optical transducers, photonic bandgap fibers and
nano-coated long period gratings) are concurrently developed.
Addressing molecular recognition through the mimic of biological
receptors is the theme of chapter 3 where the development
of optical biosensors based on molecularly imprinted polymers
is reviewed and recent innovations presented with special
emphasis on their analytical applications.
Chapter 4 explores the potentiality of nanostructured coatings
fabricated by means of the layer-by-layer electrostatic-self
assembly (ESA) to develop novel fiber optic refractometers,
pH sensors, chemical sensors and biosensors at nano scale.
Development of novel optical transduction schemes is the subject
of chapter 5 where modifications of fiber Bragg gratings are
used to develop advanced surface sensitive chemical or biological
sensors for specific applications.
Remarkable advancements in the field of bio-detection is provided
in chapter 6 dealing with the use of photonic crystals to
enable the design and fabrication of high-sensitivity and
compact novel optical sensors. The unique characteristics
and versatility of this new technology are analysed to tailor
the sensing performances of this new class of devices.
In chapter 7, several application oriented examples are presented
to outline the relevance of the features extraction and data
processing techniques in the development of efficient sensors
system for in field practices.
Applications of optical sensors in medicine is discussed in
chapter 8 where the issue of the clinical validation and the
special qualifications and approvals requested for biomedical
sensors is addressed.
Chapter 9 discusses the enormous potentiality of direct spectroscopic
methods in chemical sensing illustrating the exploitation
of tunable diode laser spectroscopy in the near infrared range
for environmental monitoring.
This special issue is thus aimed to provide multidisciplinary
knowledge that is of novel trend in the active area of chemical,
biological and environmental monitoring applications at the
edge of the Nano-era.
The authors, chosen from a list of multidisciplinary international
team of researchers, are experts in their fields and are authoritative
in respect of their contribution. The Editors would like to
express their sincere appreciation and gratitude to all authors
for their efforts in preparing high quality contributions
as chapters for this special issue.
Aims and Scope
Fiber optic sensing technology continues to be the subject
of significant research endeavour investigating both the phenomena
which can be utilized in sensing and the applications of techniques
established within the laboratory. The ongoing interest is
stimulated at the basic level by an ever increasing portfolio
of technologies through which light may be caused to interact
with chemical or biological conditions which surround it.
In parallel the applications oriented research, in bioscience
area has specifically highlighted one or more of the unique
benefits which fiber sensor technology offer. In addition,
sensor technologies and nanotechnology have come together,
in recent years, to provide new opportunities using nanometer-scale
structures for chemical and biological applications. There
is considerable promise in the use of such ultra-small fiber
optic devices for sensing. For example, it is possible that
some phenomena hitherto below detection levels might now be
sensed by nanostructures. Fiber Optic Chemical Nanosensors
or Bio-nanosensors may be able to provide sensitivity down
to the single molecule level. On the other hand, additional
difficulties may well present themselves, including the fundamental
challenge of the integration of physical structures and devices
on the nanometer scale, as well as their integration into
the micro-scale world.
This special issue will contribute toward encapsulating recent
exciting developments in the incorporation of new transduction
mechanisms, novel materials and integration methods whilst
in parallel covering the continually expanding world of field
trials and application assessments, with special attention
to explore new perspectives and outline technological challenges.
Andrea Cusano / Antonello Cutolo
Guest Editors
Optoelectronic Division
Engineering Department
University of Sannio
Italy
and
Michele Giordano
Institute for Composite and
Biomedical Materials
CNR, Napoli
Italy
[Back to top]
New Trends in Fiber-Optic Chemical and Biological Sensors
Guillermo Orellana and David Haigh
The most relevant contributions in the field of fiber-optic
chemical sensors and biosensors in the last five years are
reviewed. Gas optodes (including oxygen, hydrogen, carbon
dioxide and ammonia), humidity sensors, monitors for pH, cations
and anions, and sensors for organic compounds constitute the
different sections. Optical fiber biosensors based on enzymes,
antibodies, nucleic acids and whole microorganisms serve to
illustrate the state-of-the-art in this active area. Selected
examples of absorbance-based, luminescent, evanescent wave,
Fabry-Perot, chemiluminescent and surface plasmon resonance-based
sensors and biosensors, among other techniques used for interrogate
the sensitive part of the devices, are described.
[Back to top]
Integrated Development of Chemoptical Fiber Nanosensors
Andrea Cusano, Michele Giordano, Antonello
Cutolo, Marco Pisco and Marco Consales
The development of fiber optic chemical sensors based
on the integrated design of novel sensitive nano-coatings
combined with advanced sensing configurations is reported
in the present study. Different sensitive coating materials
have been exploited togheter with their deposition techniques,
i.e nano-porous polymers deposited by using dip coating, carbon
nanotubes deposited by Langmuir-Blodgett method and metal
oxides, prepared by electrostatic spray pyrolysis. In accordance
to the chemo-optical properties of these materials novel sensing
schemes based on nano-coated Long Period Fiber Gratings, modified
Fabry-Perot interferometers involving near field effect and
photonic bandgap modification in Hollow-core Optical Fibers,
have been proposed, respectively, to provide the best sensing
performance. Experimental results reveal the potentiality
of the integated approach that simultaneously accounts for
the selection of the coating materials and of the fiber optic
sensing scheme in developing optical devices for a wide range
of applications related to the environmental monitoring either
in air and water environments.
[Back to top]
Molecularly Imprinted Polymers as Selective Recognition Elements
in Optical Sensing
María C. Moreno-Bondi, Fernando Navarro-Villoslada,
Elena Benito-Peña and Javier L. Urraca
Molecular imprinted polymers (MIPs) are molecular recognition
elements that can be tailored towards a wide variety of target
molecules. These human-made materials are relatively easy
to prepare and have found a broad application as substitutes
of antibodies or enzymes. They have been successfully applied
to the development of chromatographic or solid phase extraction
methods and have attracted a great interest for the development
of electrochemical, piezoelectrical or optical sensors. In
parallel with the classification of biosensors, MIP-based
devices can work according to two different detection schemes:
affinity sensors (“plastic-bodies”) and catalytic
sensors (“plastic-enzymes”). These devices can
be interrogated using different optical techniques, such as
fluorescence, light absorption (UV-Vis, Infrared) spectroscopy,
chemiluminescence, surface plasmon resonance, or Raman scattering.
This paper reviews the main developments and applications
of MIPs in the area of optical sensors with special emphasis
on their analytical applications.
[Back to top]
Fiber-Optic Chemical Nanosensors by Electrostatic Molecular
Self-Assembly
Ignacio Del Villar, Ignacio R. Matias and
Francisco J. Arregui
A review of optical fiber sensors based on nanostructured
coatings fabricated by means of the layer-by-layer electrostatic-self
assembly (ESA) method is presented here. The modification
of the optical properties of these sensing coatings by the
target parameter can induce changes in the reflected or transmitted
spectrum. This property can be exploited for the development
of refractometers, pH sensors, chemical sensors, biosensors
and other applications. In addition to the experiments performed,
the theory of some of these phenomena have been also studied
in order to understand the behavior of the sensors and to
improve their sensing characteristics.
[Back to top]
Real-Time Monitoring of Siloxane Monolayer Film Formation
on Silica Using a Fiber Bragg Grating
Christopher J. Stanford, Mario Dagenais,
Ju-Hee Park and Philip DeShong
We present a series of experiments to study the silanization
of the silica surface of a fiber Bragg grating biosensor.
A simple 4-layer attachment model is developed to describe
the bonding of 3-aminopropyl triethoxysilane (APTES) or 3-aminopropylethoxydimethylsilane
(APMDS) to the silica surface when both APTES and APMDS are
dissolved in water or in pure ethanol. An adsorbed water layer
is created during the attachment of APTES and APMDS and is
necessary to explain the results in water and in ethanol.
It is found that a monolayer of APMDS attaches to the silica
surface when APMDS is diluted in either water or ethanol.
In the case of APTES, it is found that a 1-2 and 5 APTES layers
attach to the glass surface when APTES is diluted in water
and in ethanol, respectively.
[Back to top]
High Coupling Efficiency in 2D Guided-Wave Photonic Band Gap
Extended Microcavities for Sensing Applications
Caterina Ciminelli, Richard M. De La Rue
and Mario N. Armenise
Label-free techniques for sensing are of great interest
for identification of molecules on a functional surface. Currently,
a growing research activity dealing with optical approaches
does contribute to the development of new devices.
A remarkable advance in the field of bio-detection is given
by the use of photonic crystals enabling to design and fabricate
high-sensitivity and compact novel optical sensors. Many photonic
crystal sensors on several different materials have been proposed
in literature. However, further improvement of the sensitivity
requires an additional research effort on the optimization
of both the design and fabrication process.
In this paper we report on the solution of the mode-mismatch
occurring at the input and output interfaces of the micro-cavity.
Mode-mismatch is responsible for the increase of the scattering
and degradation of transmission characteristics of the photonic
crystal. Optimization of the sensor design can be achieved
by using an appropriate tapering of some hole rows into reflectors.
Numerical results have proved that two physical effects occur
simultaneously, i.e. conventional tapering which is dominant
at high resonant wavelengths, and resonant conditions of the
external cavity, when the radius of the holes in the external
row is greater than that of the internal one. This last effect
is more clear at low wavelength.
[Back to top]
Scattered Colorimetry and Multivariate
Data Processing as an Objective Tool for Liquid Classification
and Mapping
Leonardo Ciaccheri and Anna G.
Magnani
Scattered colorimetry, that is multi-angle and multi-wavelength
absorption spectroscopy performed in the visible spectral
range, provides an integrated and global measurement of the
color and turbidity of liquids. By a multivariate processing
of the spectral data, the liquids can be mapped, classified
and compared according to their peculiar characteristics.
Details of the instrumentation and data processing are given,
and the results achieved by analyzing many different types
of liquids such as extra-virgin olive oil, beer, detergent
in water and lubricant oil, are presented.
[Back to top]
Fiber Optic Sensors for Biomedical Applications
Francesco Baldini, Ambra Giannetti, Andrea
A. Mencaglia and Cosimo Trono
Biomedicine is surely the area where the optical fibre
sensors can play an important role. Thanks to their potential
miniaturisation and their easy handling they are offering
unique performances in invasive or minimally invasive applications.
The immunity to electromagnetic interference and the absence
of electrical contact make the optical fibres useful also
in the case of non invasive applications for the setting of
the interrogation optoelectronic unit in a safer location,
keeping only the sensing element close to the patient’s
bedside. As a matter of fact, there are many optical fibre
sensors designed for biomedical applications and described
in the literature, but the greater part of them stops at the
prototype level, without entering the hospital. The clinical
validation, which is the necessary step after the characterisation
of the laboratory prototype, is often an insurmountable obstacle
due to the requirements of compliance with the European Directives
on Medical Devices or with the regulations of the Food and
Drug Administration. The strategy followed for the clinical
validation in the case of optical fibre sensors developed
at the Institute of Applied Physics for the detection of bile-containing
refluxes, gastric carbon dioxide and interstitial pH is described.
An example for potential non-invasive applications in point
of care testing is also given with a novel optical platform
for the interrogation of optical biochips.
[Back to top]
Chemical Sensor Networks for Gas Detection and Environmental
Monitoring
Kevin Duffin, Walter Johnstone, Andrew McGettrick,
Dave Moodie, George Stewart, Graham Thursby and Brian
Culshaw
This paper reviews the principles and prospects for optical
fibre based measurement techniques for determining gas concentrations.
Most of these exploit the precision and versatility of tuneable
diode laser spectroscopy in the near infrared. We demonstrate
the potential offered by large area multipoint totally passive
networks and establish the performance potential which these
may offer in hostile environments. These benefits include
more than adequate sensitivity for most applications, automatic
recalibration of both zero point and scale factor and the
ability to precisely determine line shape information and
in some cases perform detailed line spectrum analysis to determine
concentration, pressure and temperature simultaneously. We
also briefly describe the principles and application of photo
acoustic spectroscopy and outline the performance improvements
which tuneable diode laser systems also offer in this context.
These studies have illustrated that, in appropriate niche
applications, fibre based gas measurement systems offer substantial
long term engineering potential.
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