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3 SENSING BASED ON LOCALIZED SURFACE PLASMON RESONANCE                        APPLICATIONS




                                       analyte

                                                                                increased thickness
                               ligand (receptor)


                                      Substrate or surface of nanoparticles
                  Figure 3.2
                  Principle of affinity biosensor. When analyte molecules are bound to receptors, the average thickness of surface layer
                  increases.

                  (affinity biosensor) and the other is a Raman sensor             gold nanoparticle
                  that provides a vibration spectrum. The former is
                  based on the feature of LPR that the resonance con-
                  dition is sensitive to the dielectric constants of the                        analyte
                  ambient medium, and the latter is based on the phe-
                  nomenon that a large electric field is produced at    core(φ=5~50μm)
                  the resonance condition.  The large electric field
                  provides us with a huge enhancement of the Raman
                  signal. This is called surface enhanced Raman scat-       clad
                  tering (SERS). Since Raman signal is usually weak,                              receptor
                  it should be enhanced to probe the signal from very                      silane coupling agent
                  thin films or nanometer structures. Both sensors
                  have different characters as described below.  Figure 3.3
                    The affinity biosensor has been widely used in
                  these days. Its principle is illustrated in Fig. 3.2. The  Schematic picture of the optical fiber sensor [8]. Gold
                                                                 nanoparticles with receptor molecules are immobilized at
                  receptor molecules, which have affinity to the analyte  an endface of an optical fiber. When sample solution
                  molecules such as proteins and DNA, are immobi-  involves analyte molecules, they bound to the receptor, and
                  lized to a surface of a substrate or nanoparticles. Gold  change in the scattering efficiency occurs. As a result, the
                  is used as a substrate or nanoparticle materials  return light intensity and spectrum are changed.
                  because it is inert. When a sample solution involves
                  analyte molecules, they react with the receptor mole-
                  cules immobilized on the surface, resulting in an  LPR sensor that the authors have developed is shown in
                  increase in a thickness of the surface dielectric layer.  Fig. 3.3 [8]. The return light from the endface of the
                  Although the size of DNA and proteins are in the  optical fiber is measured for biosensing.  The gold
                  range of 1–10 nm, the average thickness increase is  nanoparticles are immobilized at the endface with a
                  about in the order of 0.01–0.1 nm, because the mole-  surface coverage of 10–30%. The return light involves
                  cules do not form a densely packed structure.  both components of reflected light at the surface and
                  Therefore highly sensitive method that can probe such  scattered light by the particles. Since the diameter of
                  a small increase in thickness is needed. The method  the optical fiber is small,  100  m (the core diameter
                  widely used is labeling with fluorescent choro-  is 5–50  m), we can probe proteins in a solution of 50
                  mophore. It is a very sensitive method, but labeling  nL using a special sample holder, whereas a current
                  process is required. Label-free methods, surface plas-  SPR system requires a sample volume of  50  L. This
                  mon resonance (SPR) [4–6] in attenuated total reflec-  feature has a great advantage because the amount of
                  tion (ATR) geometry and quartz crystal microbalance  biological molecules is usually little.
                  (QCM) [7], have been developed.  They are good  For exhaustive investigation of proteins and DNA,
                  probes that can monitor the small increase in thick-  the sensing array is needed to perform multichannel
                  ness of the surface layer. However it is difficult to  sensing. DNA chips have been widely used in these
                  make the probes with a size of micrometers.    days, but labeling process is required. As a label-free
                    On the other hand, LPR sensors using metallic  detection, the SPR sensing array using ATR optics has
                  nanoparticles have the following remarkable features.  been investigated. LPR in metallic nanoparticles can
                  The LPR sensor probes are small and the optical setup  also be used for label-free sensing array. Since this
                  is simple. In principle, the sensor can be made with one  system is simple, it is possible to make a high-density
                  nanoparticle. A schematic picture of the optical fiber  sensing array chip.

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