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wuxuepeng1

金虫 (小有名气)

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专业: 金属有机化学

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II. Using Fluoro/Lumophores for Signaling:
The advantages of molecular fluorescence or lumi- nescence  for  sensing and switching can be  sum- marized;7,8 high  sensitivity of detection down  to the single molecule,38a,40-44  “on-off” switchability, feasi- bility  of human-molecule communication, subnan- ometer spatial  resolution with submicron visuali- zation34-38  and  submillisecond temporal resolution. Furthermore, many of the  structural features which control (reduce) fluorescence efficiency have  been delineated;45-51  double-bond torsion, low energy nπ* levels, “heavy” atoms, weak  bonds, and  opportunities for photoinduced electron transfer (PET) or electronic energy transfer (EET). The importance of extensive delocalization in  compensating for  these negative effects  has  also been  appreciated.  Therefore, consid- erable opportunities exist for modulating these struc- tural features via chemical or physical means at the molecular level.
Our emphasis  will be on the transduction  of discrete and  stoichiometric recognition events into fluorescence signals. However, nonstoichiometric interactions such  as solvation have much to teach us in  this field. In  fact,  it will  become  clear that the information gleaned from the fluorescence effects  due to nonstoichiomeric interactions is not only important in  its  own  right.  Such  data can  be adapted, some- times rather directly, by designers of molecular and atomic recognition systems.
The  plan of the review is  as  follows. First,  we consider emissive photophysical effects  arising from monofluoro/lumophore components.  Additional com- ponents if present will only serve in auxiliary capaci- ties. The  supramolecular aspects will  mainly arise from the  necessary interaction of the  environment or guest with the  fluoro/lumophore.  Most  of the  prin- cipal  types of excited states encountered by organic and  inorganic chemists will  be  represented in  sec- tions III-VII.  From then on, the  photophysical phe- nomena themselves take on a supramolecular char- acter, i.e. two or more  components are  essential for the  phenomenon. Their perturbation by the  environ- ment/guest will form the  second layer of supramolecu- larity.  One  of these phenomena, photoinduced elec- tron transfer (PET)  can  occur  in  monofluoro/lumophore systems (section VIII). Others require multi- fluorophore assemblies for their operation. Monomer/ excimer equilibria  and electronic energy transfer (EET) are taken up in sections IX and  X, respectively.

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