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| [[Image:Raman energy levels.svg|350px|thumb|Energy-level diagram showing the states involved in Raman signal. The line thickness is roughly proportional to the signal strength from the different transitions.]]
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| '''Raman spectroscopy''' ({{IPAc-en|ˈ|r|ɑː|m|ən}}; named after Sir [[C. V. Raman]]) is a [[Spectroscopy|spectroscopic]] technique used to observe vibrational, rotational, and other low-frequency modes in a system.<ref name="Gardiner">{{cite book| last = Gardiner| first = D.J.| authorlink = | title = Practical Raman spectroscopy| publisher = [[Springer-Verlag]]| series = | year = 1989| doi = | isbn = 978-0-387-50254-0}}</ref>
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| It relies on [[inelastic scattering]], or [[Raman scattering]], of [[monochromatic]] light, usually from a [[laser]] in the [[visible spectrum|visible]], [[infrared|near infrared]], or [[ultraviolet|near ultraviolet]] range. The laser light interacts with molecular vibrations, [[phonon]]s or other excitations in the system, resulting in the energy of the laser photons being shifted up or down. The shift in energy gives information about the vibrational modes in the system. [[Infrared spectroscopy]] yields similar, but complementary, information.
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| Typically, a sample is illuminated with a laser beam. Light from the illuminated spot is collected with a [[lens (optics)|lens]] and sent through a [[monochromator]]. Wavelengths close to the laser line due to elastic [[Rayleigh scattering]] are filtered out while the rest of the collected light is dispersed onto a detector.
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| Spontaneous [[Raman scattering]] is typically very weak, and as a result the main difficulty of Raman spectroscopy is separating the weak inelastically scattered light from the intense Rayleigh scattered laser light. Historically, Raman [[spectrometer]]s used [[holographic grating]]s and multiple dispersion stages to achieve a high degree of laser rejection. In the past, [[photomultiplier]]s were the detectors of choice for dispersive Raman setups, which resulted in long acquisition times. However, modern instrumentation almost universally employs [[Band-stop filter|notch or edge filters]] for laser rejection and spectrographs (either axial transmissive (AT), [[Monochromator#Czerny-Turner monochromator|Czerny-Turner (CT) monochromator]], or FT ([[Fourier transform spectroscopy]] based), and [[Charge-coupled device|CCD]] detectors.
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| There are a number of advanced types of Raman spectroscopy, including [[Surface enhanced Raman spectroscopy|surface-enhanced Raman]], [[Resonance Raman spectroscopy|resonance Raman]], tip-enhanced Raman, polarised Raman, stimulated Raman (analogous to [[stimulated emission]]), transmission Raman, spatially offset Raman, and hyper Raman.
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| == Theoretical basis ==
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| The Raman effect occurs when light impinges upon a [[molecule]] and interacts with the [[molecular orbital|electron cloud]] and the [[Chemical bond|bonds]] of that molecule. For the spontaneous Raman effect, which is a form of [[light scattering]], a [[photon]] excites the molecule from the [[Stationary state#Ground state|ground state]] to a [[Virtual state (physics)|virtual energy state]]. When the molecule relaxes it emits a photon and it returns to a different [[Rigid rotor#Quantum mechanical rigid rotor|rotational]] or [[molecular vibration|vibrational state]]. The difference in energy between the original state and this new state leads to a shift in the emitted photon's frequency away from the excitation wavelength. The Raman effect, which is a light scattering phenomenon, should not be confused with absorption (as with [[fluorescence]]) where the molecule is excited to a discrete (not virtual) energy level.
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| If the final vibrational state of the molecule is more energetic than the initial state, the emitted photon will be shifted to a lower frequency for the total energy of the system to remain balanced. This shift in frequency is designated as a [[Stokes shift]]. If the final vibrational state is less energetic than the initial state, then the emitted photon will be shifted to a higher frequency, and this is designated as an anti-Stokes shift. Raman scattering is an example of inelastic scattering because of the energy transfer between the photons and the molecules during their interaction.
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| A change in the molecular polarization potential—or amount of deformation of the electron cloud—with respect to the vibrational coordinate is required for a molecule to exhibit a Raman effect. The amount of the polarizability change will determine the Raman scattering intensity. The pattern of shifted frequencies is determined by the rotational and vibrational states of the sample. This dependence on the polarizability differs from Infrared spectroscopy where the interaction between the molecule and light is determined by the [[molecular dipole moment|dipole moment]]; this contrasting feature allows one to analyze transitions that might not be IR active via Raman spectroscopy, as exemplified by the [[rule of mutual exclusion]] in [[centrosymmetry|centrosymmetric molecules]].
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| == History ==
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| <!-- Image with inadequate rationale removed: [[image:CVRaman.jpg|right|thumb|upright|Sir Chandrasekhara V. Raman.]] -->
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| Although the inelastic scattering of light was predicted by [[Adolf Smekal]] in 1923,<ref><A. Smekal: Zur Quantentheorie der Dispersion. In: Die Naturwissenschaften. 11, Nr. 43, 1923, S. 873-875, {{doi|10.1007/BF01576902}}.</ref> it is not until 1928 that it was observed in practice. The Raman effect was named after one of its discoverers, the Indian scientist [[Sir C. V. Raman]] who observed the effect by means of sunlight (1928, together with [[K. S. Krishnan]] and independently by [[Grigory Landsberg]] and [[Leonid Isaakovich Mandelstam|Leonid Mandelstam]]).<ref name="Gardiner" /> Raman won the [[Nobel Prize in Physics]] in 1930 for this discovery accomplished using sunlight, a narrow band photographic filter to create monochromatic light, and a "[[crossed filter]]" to block this monochromatic light. He found that a small amount of light had changed frequency and passed through the "crossed" filter.
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| Systematic pioneering theory of the Raman effect was developed by Czechoslovak physicist [[George Placzek]] between 1930 and 1934.<ref>Placzek G.: "Rayleigh Streeung und Raman Effekt", In: Hdb. der Radiologie, Vol. VI., 2, 1934, p. 209</ref> The mercury arc became the principal light source, first with photographic detection and then with spectrophotometric detection. At the present time, lasers are used as light sources.
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| == Raman shift ==
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| Raman shifts are typically reported in [[wavenumber]]s, which have units of inverse length, as this value is directly related to energy. In order to convert between spectral wavelength and wavenumbers of shift in the Raman spectrum, the following formula can be used:
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| :<math>\Delta w = \left( \frac{1}{\lambda_0} - \frac{1}{\lambda_1} \right) \ , </math>
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| where <math>\Delta w</math> is the Raman shift expressed in wavenumber, λ<sub>0</sub> is the excitation wavelength, and λ<sub>1</sub> is the Raman spectrum wavelength. Most commonly, the unit chosen for expressing wavenumber in Raman spectra is inverse centimeters (cm<sup>−1</sup>). Since wavelength is often expressed in units of nanometers (nm), the formula above can scale for this unit conversion explicitly, giving
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| :<math>\Delta w (\text{cm}^{-1}) = \left( \frac{1}{\lambda_0 (\text{nm})} - \frac{1}{\lambda_1 (\text{nm})} \right) \times \frac{(10^{7}\text{nm})}{(\text{cm})} . </math>
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| == Applications ==
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| Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to the [[chemical bond]]s and symmetry of molecules. Therefore, it provides a fingerprint by which the molecule can be identified. For instance, the vibrational frequencies of SiO, Si<sub>2</sub>O<sub>2</sub>, and Si<sub>3</sub>O<sub>3</sub> were identified and assigned on the basis of normal coordinate analyses using infrared and Raman spectra.<ref name="R. K. Khanna and D. D. Stranz">{{cite journal | last = Khanna| first = R.K.| authorlink = | title = Raman-spectroscopy of oligomeric SiO species isolated in solid methane| journal = [[Journal of Chemical Physics]] | year = 1981| doi = 10.1063/1.441393| isbn = | volume = 74 | issue = 4 | pages = 2108 |bibcode = 1981JChPh..74.2108K }}</ref> The fingerprint region of organic molecules is in the ([[wavenumber]]) range 500–2000 cm<sup>−1</sup>. Another way that the technique is used is to study changes in chemical bonding, as when a substrate is added to an enzyme.
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| Raman gas analyzers have many practical applications. For instance, they are used in medicine for real-time monitoring of anaesthetic and respiratory gas mixtures during surgery.
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| In [[solid-state physics]], spontaneous Raman spectroscopy is used to, among other things, characterize materials, measure [[temperature]], and find the crystallographic orientation of a sample. As with single molecules, a given solid material has characteristic [[phonon]] modes that can help an experimenter identify it. In addition, Raman spectroscopy can be used to observe other low frequency excitations of the solid, such as [[plasmon]]s, [[magnon]]s, and [[BCS theory|superconducting gap]] excitations. The spontaneous Raman signal gives information on the population of a given phonon mode in the ratio between the Stokes (downshifted) intensity and anti-Stokes (upshifted) intensity.
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| Raman scattering by an anisotropic [[crystal]] gives information on the crystal orientation. The [[Polarization (waves)|polarization]] of the Raman scattered light with respect to the crystal and the polarization of the laser light can be used to find the orientation of the crystal, if the [[crystal structure]] (to be specific, its [[crystallographic point group|point group]]) is known.
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| Raman active fibers, such as aramid and carbon, have vibrational modes that show a shift in Raman frequency with applied stress. [[Polypropylene]] fibers also exhibit similar shifts. The radial breathing mode is a commonly used technique to evaluate the diameter of carbon nanotubes. In nanotechnology, a Raman microscope can be used to analyze nanowires to better understand the composition of the structures.
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| [[Spatially offset Raman spectroscopy]] (SORS), which is less sensitive to surface layers than conventional Raman, can be used to discover [[counterfeit drug]]s without opening their packaging, and for non-invasive monitoring of biological tissue.<ref>{{cite news | url=http://news.bbc.co.uk/2/hi/health/6314287.stm | publisher=BBC News |date=2007-01-31 | accessdate=2008-12-08 | title=Fake drugs caught inside the pack}}</ref> Raman spectroscopy can be used to investigate the chemical composition of historical documents such as the [[Book of Kells]] and contribute to knowledge of the social and economic conditions at the time the documents were produced.<ref>[http://www.nytimes.com/2007/05/28/world/europe/28kells.html Irish classic is still a hit (in calfskin, not paperback) – New York Times<!-- Bot generated title -->], nytimes.com</ref> This is especially helpful because Raman spectroscopy offers a non-invasive way to determine the best course of [[Preservation (library and archival science)|preservation]] or [[art conservation|conservation]] treatment for such materials.
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| Several research projects demonstrated usage of Raman spectroscopy as a means to detect [[explosive]]s using laser beams from safe distance ([[Portendo]], 2008,<ref>{{cite web |url=http://www.janes.com/news/transport/business/jar/jar080829_1_n.shtml |title=Raman spectroscopy portends well for standoff explosives detection |accessdate=2008-08-29 |author=Ben Vogel |date=29 August 2008 |publisher=Jane's}}</ref> [[TU Vienna]], 2012<ref>[http://www.eurekalert.org/pub_releases/2012-02/vuot-few022712.php "Finding explosives with laser beams"], a [[TU Vienna]] press-release</ref>).
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| Raman spectroscopy has also been used to confirm the prediction of existence of low-frequency phonons
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| <ref>Kuo-Chen Chou and Nian-Yi Chen (1977) The biological functions of low-frequency phonons. Scientia Sinica, 20, 447–457.</ref>
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| in proteins and DNA (see, e.g.,
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| <ref>Urabe, H., Tominaga, Y. and Kubota, K. (1983) Experimental evidence of collective vibrations in DNA double helix Raman spectroscopy. Journal of Chemical Physics, 78, 5937–5939.</ref>
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| <ref>Chou, K.C. (1983) Identification of low-frequency modes in protein molecules. Biochemical Journal, 215, 465–469.</ref>
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| <ref>Chou, K.C. (1984) Low-frequency vibration of DNA molecules. Biochemical Journal, 221, 27–31.</ref>
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| <ref>Urabe, H., Sugawara, Y., Ataka, M. and Rupprecht, A. (1998) Low-frequency Raman spectra of lysozyme crystals and oriented DNA films: dynamics of crystal water. Biophys J, 74, 1533–1540.</ref>)
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| greatly stimulating the studies of [[low-frequency collective motion in proteins and DNA]] and their biological functions.<ref>Kuo-Chen Chou (1988) Review: Low-frequency collective motion in biomacromolecules and its biological functions. Biophysical Chemistry, 30, 3–48.</ref><ref>Chou, K.C. (1989) Low-frequency resonance and cooperativity of hemoglobin. Trends in Biochemical Sciences, 14, 212.</ref>
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| Raman reporter molecules with [[olefin]] or [[alkyne]] moieties are being developed to allow for tissue imaging with SERS-labeled [[antibodies]].<ref>S. Schlücker et al. (2011). "Design and synthesis of Raman reporter molecules for tissue imaging by immuno-SERS microscopy". Journal of Biophotonics (4) 6: 453–463. [http://onlinelibrary.wiley.com/doi/10.1002/jbio.201000116/abstract ] {{doi|10.1002/jbio.201000116}}</ref>
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| == Microspectroscopy ==
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| Raman spectroscopy offers several advantages for [[microscopy|microscopic]] analysis. Since it is a scattering technique, specimens do not need to be fixed or sectioned. Raman spectra can be collected from a very small volume (< 1 µm in diameter); these spectra allow the identification of species present in that volume. Water does not generally interfere with Raman spectral analysis. Thus, Raman spectroscopy is suitable for the microscopic examination of [[mineral]]s, materials such as polymers and ceramics, [[cell (biology)|cell]]s, [[proteins]] and forensic trace evidence. A [[Raman microscope]] begins with a standard optical microscope, and adds an excitation laser, a [[monochromator]], and a sensitive detector (such as a [[charge-coupled device]] (CCD), or [[photomultiplier]] tube (PMT)). [[Fourier transform spectroscopy|FT-Raman]] has also been used with microscopes. [[microscopy#Ultraviolet microscopy|Ultraviolet microscopes]] and UV enhanced optics must be used when a UV laser source is used for Raman microspectroscopy.
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| In ''direct imaging'', the whole field of view is examined for scattering over a small range of wavenumbers (Raman shifts). For instance, a wavenumber characteristic for cholesterol could be used to record the distribution of cholesterol within a cell culture.
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| The other approach is ''[[hyperspectral imaging]]'' or ''[[chemical imaging]]'', in which thousands of Raman spectra are acquired from all over the field of view. The data can then be used to generate images showing the location and amount of different components. Taking the cell culture example, a hyperspectral image could show the distribution of cholesterol, as well as proteins, nucleic acids, and fatty acids. Sophisticated signal- and image-processing techniques can be used to ignore the presence of water, culture media, buffers, and other interferents.
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| Raman microscopy, and in particular [[confocal microscopy]], has very high spatial resolution. For example, the lateral and depth resolutions were 250 nm and 1.7 µm, respectively, using a confocal Raman microspectrometer with the 632.8 nm line from a [[Helium-neon laser|Helium-Neon]] [[laser]] with a pinhole of 100 µm diameter. Since the objective lenses of microscopes focus the laser beam to several micrometres in diameter, the resulting photon flux is much higher than achieved in conventional Raman setups. This has the added benefit of enhanced [[fluorescence quenching]]. However, the high photon flux can also cause sample degradation, and for this reason some setups require a thermally conducting substrate (which acts as a heat sink) in order to mitigate this process.
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| By using Raman microspectroscopy, ''in vivo'' time- and space-resolved Raman spectra of microscopic regions of samples can be measured. As a result, the [[fluorescence]] of water, media, and buffers can be removed. Consequently ''in vivo'' time- and space-resolved Raman spectroscopy is suitable to examine [[proteins]], [[cell (biology)|cell]]s and [[organ (anatomy)|organs]].
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| Raman microscopy for biological and medical specimens generally uses [[near-infrared]] (NIR) lasers (785 nm diodes and 1064 nm [[Nd:YAG]] are especially common). This reduces the risk of damaging the specimen by applying higher energy wavelengths. However, the intensity of NIR Raman is low (owing to the ω<sup>4</sup> dependence of Raman scattering intensity), and most detectors require very long collection times. Recently, more sensitive detectors have become available, making the technique better suited to general use. Raman microscopy of inorganic specimens, such as rocks and ceramics and polymers, can use a broader range of excitation wavelengths.<ref>{{cite journal |author=Ellis DI, Goodacre R |title=Metabolic fingerprinting in disease diagnosis: biomedical applications of infrared and Raman spectroscopy |journal=Analyst |volume=131 |issue=8 |pages=875–85 |date=August 2006 |pmid=17028718 |doi=10.1039/b602376m|bibcode = 2006Ana...131..875E |last2=Goodacre }}</ref>
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| == Polarized analysis ==
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| The polarization of the Raman scattered light also contains useful information. This property can be measured using (plane) polarized laser excitation and a [[polarizer|polarization analyzer]]. Spectra acquired with the analyzer set at both perpendicular and parallel to the excitation plane can be used to calculate the [[depolarization ratio]]. Study of the technique is useful in teaching the connections between [[group theory]], symmetry, Raman activity, and peaks in the corresponding Raman spectra.
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| The spectral information arising from this analysis gives insight into molecular orientation and vibrational symmetry. In essence, it allows the user to obtain valuable information relating to the molecular shape, for example in synthetic chemistry or polymorph analysis. It is often used to understand macromolecular orientation in crystal lattices, [[liquid crystal]]s or polymer samples.<ref name="Joseph M. Grzybowski, R. K. Khanna, E. R. Lippincott">{{cite book| last = Khanna| first = R.K.| authorlink = | title = Evidence of ion-pairing in the polarized Raman spectra of a Ba2+CrO doped KI single crystal| publisher = [[John Wiley & Sons| John Wiley & Sons, Ltd]]| series = | year = 1957| doi = 10.1002/jrs.1250040104| isbn = }}</ref>
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| == Variations ==
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| Several variations of Raman spectroscopy have been developed. The usual purpose is to enhance the sensitivity (e.g., surface-enhanced Raman), to improve the spatial resolution (Raman microscopy), or to acquire very specific information (resonance Raman).
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| * '''[[Surface Enhanced Raman Spectroscopy|Surface-enhanced Raman spectroscopy]] (SERS)''' – Normally done in a silver or gold colloid or a substrate containing silver or gold. Surface [[plasmons]] of silver and gold are excited by the laser, resulting in an increase in the electric fields surrounding the metal. Given that Raman intensities are proportional to the electric field, there is large increase in the measured signal (by up to 10<sup>11</sup>). This effect was originally observed by [[Martin Fleischmann]] but the prevailing explanation was proposed by Van Duyne in 1977.<ref>{{cite journal |author = Jeanmaire DL, van Duyne RP | title = Surface Raman Electrochemistry Part I. Heterocyclic, Aromatic and Aliphatic Amines Adsorbed on the Anodized Silver Electrode |journal = [[Journal of Electroanalytical Chemistry]] | volume = 84 | pages =1–20 | publisher = Elsevier Sequouia S.A. | year = 1977 | doi = 10.1016/S0022-0728(77)80224-6 }}</ref> A comprehensive theory of the effect was given by Lombardi and Birke.<ref>{{cite journal|author=Lombardi JR, Birke RL|title= A Unified Approach to Surface-Enhanced Raman Spectroscopy |journal = [Journal of Physical Chemistry C]| volume=112|pages= 5605–5617 | publisher = American Chemical Society | year = 2008 | doi = 10.1021/jp800167+CCC |doi_inactivedate=2014-02-01}}</ref>
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| * '''[[Resonance Raman spectroscopy]]''' – The excitation wavelength is matched to an electronic transition of the molecule or crystal, so that vibrational modes associated with the excited electronic state are greatly enhanced. This is useful for studying large molecules such as [[polypeptide]]s, which might show hundreds of bands in "conventional" Raman spectra. It is also useful for associating normal modes with their observed frequency shifts.<ref>{{cite journal| author= Chao RS, Khanna RK, Lippincott ER | title = Theoretical and experimental resonance Raman intensities for the manganate ion| journal=J Raman Spectroscopy | year = 1974| doi = 10.1002/jrs.1250030203| volume= 3| issue= 2–3| pages= 121|bibcode = 1975JRSp....3..121C | last2= Khanna | last3= Lippincott }}</ref>
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| * '''Surface-enhanced resonance Raman spectroscopy (SERRS)''' – A combination of SERS and resonance Raman spectroscopy that uses proximity to a surface to increase Raman intensity, and excitation wavelength matched to the maximum absorbance of the molecule being analysed.
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| * '''[[Angle Resolved Raman Spectroscopy|Angle-resolved Raman spectroscopy]]''' – Not only are standard Raman results recorded but also the angle with respect to the incident laser. If the orientation of the sample is known then detailed information about the phonon dispersion relation can also be gleamed from a single test.<ref>{{cite journal| author= Zachary J. Smith and Andrew J. Berger | title = Integrated Raman- and angular-scattering microscopy| journal=Opt. Lett. | year = 2008| doi = 10.1364/OL.33.000714| volume= 3 | issue= 7 | pages= 714–716|bibcode = 2008OptL...33..714S | last2= Berger }}</ref>
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| * '''Hyper Raman''' – A [[non-linear optics|non-linear]] effect in which the vibrational modes interact with the [[second harmonic generation|second harmonic]] of the excitation beam. This requires very high power, but allows the observation of vibrational modes that are normally "silent". It frequently relies on SERS-type enhancement to boost the sensitivity.<ref>{{cite journal | author = Kneipp K | title=Surface-Enhanced Non-Linear Raman Scattering at the Single Molecule Level | journal = Chem. Phys. | volume = 247 | year = 1999 | pages = 155–162 | doi = 10.1016/S0301-0104(99)00165-2 |bibcode = 1999CP....247..155K | author-separator = | author2 = and others | displayauthors = 1 | last3 = Itzkan | first3 = Irving | last4 = Dasari | first4 = Ramachandra R. | last5 = Feld | first5 = Michael S. }}</ref>
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| * '''Spontaneous Raman spectroscopy (SRS)''' – Used to study the temperature dependence of the Raman spectra of molecules.
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| * '''Optical tweezers Raman spectroscopy (OTRS)''' – Used to study individual particles, and even biochemical processes in single cells trapped by [[optical tweezers]].
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| * '''Stimulated Raman spectroscopy''' – A spatially coincident, two color pulse (with polarization either parallel or perpendicular) transfers the population from ground to a [[Rovibrational coupling|rovibrationally]] excited state, if the difference in energy corresponds to an allowed Raman transition, and if neither frequency corresponds to an electronic resonance. Two photon UV ionization, applied after the population transfer but before relaxation, allows the intra-molecular or inter-molecular Raman spectrum of a gas or molecular cluster (indeed, a given conformation of molecular cluster) to be collected. This is a useful [[molecular dynamics]] technique.
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| * '''[[Spatially offset Raman spectroscopy]] (SORS)''' – The Raman scattering beneath an obscuring surface is retrieved from a scaled subtraction of two spectra taken at two spatially offset points
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| * '''[[Coherent anti-Stokes Raman spectroscopy]] (CARS)''' – Two laser beams are used to generate a coherent anti-Stokes frequency beam, which can be enhanced by resonance.
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| * '''[[Raman optical activity]] (ROA)''' – Measures vibrational optical activity by means of a small difference in the intensity of Raman scattering from chiral molecules in right- and left-circularly polarized incident light or, equivalently, a small circularly polarized component in the scattered light.<ref>{{cite journal | author = Barron LD, Hecht L, McColl IH, Blanch EW| title = Raman optical activity comes of age | journal = Molec. Phys. | year=2004 | issue = 8 | pages = 731–744 | volume = 102 | doi=10.1080/00268970410001704399|bibcode = 2004MolPh.102..731B | last2 = Hecht| last3 = McColl| last4 = Blanch}}</ref>
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| * '''[[Transmission raman|Transmission Raman]]''' – Allows probing of a significant bulk of a [[turbid]] material, such as powders, capsules, living tissue, etc. It was largely ignored following investigations in the late 1960s ([[Bernhard Schrader|Schrader]] and Bergmann, 1967)<ref>{{cite journal | author = B. Schrader | journal = Anal. Chem. | pages = 225–230 | year = 1967| authorlink = Bernhard Schrader }}</ref> but was rediscovered in 2006 as a means of rapid assay of [[pharmaceutical]] [[dosage forms]].<ref>{{cite journal | author = P. Matousek, A. W. Parker | title = Bulk Raman Analysis of Pharmaceutical Tablets | journal = Applied Spectroscopy | year = 2006 | volume = 60 | pages = 1353–1357 | doi = 10.1366/000370206779321463 | pmid = 17217583 | issue = 12|bibcode = 2006ApSpe..60.1353M | last2 = Parker }}</ref> There are also medical diagnostic applications.<ref>{{cite journal | title = Prospects for the diagnosis of breast cancer by noninvasive probing of calcifications using transmission Raman spectroscopy | journal = Journal of Biomedical Optics | volume = 12 | year = 2007 | pages = 024008 | author = P. Matousek, N. Stone | doi = 10.1117/1.2718934 | pmid = 17477723 | issue = 2|bibcode = 2007JBO....12b4008M | last2 = Stone }}</ref>
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| * '''[[Inverse Raman effect|Inverse Raman spectroscopy]]'''.
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| * '''[[Tip-Enhanced Raman Spectroscopy|Tip-enhanced Raman spectroscopy]] (TERS)''' – Uses a metallic (usually silver-/gold-coated AFM or STM) tip to enhance the Raman signals of molecules situated in its vicinity. The spatial resolution is approximately the size of the tip apex (20–30 nm). TERS has been shown to have sensitivity down to the single molecule level and holds some promise for [[bioanalysis]] applications.<ref>Hermann P, Hermeling A, Lausch V, Holland G, Möller L, Bannert N and Naumann D. (2011). "Evaluation of tip-enhanced Raman spectroscopy for characterizing different virus strains". ''Analyst'' '''136''' (2): 1148–1152. [http://pubs.rsc.org/en/content/articlelanding/2011/an/c0an00531b ] {{doi|10.1039/C0AN00531B}}</ref>
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| * '''[[Surface plasmon polariton]] enhanced Raman scattering (SPPERS)''' – This approach exploits apertureless metallic conical tips for near field excitation of molecules. This technique differs from the TERS approach due to its inherent capability of suppressing the background field. In fact, when an appropriate laser source impinges on the base of the cone, a TM0 mode <ref>{{cite journal|last1=Novotny|first1=L|last2=Hafner|first2=C|title=Light propagation in a cylindrical waveguide with a complex, metallic, dielectric function|journal=Physical Review E|volume=50|issue=5|page=4094|year=1994|doi=10.1103/PhysRevE.50.4094|bibcode = 1994PhRvE..50.4094N }}</ref> (polaritonic mode) can be locally created, namely far away from the excitation spot (apex of the tip). The mode can propagate along the tip without producing any radiation field up to the tip apex where it interacts with the molecule. In this way, the focal plane is separated from the excitation plane by a distance given by the tip length, and no background plays any role in the Raman excitation of the molecule.<ref>{{cite journal|last1=De Angelis|first1=F|last2=Das|first2=G|last3=Candeloro|first3=P|last4=Patrini|first4=M|last5=Galli|first5=M|last6=Bek|first6=A|last7=Lazzarino|first7=M|last8=Maksymov|first8=I|last9=Liberale|first9=C|title=Nanoscale chemical mapping using three-dimensional adiabatic compression of surface plasmon polaritons|journal=Nature Nanotechnology|volume=5|page=67|year=2010|doi=10.1038/nnano.2009.348|bibcode = 2010NatNa...5...67D |last10=Andreani|first10=Lucio Claudio|last11=Di Fabrizio|first11=Enzo}}</ref><ref>{{cite journal|last1=De Angelis|first1=F|last2=Proietti Zaccaria|first2=R|last3=Francardi|first3=M|last4=Liberale|first4=C|last5=Di Fabrizio|first5=E|title=Multi-scheme approach for efficient surface plasmon polariton generation in metallic conical tips on AFM-based cantilevers|journal=Optics Express|volume=19|issue=22|page=22268|year=2011|doi=10.1364/OE.19.022268|bibcode = 2011OExpr..1922268D }}</ref><ref>{{cite journal|last1=Proietti Zaccaria|first1=R|last2=Alabastri|first2=A|last3=De Angelis|first3=F|last4=Das|first4=G|last5=Liberale|first5=C|last6=Toma|first6=A|last7=Giugni|first7=A|last8=Razzari|first8=L|last9=Malerba|first9=M|title=Fully analytical description of adiabatic compression in dissipative polaritonic structures|journal=Physical Review B|volume=86|issue=3|page=035410|year=2012|doi=10.1103/PhysRevB.86.035410|bibcode = 2012PhRvB..86c5410P |last10=Sun|first10=Hong Bo|last11=Di Fabrizio|first11=Enzo}}</ref><ref>{{cite journal|last1=Proietti Zaccaria|first1=R|last2=De Angelis|first2=F|last3=Toma|first3=A|last4=Razzari|first4=L|last5=Alabastri|first5=A|last6=Das|first6=G|last7=Liberale|first7=C|last8=Di Fabrizio|first8=E|title=Surface plasmon polariton compression through radially and linearly polarized source|journal=Optics Letters|volume=37|issue=4|page=545|year=2012|doi=10.1364/OL.37.000545|bibcode = 2012OptL...37..545Z }}</ref>
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| ==See also==
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| * [[Raman microscope]]
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| == References ==
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| {{reflist|2}}
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| == External links ==
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| * [http://www.doitpoms.ac.uk/tlplib/raman/index.php DoITPoMS Teaching and Learning Package – Raman Spectroscopy] – an introduction to Raman spectroscopy, aimed at undergraduate level.
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| * An introduction to recent advances and current areas of development in biomedical Raman spectroscopy (including video-rate biomedical imaging). [http://pubs.rsc.org/en/content/articlepdf/2013/AN/C3AN00698K ''Raman spectroscopy as a diagnostic tool,'' Analyst, 2013, 138, 3871-3884]
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| {{BranchesofSpectroscopy}}
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| {{DEFAULTSORT:Raman Spectroscopy}}
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| [[Category:Raman spectroscopy| ]]
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