Two main techniques are applied in order to detect molecular vibrational motions which are: • Infrared spectroscopy(IR). • Raman spectroscopy. Raman Spectroscopy has its unique properties which have been used very commonly and widely in Inorganic, Organic, Biological systems etc. IR is an absorption spectroscopy which measures the transmitted light . Raman spectroscopy measures the scattered light. Raman spectroscopy has some advantages over IR spectroscopy as follows: 1. Raman Spectroscopy can be used in aqueous solutions (while water can absorb the infrared light strongly and affect the IR spectrum). 2. Because of the different selection rules, vibrations inactive in IR spectroscopy may be seen in Raman spectroscopy. 3. There is no destruction to the sample in Raman Spectroscopy. In IR spectroscopy, samples need to disperse in transparent matrix. For example grind the sample in solid KBr. In RS, no such destructions are needed. 4. Glass vials can be used in Raman. 5. Raman Spectroscopy needs relative short time. So we can do Raman Spectroscopy detection very quickly. Basic Applications of Raman Spectroscopy • Qualitative tool for identifying the molecules from their vibrations. • Quantitative Raman measurements (e.g Fabric dyes studied at 30-50 ppb). Application Fields • Analytical applications(Inorganic/Organic Chemistry) • Pharmaceutical/biomedical(Food Analysis) • Material Science/Nanotechnology • Forensic/Anti-crime • Geology/Mineralogy/Gemmology • Archaeology/Art/Heritage Raman Spectroscopy application in Inorganic systems
X-ray diffraction (XRD) is used to determine the
structure of solids in inorganic systems but it can only be applied to solid state and some small reactive molecules only exist in gas phase. Also, XRD cannot distinguish between the following bonds: –CN vs. –NC, –OCN vs. –NCO,–CNO vs. – ONC, -SCN vs. –NCS. so Raman spectroscopy can be used to determine the structure of molecules. Example • In the study of Xenon Tetrafluoride. There are 3 strong bands in IR and Raman shows 2 strong bands and 2 weaker bands. These information indicates that Xenon Tetrafluoride is a planar molecule and has a symmetry of D4h. • Homo-nuclear diatomic molecules are all IR inactive and always Raman Active. • The Vibrational energies of metal-ligand bonds are generally in range of 100 to 700 cm-1, which is difficult to study in IR but easy in Raman. • Studies of boric acid solutions show that the anion formed by acid dissociation is the tetrahedral B(OH)4- rather than H2BO3-. • Dissociation constants for strong acids such as HNO3, H2SO4 and H2SeO4 have been calculated from Raman measurements. • Metal-oxygen bonds are also Raman active. Spectra for such species as VO34- , Al(OH)4- , Si(OH)62- have been obtained. Raman Spectroscopy Application in Organic Systems
Qualitative analysis of organic compounds can be
done base on the characteristic vibrations table. RS is similar to IR in that they have regions that are useful for functional group detection and fingerprint regions that permit the identification of specific compounds. • Olefinic Functional Group Information The double-bond stretching vibration for olefins results in weak and sometimes undetected IR absorption. On the other hand, the Raman band (which like the IR band, occurs at about 1600 cm -I) is intense, and its position is sensitive to the nature of substituents as well as to their geometry. • Estimation of ring size in paraffins They have a characteristic Raman band in the region of 700 to 1200cm-1.This band has been attributed to a breathing vibration in which the nuclei move in and out symmetrically with respect to the center of the ring. The position of the band decreases continuously from 1190 cm- for cyclo- propane to 700 cm-I for cyclo-octane, Raman spectroscopy thus appears to be an excellent diagnostic tool for the estimation of ring size in paraffins. Surface Enhanced Raman Spectroscopy (SERS) Applications One method to amplify weak Raman signals is to utilize surface enhanced Raman scattering (SERS). It is a sensitive technique which offers orders of magnitude increases in Raman intensity. Enhancement factors can be as much as 103 to 1010 times which are sufficient to detect even single molecule. Using Surface-enhanced Raman spectroscopy (SERS) can be a more promising choice for obtaining a faster detection of COVID-19 than the PCR. PCR protocol amplifies the single segment of DNA to 100 billion copies after 40 doubling cycles to provide sufficient intensities of fluorescent signals for virus detection, which takes hours. While SERS is using ramen scattering technique that needs single molecule only by selecting the SERS laser on it which gives us a high intensity signals that can be analyzed within minutes as it doesn’t need any amplification of the RNA or DNA. It is a portable device permits testing for COVID-19 to be used widely in any community, for instance in rural areas, schools, and work facilities, by anyone. Select a laser ray on a sample taken from a patient, use the silver and gold nanoparticles as dye to coat the DNA to produce signals, and finally analyze the signal to give the Raman fingerprint of COVID-19’s DNA. Raman Spectroscopy Applications in Archaelogoy 1. The Raman microprobe has played a critical role in the authentication of some presumed ancient documents such as the Vinland map. In the map, the presence of TiO2, in the ink was shown by Raman microscopy. 2. Raman microscopy supported by X‐ray diffraction (XRD) was used to detect traces of mineralogical phases of volcanic origin and contaminations in red and yellow pigments recovered from the archaeological site of Pompeii after being buried for hundreds of years. References • Skoog Holler crouch - Principles of instrumental analysis 6th edition 2007. • Journal of Pharmaceutical and Biomedical Analysis Volume 147, 5 January 2018, Pages 458-472. • https://www.nature.com/subjects/raman-spectroscopy