An International Quarterly Research Journal

ACL

                                                                                                      ISSN : 0971 - 9822

                                                                           Vol 18,  No 1&2,  Jan-June, 2014

Asian Chemistry Letters                                                                                                         Vol. 18, Nos. 1&2 (2014)1-45

 

Raman spectroscopy through 50 years: A personal retrospective from Copenhagen

 

 Ole Faurskov Nielsen

Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Copenhagen, Denmark

____________________________________________________________________________________________________________________________________

Raman spectra in the pre-laser period with mercury arc excitation and exposure time up to 20 hours illustrate how time consumning it was to obtain spectra, even of liquids. The initial laser period from 1968 includes Raman spectra with He/Ne laser excitation of single crystals and temperature studies. Low wavenumber Raman spectra in the R(v) representation were presented for the first time in 1978 at the sixth ICORS meeting in Bangalore celebrating the 50th anniversary of Raman’s discovery. Low wavenumber bands around 60 cm-1 for CH3I and CD3I were assigned to librational motions due to the observed isotope effects. A comparison of far-IR and R(v) spectra of a large number of molecular liquids confirmed the concept of librational motions. Temperature studies revealed the presence of either damped or even overdamped molecular librations. R(v) spectra of hydrogen bonded acetic acid in the liquid state showed the existence of centrosymmetric dimers. A common convention for axis direction in the presentation of Raman spectra is proposed. Collectivity of vibrational motions in biomolecules are presented in terms of resonance energy transfer (RET) and coalescence of bands in mixtures of isotopomers (CBMI). Results are presented for liquid amide isotopomers and aspects of signal transducing along hydrogen bonded patterns in proteins are discussed. Surface enhanced Raman spectroscopy (SERS) are used in combination with various types of calculations to elucidate the geometry of molecular binding to a silver surface. In particular DNA intercalating molecules were investigated. Raman spectroscopy is used in structural analyses of peptides and proteins in both the solid sate and in aqueous solutions. Fluorescence is avoided by use of laser excitation in the NIR-region. A band around 170-180 cm-1 in the R(v) representation of 2H-, 17O-, 18O-isotopomers of liquid water is assigned to hydrogen bonded water molecules in a tetrahedral conformation. A sharp band at 110 cm-1 in nucleotides is assigned to an out-of –plane mode for atoms in Watson-Crick base pairing. A simlar out-of-plane mode were found around 100-110 cm-1 in Raman spectra of isotopically 2H-, 13C-, 15N-, 18O-substituted amides. This mode might be important for breaking of hydrogen bonds in proteins. Examples show the importance of Raman spectroscopy as a non invasive technique in studies af art and archaelogical objects. Raman spectroscopy is a feasible method for investigating the structure of proteins and lipids in intact human skin, hair and nail. Examples are given for mummified skin and human skin with both benign and malignant skin diseases. The chemical composition of meteorites and inorganic compounds of interest in heterogenous catalysis is investigated. Low wavenumber Raman spectra in the R(v) representation is a very important tool in studies of osmotic coefficients and water activities of strong electrolytes in the context of atmospheric aerosols and preservation of foodstuff. © Anita Publications.All rights reserved.

Keywords: IR spectra, Raman spectra, Raman shifts (cm-1), Electronic transitions, Emission spectra, Molecular polarisability.

Total Refs: 178

____________________________________________________________________________________________________________________________________

Refs:

  1. Raman C V, Krishnan K S, Nature, 121(1928)501.
  2. Landsberg G, Mandelstam L, Naturwissenschaften, 16(1928)557 .
  3. Smekal A, Naturwissenschaften, 11(1923)873.
  4. Langseth A, Spektroskopiske Studier, Bianco Lunos Bogtrykkeri A/S, Copenhagen, (1930).
  5. Bak B, Elementary Introduction to Molecular Spectra, North-Holland Publishing Company, Amsterdam (1962).  
  6. Christensen D H, Nielsen O F, J  Mol  Spectrosc, 24(1967)477.
  7. Christensen D H, Nielsen J T, Nielsen O F, J  Mol  Spectrosc, 25(1968)197.
  8. Baranska H, Christensen D H, Nicolaisen F M, Nielsen O F, Klaeboe P, Acta Chem  Scand, 25(1971)2364.
  9. Christensen D H, Jensen P W, Nielsen J T, Nielsen O F, Spectrochim  Acta, 29A(1973)1393.
  10. Bjarnov E, Christensen  D H, Nielsen O F, Augdahl E, Kloster-Jemsen E, Rogstad A, Spectrochim  Acta30A(1974)1255.
  11. Rogstad A, Klaboe P, Baranska H, Bjarnov E, Christensen D H, Nicolaisen F, Nielsen O F, Cyvin B N, Cyvin S J, J  Mol Struct, 20(1974)403.
  12. Winther F, Guarnieri A, Nielsen O F, Spectrochim  Acta, 31A(1975)689.
  13. Knudsen J M, Larsen E, Moreira J E, Nielsen O F, Acta Chem  Scand, A 29(1975)833.
  14. Bak B, Christensen D H, Kristiansen N A, Nicolaisen F, Nielsen O F,  Acta Chem  Scand, A 37(1983)601.
  15. Nicolaisen F M, Nielsen O F, Vala M, J  Mol Struct, 13(1972)349.
  16. Eriksson A, Nielsen O F, J  Mol Struct, 48(1978)343.
  17. Anthoni U, Nielsen P H, Nielsen O F, J  Mol Struct,116(1984)175.
  18. Anthonsen J W, Christensen D H, Nielsen J T, Nielsen O F, Spectrochim  Acta, 32A(1976)971.
  19. Hornig D F, J  Chem  Phys, 16(1948)1063.
  20. Winston H, Halford R S, J  Chem  Phys, 17(1949) 607.
  21. Proceedings of the Second International Conference on Light Scattering in Solids, (ed Balkanski M) Paris, July 19-23, Flammarion Sciences, (1971).
  22. Light Scattering in Solids IX, Novel Materials and Techniques, (eds Cardona M and Merlin R) Topics in Applied Physics, Springer Verlag, Heidelberg, 108(2007)1.
  23. Nielsen O F, Christensen D H, Lund P A, Praestgaard E in Proceedings of the Sixth International Conference on Raman Spectroscopy, eds Schmid E D, Krishnan R S, Kiefer W, Schrötter H W, Heyden and Son Ltd, London, Philadelphia, Rheine, 2(1978)208.
  24. Mallinson P D, J Mol Spectrosc, 55(1975)94.
  25. Brooker M H, Nielsen O F, Praestgaard E, J Raman Spectrosc, 19(1988)71.
  26. Murphy W F, Brooker M H, Nielsen O F, Praestgaard E, Bertie J E, J Raman Spectrosc, 20(1989)695.
  27. Nielsen O F, Annu  Rep  Prog  Chem  Sect  C,  90(1993)3.
  28. Nielsen O F, Annu  Rep  Prog  Chem  Sect  C, 93(1997)57.
  29. Kirilllov S A, Perova T S, Nielsen O F, Praestgaard E, Rasmussen U, Kolomiyets T M, Voyiatzis G A, Anastasiadis S H, J  Mol  Struct,  479(1999)271
  30. Kirillov S A, Nielsen O F, J  Mol  Struct,  526(2000)317.
  31. Baranov A V, Perova T S, Petrov V I, Vij J K, Nielsen O F, J Raman Spectrosc, 31(2000)819.
  32. Lund P-A, Nielsen O F, Praestgaard E, Chem  Phys, 28(1978)167.
  33. Rønne C, Jensby K, Loughnane, B J, Fourkas J, Nielsen O F, Keiding S R, J  Chem  Phys, 113(2000)3749.\
  34. Perova T S, Christensen D H, Nielsen O F, Vibrational Spectrosc, 15(1997)61.
  35. Perova T S, Vij J K, Christensen D H, Nielsen O F, J  Mol  Struct,  479(1999)111,
  36. Nielsen O F, Christensen D H, Fajolles C, J Mol  Liq, 45(1990)77.
  37. Nielsen O F, Fajolles C, Lund P-A, Praestgaard E, J Mol  Liq, 43(1989)13.
  38. Colaianni S E M, Nielsen O F, J  Mol  Struct,  347(1995)267.
  39. Nielsen O F, J Raman Spectrosc, 20(1989)221.
  40. Nielsen O F, Lund P A, J Chem  Phys, 78(1983)652.
  41. Mills I, Cvitas T, Homann K, Kallay N, Kuchitsu K, Quantities, Units and Symbols in Physical Chemistry, Blackwell Scientific Publications, Oxford, London, Edinburgh, Boston, Palo Alto, Melbourne, Second Edition, (1988).
  42. Cohen E R, Cvitas T, Frey J G, Holmström B, Kuchitsu K, Marquardt R, Mills I, Pavese F, Quack M, Stohner J, Strauss H L, Takami M, Thor A J, Quantities, Units and Symbols in Physical Chemistry, IUPAC 2007, RSC Publishing, Cambridge, UK, Third Edition, (2007).
  43. Tu A T, in Spectroscopy of Biological Systems (eds Clark R J H and Hester R E) ,John Wiley and Sons, Chichester, New York, Brisbane, Toronto, Singapore, 13(1986)47.
  44. Dawson P, J Phys Chem  Solids, 36(1975)1401.
  45. Decius J C, Hexter R M, in Molecular Vibrations in Crystals McGraw-Hill Inc. United States of America, (1977).
  46. Nielsen O F, Jacobsen K L, Westh P, Radovic T, Larsen B D, Christensen D H, J  Mol  Struct, 598(2001) 9.
  47. Olejnik S, Posner A M, Quirk J P, Clays and Clay Minerals, 19(1971)83.
  48. Nielsen O F, Mortensen A, Yarwood J, Shelley V, J  Mol  Struct,  378(1996)1
  49. Mortensen A, Nielsen O F, Yarwood J, Shelley V,  J  Phys Chem,  98(1994)5221.
  50. Mortensen A, Nielsen O F, Spectrochim. Acta,  A 51(1995)1345.
  51. Mortensen A, Nielsen O F, Yarwood J, Shelley V, Vibrational Spectrosc, 8(1994)37.
  52. Mortensen A, Nielsen O F, Yarwood J, Shelley V, J Raman Spectrosc, 26(1995)669.
  53. Mortensen A, Nielsen O F, Yarwood J, Shelley V, J Phys Chem, 99(1995)4435.
  54. Nielsen O F, Asian J Phys,7(1998)179.
  55. Nielsen O F, Asian J  Phys, 9(2000)139.
  56. Nielsen O F, Johansson C, Christensen D H, Hvidt S, Flink J, Hansen S H, Poulsen F, J  Mol  Struct,  552 (2000)71.
  57. Guo H, Karplus M, J  Phys  Chem,  98(1994)7104.
  58. Torii H, Tasumi T, Kanazawa T, Tasumi M, J  Phys  Chem, B 102(1998)309.
  59. Chen X G, Schweitzer-Stenner R, Krimm S, Mirkin N G, Asher S A,  J Am  Chem Soc, 116(1994)11141.
  60. Sieler G, Schweitzer-Stenner R, J Am  Chem Soc,119(1997)1720.
  61. Nielsen O F, Johannson C, Jacobsen K L, Christensen D H, Wiegell M R, Pedersen T, Gniadecka M, Wulf H C, Westh P, Proceedings SPIE,  4098(2000)160.
  62. Fleischmann M, Hendra P J, Mcquillan A J, Chem  Phys  Lett, 26 (1974) 163.
  63. Albrecht M G, Creighton J A, J. Am . Chem. Soc, 99, (1977) 5215.
  64. Le Pecq J-B, Xuong N D, Gosse C, Paoletti C, Proc Nat  Acad Sci, USA, 71(1974)5078.
  65. Dodin G, Schwaller M-A, Aubard J, Paoleti C, Eur J Biochem, 176(1988)371.
  66. Aubard J, Bernard S, Levi G, Grosroyat H, Christensen D H, Sørensen G O, Nielsen O F, J Raman Spectrosc, 24(1993)681.
  67. Binoy J, Joe I H, Jayakumar V S, Nielsen O F, Aubard J, Laser Phys Lett, 2(2005)544.
  68. Nissum M, Nielsen O F, Jensen F, Jensen P W, J  Raman Spectrosc, 26(1995)1009.
  69. Nissum M, Jacobsen J P, Nielsen O F, Jensen P W, Biospectroscopy, 3(1997)207.
  70. Egholm M, Buchardt O, Nielsen P E, Berg R H, J Am  Chem Soc, 114(1992)1895.
  71. Colaianni S E M, Aubard J, Hansen S H, Nielsen O F, Vibrational Spectrosc, 9(1995)111.
  72. Nielsen O F, in Methods for Structural Analysis of Protein Pharmaceuticals  (eds Jiskoot W, Crommelin D J A), AAPS Press, Arlington USA, (2005) 167.
  73. Brooker M H, Nielsen O F, Christensen D H, J Raman Spectrosc, 26(1995)331.
  74. Refstrup P, Nielsen O F, Bang S, Asian J  Phys, 11(2002)1.
  75. Asher S A, Anal Chem,  65(1993)59.
  76. Thomas G J, Annu  Rev Biophys Biomol  Struct, 28 (1999) 1.
  77. Soldatova A V, Ibrahim M, Olson J S, Czernuszewicz R S, Spiro T G, J Am  Chem Soc, 132(2010)4614.
  78. Abdali S, Refstrup P, Nielsen O F, Bohr H, Biopolymers (Biospectroscopy), 72(2003)318.
  79. Merrifield RB, J Am  Chem Soc, 85(1963)2149.
  80. Larsen B D, Holm A, Christensen D H, Werner F, Nielsen O F, Innovation and Perspectives in Solid Phase Synthesis, Peptides, Polypeptides and Oligonucleotides,(ed Epton R) Intercept Limited, Andower, UK, (1992)363.
  81. Larsen B D, Christensen D H, Holm A, Zillmer R, Nielsen O F, J Am  Chem Soc,115(1993)6247.
  82. Ryttersgaard J, Larsen B D, Holm A, Christensen D H, Nielsen O F, Spectrochim  Acta,  A 53(1997)91.
  83. Hansen C L, Hansen P R, Callisen T H, Bauer R, Nielsen O F, J Raman Spectrosc, 33(2002)142.
  84. Nielsen O F, Chem  Phys  Lett,  60(1979)515.
  85. Strutt J W (Lord Rayleigh), The Theory of Sound, 2nd edn, Macmillan, London, Vol I, (1894)110.
  86. Brodersen S, J  Mol  Spectrosc, 3(1959)450.
  87. Walrafen G E, in Water. A Comprehensive Treatise, (ed Franks F) Plenum Press, New York-London, (1972) 151.
  88. Frosch M, Bilde M, Nielsen O F, J Phys Chem A, 114(2010)11933.
  89. Sobron F, Puebla F, Rull F, Nielsen O F, Chem  Phys Lett, 185(1991)393.
  90. Gaiduk V I, Nielsen O F, Perova T S, J  Mol  Liq, 95(2002)1.
  91. Gaiduk V I, Nielsen O F, Crothers D S F, J  Mol  Liq, 137(2008)92.
  92. Nielsen O F, Lund P-A, Praestgaard E, J Raman Spectrosc, 9(1980)286 .
  93. Nielsen O F, Lund P-A, Praestgaard E, J J Raman Spectrosc, 11(1981)92.
  94. Nielsen O F, Christensen D H, Aubard J, Dodin G, J Raman Spectrosc, 15(1984)134.
  95. Nielsen O F, Lund P-A, Petersen S B, J Raman Spectrosc, 11(1981)493.
  96. Nielsen O F, Lund P-A, Petersen S B, J Am  Chem Soc, 104(1982)1991.
  97. Nielsen O F, Lund P-A, Petersen S B, J Am  Chem Soc, 104(1982)5004.
  98. Nielsen O F, Praestgaard E, Naturens Verden, 10(1983)369.
  99. Nielsen O F, Lund P-A, Nielsen L S, Praestgaard E, Biochem  Biophys  Res  Com, 111(1983)120.
  100. Nielsen O F, Lund P-A, Chem  Phys  Lett, 78(1981)626.
  101. Nielsen O F, Christensen D H, Rasmussen O H, J  Mol  Struct,  242(1991)273.
  102. Nielsen O F, Bigio I J, Olsen I, Berquier J-M, Chem  Phys Lett, 132(1986)502.
  103. Nielsen O F, Lund P-A, Praestgaard E, J  Chem Phys, 77(1982)3878.
  104. Jensen J H, Christiansen P L, Skovgaard O, Nielsen O F, Bigio I J, Phys  Lett  A, 117(1986)123.
  105. Oestergaard N, Christiansen P L, Nielsen O F, J J  Mol  Struct (Theochem), 235(1991)423.
  106. Nielsen O F, J  Mol  Struct,  175(1988)251.
  107. Nielsen O F, Christensen D H, Praestgaard E, J  Chem Phys, 82(1985)1183.
  108. Nielsen O F, Dodin G, Acta Chem  Scand, 44(1990)1080.
  109. Nielsen O F, Christensen D H, Praestgaard E, Biochem  (Life Sci Adv), 7(1988)57.
  110. Hansen S B, Christensen D H, Nielsen O F, Spectrochim Acta, A49(1993)769.
  111. Hansen S B, Christensen D H, Nielsen O F, J  Chem Phys, 90(1993)1797.
  112. Davydov’s Soliton Revisited (eds Christiansen P L, Scott A C), NATO ASI Series B: Physics, Plenum Press, 243 (1990).
  113. Nielsen O F, in Davydov’s Soliton Revisited (eds Christiansen P L, Scott A C), NATO ASI Series B: Physics, Plenum Press, 243(1990)379.
  114. Filtenborg T, Nielsen O F, Asian Chem Lett, 15(2011)247.
  115. Kuvvetli F, Alling A, Kendix E, Kalsbeek N, Nielsen O F, Meddelelser om Konservering,  (2007)28.
  116. Kendix E, Nielsen O F, Christensen M C, J Raman Spectrosc, 35(2004)796.
  117. Saverwyns S, J Raman Spectrosc, 41(2010)1525.
  118. Brown K L, Clark R J H, Anal Chem,  74(2002)3658.
  119. Brown S, Clark R J H, Spectrochim  Acta,  A 110(2013)78.
  120. Towe K M, Clark R J H, Seaver K A, Archaeometry, 50(2008)887.
  121. Christensen M, Nielsen O F, Jensen P, Schnell U, J  Mol  Struct, 735(2005)267.
  122. Christensen M, Frosch M, Jensen P, Schnell U, Shashoua Y, Nielsen O F, J Raman Spectrosc, 37(2006) 1171.
  123. Shashoua Y, Berthelsen M-B L D, Nielsen O F, J Raman Spectrosc, 37(2006)1221.
  124. Moreno Y M, Christensen D H, Nielsen O F, Asian J Spectrosc, 4(2000)49.
  125. Kuvvetli F, Kendix E, Kalsbeek N, Nielsen O F, Meddelelser om Konservering, (2006) 62.
  126. Reeler N E A, Nielsen O F, Spaabæk L, Jørgensen M, Kjaergaard H G, Asian Chem  Lett, 17(2013)1.
  127. L. Stryer, Biochemistry Third Edition, Freeman W H and Company, New York, (1988).
  128. Gniadecka M, Wulf H C, Nielsen O F, Christensen D H, Hansen J P H, J Raman Spectrosc,  28(1997)179.
  129. Gniadecka M, Edwards H G M, Hansen J P H, Nielsen O F, Christensen D H, Guillen S E, Wulf H C J Raman Spectrosc, 30(1999)147.
  130. Edwards H G M, Gniadecka M, Petersen S, Hansen J P H, Nielsen O F, Christensen D H, Wulf H C, Vibrational Spectrosc, 28(2002)3.
  131. Petersen S, Nielsen O F, Christensen D H, Edwards H G M, Farwell D W, David R, Lambert P, Gniadecka M, Wulf H C, J Raman Spectrosc, 34(2003)375.
  132. Gniadecka M, Nielsen O F, Christensen D H, Wulf H C, J Invest  Dermatology,110(1998)393.
  133. Gniadecka M, Nielsen O F, Wessel S, Heidenheim M, Christensen D H, Wulf H C, J  Invest  Dermatology 111(1998)1129.
  134. Gniadecka M, Wulf H C, Nielsen O F, Christensen D H, Hercogova J, Photochem  Photobiol,  66(1997) 418.
  135. Gniadecka M, Wulf H C, Mortensen N M, Nielsen O F, Christensen D H,  J Raman Spectrosc, 28(1997) 125.
  136. Gniadecka M, Philipsen P A, Sigurdson S, Wessel S, Nielsen O F, Christensen D H, Hercogova J, Rossen K, Thomsen H K, Gniadecki R, Hansen L K, Wulf H C, J  Invest  Dermatology, 122(2004)443.
  137. Nielsen O F, Greve T M, Andersen K B, Engdahl A, Nelander B,  Asian Chem  Lett, 13(2009)99.
  138. Gniadecka, Nielsen O F, Wulf H C, J  Mol  Struct,  661-662(2003)405.
  139. Greve T M, Andersen K B, Nielsen O F, Spectroscopy, 22(2008)437.
  140. Greve T M, Andersen K B, Nielsen O F, Spectroscopy, 22(2008)405.
  141. Halborg J, Prause J U, Toft P B, Skjødt K, Tommerup N R, Nielsen O F, Heegaard S, Acta Ophthalmologica,  87(2009)672.
  142. Binoy J, Abraham J P, Joe I H, Jayakumar V S, Pettit G R; Nielsen O F, J Raman Spectrosc, 35(2004) 939.
  143. Sajan D, Abraham J P, Joe I H, Jayakumar V S, Aubard J, Nielsen O F,  J Mol Struct, 889(2008)129.
  144. James C, Pettit G R, Nielsen O F, Jayakumar V S, Joe I H,  Spectrochim Acta, A 70(2008)1208.
  145. Padmaja L, Ravikumar C, Sajan D, Joe I H, Jayakumar V S, Pettit G R,  Nielsen O F,  J Raman Spectrosc, 40(2009)419.
  146. Abraham J P, Joe I H, George V, Nielsen O F, Jayakumar V S, Spectrochim Acta,  A 59 (2003) 193.
  147. Binoy J, Abraham J P, Joe I H, George V, Jayakumar V S, Aubard J, Nielsen O F,  J Raman Spectrosc, 36 (2005)63.
  148. Borowicz P, Nielsen O F, Christensen D H, Adamowicz L, Les A, Waluk J, Spectrochim  Acta,   A 54 (1998)1291.
  149. Palafox M A, Nielsen O F, Lang K, Garg P, Rastogi V K, Asian Chem  Lett,  8 (2004)81.
  150. Vester J, Felby C, Nielsen O F, Barsberg S, Applied Spectrosc, 58(2004)404.
  151. Nielsen O F, Chem  Phys Lett, 66(1979)350.
  152. Nielsen O F, Lund P-A, Nicolaisen F M, Acta Chem Scand, A 34(1980)749.
  153. Nielsen O F, Lindstrom T, Lund P A, Acta Chem Scand,  A 36(1982)623.
  154. Biering I, Larsen K, Garp T, Christensen D H, Koch C B, Jensen P W, Nielsen O F, Asian Chem  Lett, 7 (2003) 99.
  155. Larsen K L, Nielsen O F, Asian Chem Lett, 7(2003)229.
  156. Larsen K L, Nielsen O F, J Raman Spectrosc, 37(2006)217.
  157. Chen Y, Hyltoft J, Jacobsen C J H, Nielsen O F, Spectrochim  Acta,  A 51(1995)2161.
  158. Chen Y, Hyltoft J, Jacobsen C J H, Christensen D H Nielsen O F, Spectrochim Acta,  A 50(1994)1879.
  159. Mortensen A, Christensen D H, Nielsen O F, Pedersen E, J Raman Spectrosc, 22(1991)47.
  160. Mortensen A, Christensen D H, Nielsen O F, Pedersen E, J Raman Spectrosc, 24(1993)667.
  161. Glerup M, Nielsen O F, Christensen D H, J  Mol  Struct,  509(1999)165.
  162. Chen Y, Christensen D H, Nielsen O F, Pedersen E,  J  Mol  Struct,  294(1993)215.
  163. Chen Y, Christensen D H, Sørensen G O, Nielsen O F, Pedersen E,  J  Mol  Struct,  299(1993)61.
  164. Chen Y, Christensen D H, Sørensen G O, Nielsen O F, Jacobsen C J H, Hyldtoft J,  J  Mol  Struct,  319 (1994)129.
  165. Chen Y, Christensen D H, Nielsen O F, Hyltoft J, Jacobsen C J H, Spectrochim  Acta,  A 51(1995)595.
  166. Piszczek P, Grodzicki A, Nielsen O F, Engelen B, J  Mol  Struct,  604(2002)19.
  167. Glerup M, Nielsen O F, Poulsen F W, J. Solid State Chem. 160 (2001) 25.
  168. Glerup M, Nielsen O F, Poulsen F W,  Asian J  Phys, 13(2004)25.
  169. Poulsen F W, Bjerrum N J, Nielsen O F, Inorg Chem, 13(1974)2693.
  170. Fehrmann R, Barner J H, Bjerrum N J, Nielsen O F, Inorg. Chem. 20 (1981) 1712.
  171. Masterton W L, Hurley C N, Chemistry, Principles and Reactions, Sixt Edition, Brooks/Cole Cengage Learning, Belmont, CA, USA (2009).
  172. Bjerrum N, Fysisk Tidsskrift 15 (1917). Translated in Niels Bjerrum. Selected Papers, ed Christiansen J A, Bohr N et al., Munksgaard, Copenhagen (1949) 58.
  173. Robinson R A, Stokes R H, Electrolyte Solutions, Butterworths, London, Sec Edition (1959).
  174. Nielsen O F, Bilde M, Frosch M, Spectroscopy: An International Journal 27 (2012) 565.
  175. Nielsen O F, in Handbook of Raman Spectroscopy (eds Lewis I R, Edwards H G M), Marcel Dekker, Inc, New York, Basel (2001) 593.
  176. Nielsen O F, in Perspectives in Modern Optics and Optical Instrumentation (eds Joseph J, Sharma A, Rastogi V K), Anita Publications, New Delhi, India, (2002) 84
  177. Nielsen O F, in Perspectives in Engineering Optic,s (eds Singh K, Rastogi V K), Anita Publications, New Delhi, India, (2002)345.
  178. Nissum M, Shabanova E, Nielsen O F, J Chem  Education, 77(2000)633.


Asian Chemistry Letters                                                                                                       Vol. 18, Nos. 1&2 (2014)47-80


New approaches to analyse plant metabolites in horticultural plants by mid infrared

and Raman spectroscopic methods


Hartwig Schulz
Julius Kühn-Institute (JKI)
Federal Research Centre for Cultivated Plants,
Institute for Ecological Chemistry, Plant Analysis and Stored Product Protection,
Königin-Luise-Straße 19,14195 Berlin, Germany

___________________________________________________________________________________________________________________________________

This review presents the application of infrared and Raman spectroscopic methods for the analysis of valuable plant substances in various horticultural plant species (fruits, vegetables, dye plants, aromatic teas, spices and medicinal plants). Usually the described measurements can be performed directly on the plant tissue, hydro-distillates or solvent extracts. Whereas near-infrared spectra can be interpreted only by application of chemometric algorithms, mid-infrared and Raman spectra obtained from the individual samples are well-structured and show characteristic key bands of the individual plant substances. In most cases these bands provide important information about the chemical composition of the investigated samples, including both primary and secondary metabolites. Based on such chemical markers, vibrational spectroscopic analyses in principle allow discriminating different plant species and even different chemotypes among the same species. Therefore, the combination of vibrational spectroscopy and hierarchical cluster analysis provides a fast, easy and reliable approach for chemotaxonomy characterisation. Applying the PLS algorithm, usually the determination of main plant substances results in comparatively high R2 and low SECV values. The ability to monitor rapidly various plant samples (fresh or air-dried plant tissue), solvent extracts or essential oils makes it possible to efficiently select high-quality single plants from wild populations as well as progenies of crossing experiments. Today, vibrational spectroscopy methods have been successfully introduced into the agricultural section and are used for qualitative and quantitative determination of various plant substances. Furthermore, sophisticated techniques allow to perform point by point measurements (mapping) or to acquire simultaneously spectra (imaging) from a small sample area. Thus, infrared and Raman spectra can be obtained more or less nondestructively from the surface or other areas in order to determine the distribution of certain components in the plant tissue even on the cellular level. Generally, the above mentioned vibrational spectroscopy techniques are increasingly used in the food and phytopharmaceutical industries in order to perform fast quality checks of incoming raw materials as well as final products and may also efficiently assist on-line control of extraction or distillation processes. © Anita Publications. All rights reserved.
Keywords: Near-infrared spectroscopy, Nd:YAG laser, Raman spectroscopy, Raman effect, Plant tissues

Total Refs : 159

___________________________________________________________________________________________________________________