Abstract
Chirality is a fundamental property of molecules, particularly important in biological systems. The ability to distinguish between enantiomers is crucial in many fields. Raman optical activity (ROA) is a powerful analytical technique that measures the small intensity difference in Raman scattering of right- and left-circularly polarized light by chiral molecules. Due to their sensitivity to stereochemistry, ROA spectra can provide an ample amount of information on both structure and conformational behavior of chiral molecules. Here we present the theoretical background to the subject and an overview of different forms of ROA measurement, including resonance ROA (RROA) and surface-enhanced ROA (SEROA). We also discuss the application of ROA spectroscopy to a variety of molecules, emphasizing the extent of structural information that can be gathered. Although ROA is still a specialized technique, recent advances have led to several new applications and developments. We show several results to illustrate how ROA is opening new opportunities in analytical chemistry. Finally, we discuss recent advances in ROA instrumentation and its advantages and limitations compared to other chiral spectroscopic techniques, such as electronic and vibrational circular dichroism. Hopefully, this chapter provides a comprehensive list of the fundamentals, applications, advancements, and future potential of ROA as a powerful analytical technique for exploring and studying chirality in molecules.
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References
S. Ostovar pour, L.D. Barron, S.T. Mutter, E.W. Blanch, in Chiral Analysis, 2nd edn., ed. by P.L. Polavarapu (Elsevier, 2018), pp. 249–291
V. Parchaňský, J. Kapitán, P. Bouř, RSC Adv. 4, 57125–57136 (2014)
L.D. Barron, Biomed. Spectrosc. Imaging 4, 223–253 (2015)
L.A. Nafie, in Encyclopedia of Spectroscopy and Spectrometry, 3rd edn., eds. by J.C. Lindon, G.E. Tranter, D.W. Koppenaal (Academic Press, Oxford, 2017), pp. 891–899
W. Hug, in Encyclopedia of Spectroscopy and Spectrometry, 3rd edn., eds. by J.C. Lindon, G.E. Tranter, D.W. Koppenaal (Academic Press, Oxford, 2017), pp. 881–890
J. Hudecová, P. Bouř, in Vibrational Spectroscopy in Protein Research (Elsevier, 2020), pp. 219–248
M. Krupová, J. Kessler, P. Bouř, ChemPlusChem 85, 561–575 (2020)
T. Wu, Phys. Chem. Chem. Phys. 24, 15672–15686 (2022)
G.G. Hoffmann, in Encyclopedia of Spectroscopy and Spectrometry, 3rd edn., eds. by J.C. Lindon, G.E. Tranter, D.W. Koppenaal (Academic Press, Oxford, 2017), pp. 853–862
L. Barron, M. Bogaard, A. Buckingham, J. Am. Chem. Soc. 95, 603–605 (1973)
L.D. Barron, Molecular Light Scattering and Optical Activity (Cambridge University Press, 2009)
L.D. Barron, A.D. Buckingham, Chem. Phys. Lett. 492, 199–213 (2010)
L.A. Nafie, Chirality 32, 667–692 (2020)
P.L. Polavarapu, Vibrational Spectra: principles and Applications with Emphasis on Optical Activity (Elsevier, 1998)
P.L. Polavarapu, Compr. Chiroptical Spectrosc. 2, 387–420 (2012)
P.L. Polavarapu, Chiroptical Spectroscopy: fundamentals and Applications (CRC Press, 2016)
L.D. Barron, S.T. Mutter, E.W. Blanch, in Chiral Analysis (Elsevier, 2018), pp. 249–291
C.D. Syme, E.W. Blanch, C. Holt, R. Jakes, M. Goedert, L. Hecht, L.D. Barron, Eur. J. Biochem. 269, 148–156 (2002)
F. Zhu, J. Kapitan, G.E. Tranter, P.D. Pudney, N.W. Isaacs, L. Hecht, L.D. Barron, Proteins: Struct. Funct. Bioinform. 70, 823–833 (2008)
M. Quack, in Quantum Systems in Chemistry and Physics: progress in Methods and Applications (Springer, 2012), pp. 47–76
S. Mason, Trends Pharmacol. Sci. 7, 20–23 (1986)
G.H. Wagnière, On Chirality and the Universal Asymmetry: reflections on Image and Mirror Image (Wiley, 2007)
R.S. Cahn, C. Ingold, V. Prelog, Angew. Chem., Int. Ed. Engl. 5, 385–415 (1966)
W.A. Bonner, Orig. Life Evol. Biosph. 25, 175–190 (1995)
J.P. Riehl, Mirror-Image Asymmetry: an Introduction to the Origin and Consequences of Chirality (Wiley, 2010)
R. Popa, J. Mol. Evol. 44, 121–127 (1997)
W.A. Bonner, in AIP Conference Proceedings (American Institute of Physics, 1996), pp. 17–49
A. Salam, J. Mol. Evol. 33, 105–113 (1991)
J.V. de Julián-Ortiz, C. de Gregorio Alapont, I. Rı́os-Santamarina, R. Garcı́a-Doménech, J. Gálvez, J. Mol. Graph. Modell. 16, 14–18 (1998)
B. Richard, C.N. Weiskopf, R.S. Gary, Anesthesiology 97, 497–502 (2002)
B. Kasprzyk-Hordern, Chem. Soc. Rev. 39, 4466–4503 (2010)
A.J. Hutt, S.C. Tan, Drugs 52(Suppl 5), 1–12 (1996)
G.A. Hembury, V.V. Borovkov, Y. Inoue, Chem. Rev. 108, 1–73 (2008)
L.D. Barron, Chirality 24, 879–893 (2012)
C. Liang, K. Mislow, J. Am. Chem. Soc. 116, 3588–3592 (1994)
S.D. Banik, N. Nandi, Biochirality: origins, Evolution and Molecular Recognition (2013), pp. 255–305
J.I. Kwiecińska, M. Cieplak, J. Phys.: Condens. Matter 17, S1565 (2005)
J. Chela-Flores, Chirality 6, 165–168 (1994)
R. Corradini, S. Sforza, T. Tedeschi, R. Marchelli, Chirality: the pharmacological, biological, and chemical consequences of molecular asymmetry 19, 269–294 (2007)
D.B. Laurence, in Strategies of Life Detection, eds. by O. Botta et al. (Springer US, Boston, MA, 2008), pp. 187–201
A. Long, O. Perraud, M. Albalat, V. Robert, J.-P. Dutasta, A. Martinez, J. Org. Chem. 83, 6301–6306 (2018)
H.-Y. Wang, S.A. Blaszczyk, G. Xiao, W. Tang, Chem. Soc. Rev. 47, 681–701 (2018)
S. Gim, G. Fittolani, Y. Nishiyama, P. H. Seeberger, Angew. Chem. Int. Edit. 59, 22577–22583 (2020)
M. O’Neill, S.M. Kelly, Adv. Mater. (Deerfield Beach, Fla.) 23, 566–584 (2011)
C. Duan, Z. Cheng, B. Wang, Small 17, 2007306 (2021)
S. Ma, J. Ahn, J. Moon, Adv. Mater. 33, 2005760 (2021)
A. Tran, C.E. Boott, M.J. MacLachlan, Adv. Mater. 32, 1905876 (2020)
M. Manoccio, M. Esposito, A. Passaseo, M. Cuscunà, V. Tasco, Micromachines 12, 6 (2020)
P. Lv, X. Lu, L. Wang, W. Feng, Adv. Func. Mater. 31, 2104991 (2021)
G.E. Fenoy, M. Rafti, W.A. Marmisollé, O. Azzaroni, Mater. Adv. 2, 7731–7740 (2021)
Y. Du, D. Cao, B. Li, H. Lü, Y. Shen, Electrochim. Acta 395, 139201 (2021)
S. Raza, X. Li, F. Soyekwo, D. Liao, Y. Xiang, C. Liu, Eur. Polym. J. 160, 110773 (2021)
S. Nagahara, Y. Okada, Y. Kitano, K. Chiba, Chem. Sci. 12, 12911–12917 (2021)
A.M. Garcia et al., Chem 4, 1862–1876 (2018)
W.H. Brooks, W.C. Guida, K.G. Daniel, Curr. Top. Med. Chem. 11, 760–770 (2011)
I.K. Reddy, R. Mehvar, Chirality in Drug Design and Development (CRC Press, 2004)
S.R. LaPlante, L.D. Fader, K.R. Fandrick, D.R. Fandrick, O. Hucke, R. Kemper, S.P. Miller, P.J. Edwards, J. Med. Chem. 54, 7005–7022 (2011)
O. Mcconnell et al., Chirality: the pharmacological, biological, and chemical consequences of molecular asymmetry 19, 658–682 (2007)
S.R. LaPlante, P.J. Edwards, L.D. Fader, A. Jakalian, O. Hucke, ChemMedChem 6, 505–513 (2011)
C. Brown, Chirality in Drug Design and Synthesis (Academic Press, 2013)
I. Agranat, H. Caner, Drug Discov. Today 4, 313–321 (1999)
J.R. Brandt, F. Salerno, M.J. Fuchter, Nat. Rev. Chem. 1, 0045 (2017)
E. Karjalainen, D.F. Izquierdo, V. Marti-Centelles, S.V. Luis, H. Tenhu, E. Garcia-Verdugo, Polym. Chem. 5, 1437–1446 (2014)
C.S. Wilcox, L.M. Greer, V. Lynch, J. Am. Chem. Soc. 109, 1865–1867 (1987)
M. Khorloo, X. Yu, Y. Cheng, H. Zhang, S. Yu, J.W. Lam, M. Zhu, B.Z. Tang, ACS Nano 15, 1397–1406 (2020)
J.A. Schmidt, J.A. Weatherby, I.J. Sugden, A. Santana-Bonilla, F. Salerno, M.J. Fuchter, E.R. Johnson, J. Nelson, K.E. Jelfs, Cryst. Growth Des. 21, 5036–5049 (2021)
R. Eelkema, B.L. Feringa, Org. Biomol. Chem. 4, 3729–3745 (2006)
K.E. Shopsowitz, H. Qi, W.Y. Hamad, M.J. MacLachlan, Nature 468, 422–425 (2010)
P. Atkins, L. Barron, Mol. Phys. 16, 453–466 (1969)
L.D. Barron, F. Zhu, L. Hecht, G.E. Tranter, N.W. Isaacs, J. Mol. Struct. 834, 7–16 (2007)
L. Barron, L. Hecht, E. Blanch, A. Bell, Prog. Biophys. Mol. Biol. 73, 1–49 (2000)
T.A. Keiderling, Chem. Rev. 120, 3381–3419 (2020)
L.D. Barron, L. Hecht, I.H. McColl, E.W. Blanch, Mol. Phys. 102, 731–744 (2004)
J.R. Escribano, L.D. Barron, Mol. Phys. 65, 327–344 (1988)
F. Zhu, N.W. Isaacs, L. Hecht, L.D. Barron, Structure 13, 1409–1419 (2005)
A.A. Bunaciu, H.Y. Aboul-Enein, Ş. Fleschin, Appl. Spectrosc. Rev. 50, 176–191 (2015)
J.B. Aitken et al., Radiat. Phys. Chem. 79, 176–184 (2010)
P.L. Polavarapu, J. Phys. Chem. 94, 8106–8112 (1990)
L. Barron, A. Buckingham, Annu. Rev. Phys. Chem. 26, 381–396 (1975)
W. Hug, in Handbook of Vibrational Spectroscopy, eds. by J.M. Chalmers, P.R. Griffiths (Wiley, 2006), pp. 745–758
L.A. Nafie, Vibrational Optical Activity: principles and Applications (Wiley, 2011)
L.A. Nafie, Annu. Rev. Phys. Chem. 48, 357–386 (1997)
A. Melcrová, J. Kessler, P. Bouř, J. Kaminský, Phys. Chem. Chem. Phys. 18, 2130–2142 (2016)
C. Mensch, L.D. Barron, C. Johannessen, Phys. Chem. Chem. Phys. 18, 31757–31768 (2016)
N.R. Yaffe, A. Almond, E.W. Blanch, J. Am. Chem. Soc. 132, 10654–10655 (2010)
A. Bell, L. Hecht, L. Barron, J. Am. Chem. Soc. 120, 5820–5821 (1998)
A.F. Bell, L. Hecht, L.D. Barron, J. Am. Chem. Soc. 119, 6006–6013 (1997)
F. Zhu, N.W. Isaacs, L. Hecht, L.D. Barron, J. Am. Chem. Soc. 127, 6142–6143 (2005)
C.V. Raman, Proc. Math. Sci. 37, 342–349 (1953)
C.V. Raman, Indian J. Phys. 2, 387–398 (1928)
C. Raman, Trans. Faraday Soc. 25, 781–792 (1929)
F.A. Miller, G.B. Kauffman, J. Chem. Educ. 66, 795 (1989)
R. Singh, F. Riess, Curr. Sci. 75, 965–971 (1998)
L. Nasdala, D.C. Smith, R. Kaindl, M.A. Ziemann, A. Beran, E. Libowitzky, Spectrosc. Methods Mineralo. 6, 281–343 (2004)
D.A. Long, Int. Rev. Phys. Chem. 7, 317–349 (1988)
R. Singh, Phys. Perspect. 4, 399–420 (2002)
G.S. Landsberg, L.I. Mandelstam, J. Russian Phys.-Chem. Soc. Phys. Sect. 60, 335 (1928)
P.L. Polavarapu, Chirality 14, 768–781 (2002)
T.M. Lowry, Optical Rotatory Power (Dover publications, 1964)
H. Landolt, The Optical Rotating Power of Organic Substances and Its Practical Applications (Chemical Publishing Company, 1902)
J. Gal, Chirality: the pharmacological, biological, and chemical consequences of molecular asymmetry 20, 5–19 (2008)
J. Gal, Nat. Chem. 9, 604–605 (2017)
H. Flack, Acta Crystallogr. A 65, 371–389 (2009)
J. Gal, Chirality 23, 1–16 (2011)
G.D. Fasman, Circular Dichroism and the Conformational Analysis of Biomolecules (Springer Science & Business Media, 2013)
B. Kahr, Chirality 30, 351–368 (2018)
S. Mitchell, Nature 166, 434–435 (1950)
D.M. Rogers, S.B. Jasim, N.T. Dyer, F. Auvray, M. Réfrégiers, J.D. Hirst, Chem 5, 2751–2774 (2019)
L.D. Barron, Molecular Light Scattering and Optical Activity (Cambridge University Press, 2004)
N. Berova, P.L. Polavarapu, K. Nakanishi, R.W. Woody, Comprehensive Chiroptical Spectroscopy, Volume 2: applications in Stereochemical Analysis of Synthetic Compounds, Natural Products, and Biomolecules, vol. 2 (Wiley, 2012)
N. Berova, P.L. Polavarapu, K. Nakanishi, R.W. Woody, Comprehensive Chiroptical Spectroscopy, Volume 1: Instrumentation, Methodologies, and Theoretical Simulations, vol. 1 (Wiley, 2011)
W. Hug, S. Kint, G.F. Bailey, J.R. Scherer, J. Am. Chem. Soc. 97, 5589–5590 (1975)
L. Hecht, L.D. Barron, W. Hug, Chem. Phys. Lett. 158, 341–344 (1989)
L.D. Barron, A.D. Buckingham, Mol. Phys. 20, 1111–1119 (1971)
H. Li, L.A. Nafie, J. Raman Spectrosc. 43, 89–94 (2012)
L.D. Barron, A.D. Buckingham, J. Am. Chem. Soc. 96, 4769–4773 (1974)
L. Hecht, L.A. Nafie, Mol. Phys. 72, 441–469 (1991)
A. Baiardi, J. Bloino, V. Barone, J. Chem. Theory Comput. 14, 6370–6390 (2018)
M.J. Frisch et al., Gaussian 16 Rev. A.03 (2016)
T. Helgaker, K. Ruud, K.L. Bak, P. Jørgensen, J. Olsen, Faraday Discuss. 99, 165–180 (1994)
K. Ruud, T. Helgaker, P. Bouř, J. Phys. Chem. A 106, 7448–7455 (2002)
P. Bouř, J. Sopková, L. Bednárová, P. Maloň, T.A. Keiderling, J. Comput. Chem. 18, 646–659 (1997)
S. Yamamoto, X. Li, K. Ruud, P. Bour, J. Chem. Theory Comput. 8, 977–985 (2012)
J. Kessler, J. Kapitán, P. Bouř, J. Phys. Chem. Lett. 6, 3314–3319 (2015)
L.A. Nafie, Appl. Spectrosc. 50, 14A-26A (1996)
M. Krupová, J. Kapitán, P. Bouř, ACS Omega 4, 1265–1271 (2019)
E.W. Blanch, L. Hecht, L.D. Barron, in Chiral Analysis, eds. by K.W. Busch, M.A. Busch (Elsevier, Amsterdam, 2006), pp. 545–594
M. Das, D. Gangopadhyay, J. Hudecová, J. Kessler, J. Kapitán, P. Bouř, Chempluschem, e202300219 (2023)
Q. Yang, J. Kapitán, P. Bouř, J. Bloino, J. Phys. Chem. Lett. 13, 8888–8892 (2022)
P. Michal, R. Čelechovský, M. Dudka, J. Kapitán, M. Vůjtek, M. Berešová, J. Šebestík, K. Thangavel, P. Bouř, J. Phys. Chem. B 123, 2147–2156 (2019)
M. Hope, J. Šebestík, J. Kapitán, P. Bouř, J. Phys. Chem. A 124, 674–683 (2020)
V. Palivec, P. Michal, J. Kapitán, H. Martinez-Seara, P. Bouř, ChemPhysChem 21, 1272–1279 (2020)
A. Kurochka, J. Průša, J. Kessler, J. Kapitán, P. Bouř, Phys. Chem. Chem. Phys. 23, 16635–16645 (2021)
L.A. Nafie, T.B. Freedman, Chem. Phys. Lett. 154, 260–266 (1989)
D. Che, L. Hecht, L.A. Nafie, Chem. Phys. Lett. 180, 182–190 (1991)
G.-S. Yu, D. Che, T.B. Freedman, L.A. Nafie, Tetrahedron: Asymmetry 4, 511–516 (1993)
G.-S. Yu, L.A. Nafie, Chem. Phys. Lett. 222, 403–410 (1994)
G.S. Yu, D. Che, T.B. Freedman, L.A. Nafie, Biospectroscopy 1, 113–123 (1995)
G.S. Yu, T.B. Freedman, L.A. Nafie, J. Raman Spectrosc. 26, 733–743 (1995)
M. Vargek, T.B. Freedman, L.A. Nafie, J. Raman Spectrosc. 28, 627–633 (1997)
L.A. Nafie, B.E. Brinson, X. Cao, D.A. Rice, O.M. Rahim, R.K. Dukor, N.J. Halas, Appl. Spectrosc. 61, 1103–1106 (2007)
M. Unno, T. Kikukawa, M. Kumauchi, N. Kamo, J. Phys. Chem. B 117, 1321–1325 (2013)
W. Hug, Appl. Spectrosc. 57, 1–13 (2003)
V. Profant, A. Jegorov, P. Bouř, V. Baumruk, J. Phys. Chem. B 121, 1544–1551 (2017)
P. Michal, J. Hudecová, R. Čelechovský, M. Vůjtek, M. Dudka, J. Kapitán, Symmetry-Basel 14, 990 (2022)
K. Dobšíková, P. Michal, D. Spalovská, M. Kuchař, N. Paškanová, R. Jurok, J. Kapitán, V. Setnička, Analyst 148, 1337–1348 (2023)
P. Fagan, L. Kocourková, M. Tatarkovič, F. Kralík, M. Kuchar, V. Setnička, P. Bouř, ChemPhysChem 18, 2258–2265 (2017)
J. Hudecová, J. Kapitán, M. Dračínský, P. Michal, V. Profant, P. Bouř, Chem.-Eur. J. 28, e202202045 (2022)
V. Schrenková, M.S.P. Kkadan, J. Kessler, J. Kapitán, P. Bouř, Phys. Chem. Chem. Phys. 25, 8198–8208 (2023)
V. Palivec, V. Kopecký, P. Jungwirth, P. Bouř, J. Kaminský, H. Martinez-Seara, Phys. Chem. Chem. Phys. 22, 1983–1993 (2020)
V. Palivec, C. Johannessen, J. Kaminský, H. Martinez-Seara, PLOS Comput. Biol. 18, e1009678 (2022)
V. Profant, C. Johannessen, E.W. Blanch, P. Bouř, V. Baumruk, Phys. Chem. Chem. Phys. 21, 7367–7377 (2019)
V. Andrushchenko, A. Kurochka, J. Kubelka, J. Kaminský, in Reference Module in Chemistry, Molecular Sciences and Chemical Engineering (Elsevier, 2022)
J. Jungwirth, J. Šebestík, M. Šafařík, J. Kapitán, P. Bouř, J. Phys. Chem. B 121, 8956–8964 (2017)
J. Kessler, S. Yamamoto, P. Bouř, Phys. Chem. Chem. Phys. 19, 13614–13621 (2017)
S. Yamamoto, S. Ishiro, J. Kessler, P. Bouř, Phys. Chem. Chem. Phys. 23, 26501–26509 (2021)
P. Michal, J. Kapitán, J. Kessler, P. Bouř, Phys. Chem. Chem. Phys. 24, 19722–19733 (2022)
M. Das, D. Gangopadhyay, J. Šebestík, L. Habartová, P. Michal, J. Kapitán, P. Bouř, Chem. Commun. 57, 6388–6391 (2021)
G.J. Li, J. Kessler, J. Cheramy, T. Wu, M.R. Poopari, P. Bouř, Y.J. Xu, Angew. Chem. Int. Edit. 58, 16495–16498 (2019)
T. Wu, G.J. Li, J. Kapitán, J. Kessler, Y.J. Xu, P. Bouř, Angew. Chem. Int. Ed. 59, 21895–21898 (2020)
G.J. Li, M. Alshalalfeh, Y.Q. Yang, J.R. Cheeseman, P. Bouř, Y.J. Xu, Angew. Chem. Int. Ed. 60, 22004–22009 (2021)
E. Machalska, G. Zajac, A.J. Wierzba, J. Kapitán, T. Andruniow, M. Spiegel, D. Gryko, P. Bouř, M. Baranska, Angew. Chem. Int. Ed. 60, 21205–21210 (2021)
G. Zając, P. Bouř, J. Phys. Chem. B 126, 355–367 (2022)
T. Wu, J. Kapitán, P. Bouř, J. Phys. Chem. Lett. 13, 3873–3877 (2022)
E. Machalska, N. Hachlica, G. Zajac, D. Carraro, M. Baranska, G. Licini, P. Bouř, C. Zonta, A. Kaczor, Phys. Chem. Chem. Phys. 23, 23336–23340 (2021)
T. Wu, J. Kapitán, V. Andrushchenko, P. Bouř, Anal. Chem. 89, 5043–5049 (2017)
T. Wu, J. Kessler, J. Kaminský, P. Bouř, Chem.-Asian J. 13, 3865–3870 (2018)
T. Wu, P. Bouř, Chem. Commun. 54, 1790–1792 (2018)
E. Brichtová, J. Hudecová, N. Vršková, J. Šebestík, P. Bouř, T. Wu, Chem.-Eur. J. 24, 8664–8669 (2018)
T. Wu, P. Bouř, V. Andrushchenko, Sci. Rep.-UK 9, 1068 (2019)
J. Sahoo, T. Wu, B. Klepetářová, J. Valenta, P. Bouř, ChemPlusChem 85, 694–700 (2020)
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Das, M., Kurochka, A., Bouř, P., Gangopadhyay, D. (2024). Chirality Revealed by Raman Optical Activity: Principles, Applications, Recent Developments and Future Prospects. In: Singh, D.K., Kumar Mishra, A., Materny, A. (eds) Raman Spectroscopy. Springer Series in Optical Sciences, vol 248. Springer, Singapore. https://doi.org/10.1007/978-981-97-1703-3_7
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