Raman and SERS Investigations of Pharmaceuticals

Transcription

1 Raman and SERS Investigations of Pharmaceuticals

2 Monica Baia Simion Astilean Traian Iliescu Raman and SERS Investigations of Pharmaceuticals 123

3 Dr. Monica Baia Faculty of Physics Molec. Spectroscopy Dept. Babes-Bolyai University M. Kogalniceanu Cluj-Napoca Romania monib@phys.ubbcluj.ro Dr. Traian Iliescu Faculty of Physics Molec. Spectroscopy Dept. Babes-Bolyai University M. Kogalniceanu Cluj-Napoca Romania ilitra@phys.ubbcluj.ro Dr. Simion Astilean Faculty of Physics Molec. Spectroscopy Dept. Babes-Bolyai University M. Kogalniceanu Cluj-Napoca Romania sastil@phys.ubbcluj.ro ISBN e-isbn DOI / Library of Congress Control Number: c 2008 Springer-Verlag Berlin Heidelberg This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Coverdesign: WMXDesign GmbH, Heidelberg Printed on acid-free paper springer.com

4 Preface In the last years it has become obvious for most researchers that interdisciplinary research is the key to success in the future of science. Therefore, only the collaborative work of chemists, biologists, physicists, and so on will lead to further developments. The present book gives an example of such an interdisciplinary work. Thus, some new derivatives have been prepared by chemists, and were analyzed by physicists in order to better understand their physical-chemical properties for upcoming tests performed by pharmacists. The book is addressed to students and researchers in the faculties of physics, chemistry, medicine and pharmacy as well as to employers in research departments of companies that are interested in designing and testing new and different types of pharmaceuticals. This book illustrates several of our recent spectroscopic investigations performed by using Raman, infrared, and surface-enhanced Raman spectroscopy (SERS) on different drugs such as tranquilizers and sedatives, antiinflammatory drugs, vitamins, drugs with antibacterial properties, etc. The book ends by presenting some recent results about the preparation and investigation of the SERS efficiency of a few ordered and disordered metallic nanostructured substrates. Because of the possibility of tuning their plasmonic response, the analysis of the adsorption of such pharmaceutical relevant molecules on this kind of SERSactive substrates could provide further insights into their adsorption behavior. Observations and suggestions will be gratefully received and may be addressed to the authors. Cluj-Napoca, January 2008 Monica Baia, Simion Astilean, and Traian Iliescu

5 About the Authors Monica Baia was born in Cluj-Napoca, Romania in She studied physics at the Babes-Bolyai University of Cluj-Napoca, in Romania, and received her PhD degree in 2003 on the vibrational characterization of coordination and biologically active compounds by means of IR absorption, Raman and surface-enhanced Raman spectroscopy (SERS) under the supervision of Prof. Dr. Dr. h.c. Wolfgang Kiefer from the University of Würzburg, in Germany. In 2003 she began her academic career as a lecturer at the Molecular Spectroscopy Department of the Babes-Bolyai University. In October, 2005 she worked for a nine month period with Prof. Dr. Jürgen Popp s group as a postdoctoral research fellow at the University of Jena, Germany. In 2007 she received the In Hoc Signo Vinces prize of the National University Research Council of Romania. Her current research interests include the elucidation of the structure and adsorption behavior of pharmaceutical and biological relevant compounds by using Raman spectroscopy and SERS, and the study of the optical and structural properties of metallic ordered and disordered nanostructures for their further use as SERS substrates in biomolecular and pollutants detection. She has about 50 refereed journal publications. Simion Astilean was born in Cornesti (Cluj), Romania in He studied physics at the Babes-Bolyai University of Cluj-Napoca, in Romania, and completed his PhD on the spectroscopic characterization of intermolecular proton transfer in 1993 under the supervision of Prof. Dr. Peter Trommsdorff at the Joseph Fourier University, Grenoble, France. He worked for many years as a visiting scientist in the UK, Israel, and France. Astilean is currently the head of the Molecular Spectroscopy Department and the Nanoscience and Nanotechnology Center at the Babes-Bolyai University. His current research focuses on the rational design, fabrication, and assembly of noble-metal nanoparticles with the aim of enabling novel methods for detection and sensing biomolecules via surface-enhanced Raman spectroscopy (SERS), surface-enhanced IR absorption (SEIRA), local surface

6 VIII About the Authors plasmon resonance (LSPR), and surface-enhanced fluorescence (SEF). He has authored and co-authored about 100 refereed journal publications, two books, and two book chapters. Traian Iliescu was born in Slatina, Romania in He studied physics at the Babes-Bolyai University of Cluj-Napoca, in Romania. He received his PhD degree in 1975 from the Babes-Bolyai University. Iliescu began his academic career in 1963 as assistant professor at the Chemical Physics Department, in the Faculty of Pharmacy in Cluj-Napoca. From 1970 onwards he has been present in the Physics faculty in Cluj-Napoca as assistant professor, and then as full professor. His first research interest was the Spolski effect in matrix at low temperatures of different aromatic compounds and then the application of Raman spectroscopy in molecular dynamics by band shape analysis, and the elucidation of the structure of different glass systems and surface-enhanced Raman spectroscopy on the compounds of pharmaceutical and biological interest. In 1990 he obtained the C. Miculescu prize of the Romanian Academy for a selection of papers related to molecular dynamics. He has authored and co-authored about 100 refereed journal publications and four books.

7 Contents 1 Introduction Fundamentals of Infrared and Raman Spectroscopy, SERS, and Theoretical Simulations Vibrations of Molecules Infrared Spectroscopy Basics FT-Infrared Measurements Raman Spectroscopy Basics FT-Raman Measurements Surface-Enhanced Raman Spectroscopy Basics Mechanisms of Surface Enhancement SERS-Active Substrates SERS Measurements Theoretical Simulations Molecular Mechanics and Electronic Structure Methods The Simulation Model DFT Methods The Basis Set Computational Details Tranquilizers and Sedatives Phenothiazine Derivatives Vibrational Analysis Adsorption on the Silver Surface Conclusions...55

8 X Contents 3.2 Anthranil Vibrational Analysis Adsorption on the Silver Surface Conclusions Anti-Inflammatory Drugs Diclofenac Sodium Vibrational Analysis Adsorption on the Silver Surface Conclusions Diclofenac Sodium β-cyclodextrin Complex Vibrational Analysis Adsorption on the Silver Surface Conclusions Molecules with Antibacterial Properties Potassium Benzylpenicillin Vibrational Analysis Adsorption on the Silver Surface Conclusions Trihydrate Amoxicillin Vibrational Analysis Adsorption on the Silver Surface Conclusions Rivanol Vibrational Analysis Adsorption on the Silver Surface Conclusions Vitamins Vitamin B Vibrational Analysis Adsorption on the Gold Surface Conclusions Vitamin PP Adsorption on the Silver Surface Conclusions Other Molecules with Pharmacological Activity Formylfuran Derivatives Formylfuran (4-Fluor-phenyl)-2-formylfuran and 5-(4-Brom-phenyl)-2-formylfuran...152

9 Contents XI 7.2 Quinoline Derivatives Isoquinoline Lepidine Phenylacridine Vibrational Analysis Adsorption on the Silver Surface Conclusions New Developments in SERS-Active Substrates Summary Index...211

10 Abbreviations FT Fourier transform SERS Surface-enhanced Raman spectroscopy SERRS Surface-enhanced resonance Raman spectroscopy DFT Density functional theory HF Hartree Fock RHF Restricted Hartree Fock 10-I-10H-P-5-O 10-Isopentyl-10H-phenothiazine-5-oxide 10-I-10H-P-5,5-D 10-Isopentyl-10H-phenothiazine-5,5-dioxide PhT Phenothiazine DCFNa Diclofenac sodium NSAIDs Nonsteroidal anti-inflammatory drugs UV Ultraviolet UV-vis Ultraviolet-visible βcd β-cyclodextrin FWHM Full width at half maximum KBP Potassium benzylpenicillin THA Trihydrate amoxicillin RIV Rivanol NAD Nicotinamide adenine dinucleotide NADP Nicotinamide adenine dinucleotide phosphate 2FF 2-Formylfuran 5-(4FP)-2FF 5-(4-Fluor-phenyl)-2-formylfuran 5-(4Br-P)-2FF 5-(4-Brom-phenyl)-2-formylfuran 9-PA 9-Phenylacridine p-atp p-aminothiophenol EF Enhancement factor LSPR Localized surface plasmon resonance