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Volume 138 | Number 14 | 2013 138 | Number Volume Analyst www.rsc.org/analyst Volume 138 | Number 14 | 21 July 2013 | Pages 3847–4204 Analyst Themed issue: Optical Diagnosis Showcasing Raman detection of early stages of As featured in: malaria infection from the Biophotonics Laboratory of Nicholas Smith at the Immunology Frontier Research Center, Osaka University, Japan. Title: Raman spectroscopic analysis of malaria disease progression via blood and plasma samples We show that Raman spectroscopy can discriminate between resonant heme and bio-crystallized hemozoin in the blood of malaria-infected patients. Both are present in blood and plasma following infection, and by multivariate analysis, their discrimination within blood samples allows early, quantitative and See Nicholas I. Smith et al., potentially automated detection of malaria, and its eff ects on the Analyst, 2013, 138, 3927. immune system. Pages 3847–4204 Pages Themed issue: Optical Diagnosis www.rsc.org/analyst ISSN 0003-2654 Registered Charity Number 207890 CRITICAL REVIEW David I. Ellis et al. Illuminating disease and enlightening biomedicine: Raman spectroscopy as a diagnostic tool 0003-2654(2013)138:14;1-X Analyst View Article Online CRITICAL REVIEW View Journal | View Issue Illuminating disease and enlightening biomedicine: Raman spectroscopy as a diagnostic tool Cite this: Analyst, 2013, 138, 3871 David I. Ellis,*a David P. Cowcher,a Lorna Ashton,a Steve O'Hagana and Royston Goodacreab The discovery of the Raman effect in 1928 not only aided fundamental understanding about the quantum nature of light and matter but also opened up a completely novel area of optics and spectroscopic research that is accelerating at a greater rate during the last decade than at any time since its inception. This introductory overview focuses on some of the most recent developments within this exciting field and how this has enabled and enhanced disease diagnosis and biomedical applications. We highlight a small number of stimulating high-impact studies in imaging, endoscopy, stem cell research, and other recent Received 8th April 2013 developments such as spatially offset Raman scattering amongst others. We hope this stimulates further Accepted 8th May 2013 interest in this already exciting field, by ‘illuminating’ some of the current research being undertaken by DOI: 10.1039/c3an00698k Creative Commons Attribution 3.0 Unported Licence. the latest in a very long line of dedicated experimentalists interested in the properties and potential www.rsc.org/analyst beneficial applications of light. Introduction volume treatise the ‘Book of Optics’ (Kit¯ab al-Man¯azir)_ in the early 11th century (leading to him being regarded as the father The properties of light have been of interest to experimentalists of modern optics1), through to one of the very rst publications for millennia. From the publication of Ibn al-Haytham's seven in a scientic journal, Isaac Newton's paper on the theory of the properties of light2 itself followed some years later by his 3 This article is licensed under a famous book, Opticks, in 1704. Whilst separated by seven aSchool of Chemistry, Manchester Institute of Biotechnology, The University of centuries, these two polymaths and their respective bodies of Manchester, 131 Princess Street, Manchester M1 7ND, UK. E-mail: D.Ellis@ work shared similarities, perhaps the most important being manchester.ac.uk that both were the result of systematic and methodical experi- Open Access Article. Published on 31 May 2013. Downloaded 01/12/2014 16:39:35. bManchester Centre for Integrative Systems Biology, Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK mentation. In the century following the publication of Newton's David Ellis was educated on the David Cowcher obtained an Welsh coast at the University of undergraduate Masters degree Wales, Aberystwyth, obtaining a in Chemistry and Forensic BSc in Environmental Science Science in 2009 from the and a PhD in Analytical University of Manchester, which Biotechnology/Microbiology. His included a year working as an research involving the rapid and analytical chemist for Glax- quantitative detection of food- oSmithKline. He is currently borne bacteria using FT-IR and studying for a PhD with Roy machine learning has been Goodacre at the Manchester widely publicised, featuring on Institute of Biotechnology, BBC TV and radio, the Science University of Manchester, on the Museum in London, as well as development of enhanced the national and international press (e.g. WIRED). He now works Raman scattering methods for at the Manchester Institute of Biotechnology (MIB), as a Senior biochemical analysis. Experimental Officer undertaking research and managing the labs of Roy Goodacre (http://biospec.net) and Doug Kell (http:// dbkgroup.org), in the School of Chemistry, University of Man- chester, UK. This journal is ª The Royal Society of Chemistry 2013 Analyst, 2013, 138, 3871–3884 | 3871 View Article Online Analyst Critical Review Opticks, as early as the mid-1800s, the interaction of light concerning the molecular scattering of light in liquids and within tissue was being used by physicians to assist in disease solids.9 These experiments opened up a deep interest in C.V. recognition.4 Raman and a new eld of research on his return to Kolkata It was during a sea voyage from India to England in 1921 that (Calcutta) on the scattering of light,5 as well as the publication the brilliant Indian physicist C.V. Raman, another renowned of another article on the molecular diffraction and quantum experimentalist, undertook some on-board experiments which structure of light in the following year.10 were later submitted to Nature in a letter called the ‘The Colour Raman and collaborators such as K.S. Krishnan began a of the Sea’.5 Unable to accept Lord Rayleigh's6 explanation that series of seminal experiments concerning the scattering of light the colour of the sea was just a reection of the colour of the in a large number of liquids, as well as theories about the sky,7 Raman's experiments showed that the colour of the sea potential applications of their experiments, which culminated was in fact a direct result of the molecular scattering of light and in their discovery of the inelastic scattering effect named aer independent of absorption or the reection of light from the Raman in 1928 on 28 February,11 and his award of the Nobel sky.8 This was very closely followed by another letter to Nature Prize for Physics in 1930. This discovery was also independently observed by Landsberg and Mandelstam later in 1928 (see Fig. 1 for a timeline of events in Raman spectroscopy). There was a great deal of interest in the Raman effect and this not only aided Lorna Ashton studied for her BSc the fundamental understanding about the quantum nature of with the Open University before light, and its interaction with matter at the molecular level, but joining the University of Man- also opened up a completely novel area of optics and spectro- chester where she obtained her scopic research that is, particularly in terms of biological and PhD in Biomolecular Sciences biomedical applications,12,13 accelerating at a greater rate and Raman Optical Activity. She during the last decade than at any time since its inception. has since worked as a post Creative Commons Attribution 3.0 Unported Licence. Whereas infrared (IR) spectroscopies measure the absorp- doctoral research associate spe- tion of energy, Raman spectroscopy measures the exchange of cialising in Raman Spectroscopy energy with electromagnetic (EM) radiation of a particular and two-dimensional correlation wavelength, usually provided by a monochromatic light source analysis for the characterisation such as a laser in the visible to near-IR portion of the EM; of conformational transitions in although it is also possible to conduct experiments in the near- biomolecules. Lorna is currently and deep-UV. From the exchange in EM energy a measurable working as part of a BBSRC funded project for rapid evolution of Raman shi in the wavelength of incident laser light is enzymes and synthetic microorganisms developing Raman spec- observed, this is also referred to as the inelastic light scattering This article is licensed under a troscopy as a high-throughput analytical technique for industrial effect.14–16 It is usually the Stokes shi which is measured, as bioprocesses. Open Access Article. Published on 31 May 2013. Downloaded 01/12/2014 16:39:35. Steve O'Hagan gained BSc and Roy Goodacre is a PhD graduate MSc degrees in Chemistry at the from the University of Bristol University of Manchester. The (UK) where he studied mass MSc research was to character- spectrometry of microbial ise ‘Molecular Beam Sources’ systems. Aer a postdoc, Well- using mass spectrometry and come Trust fellowship and TOF kinetic energy measure- lectureship in the University of ments; computer simulations Wales, Aberystwyth, he is now were also used. Steve gained a Professor of Biological Chem- PhD in Chemistry at the istry at the University of Man- University of Warwick; several chester (UK). His group's main mass spectrometry and chemo- areas of research (http:// metric techniques were www.biospec.net/) are broadly employed to analyse engine oils and additives. Aer several years within analytical biotechnology, metabolomics and systems working for commercial laboratories, he joined the University of biology. His expertise involves many forms of Raman spectroscopy Manchester as a Computer Officer, working with Doug Kell's and (including deep UV resonance Raman and SERS), FT-IR spectros- Roy Goodacre's research groups. Interests include: genetic copy, and mass spectrometry, as well as advanced chemometrics, programming; laboratory automation; analytical laboratory data machine learning and evolutionary computational methods. He is analysis; chemometrics; as well as scientic visualization. Editor-in-Chief of the journal Metabolomics, on the Editorial Advisory Boards of Analyst and Journal of Analytical and Applied Pyrolysis, a founding director of the Metabolomics Society and a director of the Metabolic Proling Forum.