Raman Spectroscopy

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Igor K. Lednev, of the Department of Chemistry at the University at Albany, the StateUniversity of New York, has been developing the use of Raman spectroscopy for a varietyof forensic applications, including determining the age of blood stains and linking gunshot residues to specific ammunition–firearm combinations.

Two-dimensional (2D) Raman correlation spectroscopy is a powerful analytical technique for analyzing a system under the influence of an external perturbation. Isao Noda, of the Department of Materials Science and Engineering, at the University of Delaware and Danimer Scientific, has been developing 2D Raman correlation spectroscopy and applying it to the study of various materials, including exciting new biopolymers. He recently spoke to us about this work.

The Raman spectra of a particular face of a single crystal can be significantly different if acquired with different microscope objectives. This article explains the underlying physics of changes in relative intensity and even peak position of certain Raman bands depending on the microscope objective used to acquire the spectrum.

The Raman spectra of crystalline and amorphous solids of the same chemical composition can be significantly different primarily because of the presence or absence of spatial order and long range translational symmetry, respectively. The purpose or goal of this installment of Molecular Spectroscopy Workbench is to help readers understand the underlying physics that affect the Raman spectra of crystalline and amorphous solids. Wave vector, reciprocal space, and the Brillouin zone are explained with respect to Raman spectroscopy of solids.

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In biomedical applications of surface-enhanced Raman spectroscopy (SERS), nanoparticles can enhance the Raman signal and provide additional functionality. Duncan Graham of the University of Strathclyde has been pushing the limits of what can be achieved using functionalized nanoparticles and SERS, in applications such as cholera detection, lipid profiling in cancer cells, and assessing the efficacy of anti-cancer drugs, For this and other work he has won the 2017 Charles Mann Award, presented by the Federation of Analytical Chemistry and Spectroscopy Societies (FACSS). He recently spoke to Spectroscopy about this work. This interview is part of a series of interviews with the winners of awards that will be presented at the SciX 2017 conference in October.

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Portable instrumentation for Raman spectroscopy has rapidly evolved over the last decade, where sample testing that once occurred in the laboratory is now executed in the field (e.g. warehouse).   Portable Raman spectroscopy is a powerful technique for the rapid identification of diversely sourced raw materials used in pharmaceutical processing.  In addition to portability; reduced cost, rapid data acquisition and ease of use make this powerful technique attractive and accessible to both expert spectroscopists and non-specialists.  In most cases, the method development can be easily accomplished in the laboratory after which the instrument and methods are transferred to field for sample analysis or warehouse areas for inspection of incoming raw material.  Qualitative Raman methods for identification of raw materials typically utilize spectral libraries for sample to standard comparison.  When developing Raman spectral libraries for raw material identification, great care is required when considering critical factors (e.g. instrument type, Raman capability, container type, container interference, background interference, material variability) that can potentially influence the identity of the material.  This paper discusses portable Raman techniques and approaches for raw material identification, as well as key considerations for developing and validating Raman spectral libraries.

Controlling the orientation of the laser and Raman polarization relative to the sample orientation can provide a wealth of information in the Raman spectrum that would be difficult to achieve by other methods. Presentation of the spectra makes these effects appear straightforward, but because of multiple instrumental factors, and experimental design, it is easy to produce erroneous results. This column is going to explain what instrumental components affect the polarization effects that are observed, and how the sample setup itself affects the Raman signal.

Raman spectroscopy can be used to determine the temperature of a material when other more direct means are either impractical or not possible. The material’s temperature can affect the peak position of Raman bands. When a Raman band shifts significantly with temperature, the monitoring of the peak position can be the most straightforward manner of determining temperature provided the Raman spectrometer has sufficient spectral resolution. Another method is to determine the temperature from the ratio of the Stokes and anti-Stokes signal strengths of a given Raman band. The latter method requires the ability to detect light at wavelengths longer and shorter than that of the laser and an accurate measurement of the wavelength dependent instrument response function.

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The accurate determination of protein structure is integral to the medical and pharmaceutical communities’ ability to understand disease, and develop drugs. Current techniques (CD, IR, Raman) for protein structure prediction provide results that can be poorly resolved, while high resolution techniques (NMR, X-ray crystallography) can be both costly and time-consuming. This work proposes the use of drop coat deposition confocal Raman spectroscopy (DCDCR), coupled with peak fitting of the Amide I spectral region (1620–1720 cm-1) for the accurate determination of protein secondary structure. Studies conducted on BSA and ovalbumin show that the predictions of secondary structure content within 1% of representative crystal structure data is possible for model proteins. The results clearly demonstrate that DCDCR has the potential to be effectively used to obtain accurate secondary structure distributions for proteins.

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Spectroscopy is proud to have created a new award, the Emerging Leader in Molecular Spectroscopy Award. As its name implies, the award recognizes a young scientist, and it is designed to encourage the next generation of molecular spectroscopists. Matthew Baker, the winner of the inaugural Emerging Leader in Molecular Spectroscopy Award, is a senior lecturer in chemistry at the University of Strathclyde, in Glasgow, Scotland. At Strathclyde, Baker leads research to advance the application of analytical chemistry to real-world problems in a variety of areas, including the biomedical, clinical, defense, and security fields. His main focus is the development of spectroscopic and spectrometric molecular pathology, disease diagnosis, and the detection of pathogenic bacteria and toxic chemicals. In particular, Baker has pioneered the use of vibrational spectroscopy for clinical diagnostics.

Photoluminescence can provide information about the composition and solid state structure of a material. The high spectral resolution of a Raman spectrometer can be useful in performing photoluminescence spectroscopy of solid state materials, particularly when the emission spectra consist of narrow bands or even lines. Having the capability to perform photoluminescence and Raman spectroscopies simultaneously with the same instrument is advantageous, especially when studying 2D crystals. When used to perform photoluminescence spectroscopy, the Raman spectrometer becomes two instruments in one.

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The development of novel, nondestructive technologies for rapid analysis of evidence discovered at crime scenes is pertinent to our criminal justice system to solve the millions of violent crimes that occur each year. Without a witness, establishing the precise timeline of a crime is difficult. Therefore, technologies based on sensitive, nondestructive techniques are needed to evaluate evidence and create such a timeline. We propose the use of Raman spectroscopy to analyze the age of bloodstains for potential use as a forensics tool. Previous studies have revealed Raman spectroscopy is sensitive to changes in blood analyte concentration and different oxidative states of hemoglobin. Raman spectroscopy could allow for rapid comparison of spectra from blood stains of unknown age to spectra of known age with high temporal accuracy. Though further investigation into other substrates and biochemical components should be performed, our study reveals Raman spectroscopy has the potential to accurately and nondestructively determine the age of a bloodstain for use in criminal investigations.