Raman Spectroscopy

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.

We show Raman spectra of polymeric fibers acquired as a function of increasing stress and temperature. With knowledge of Raman band assignments, it becomes possible to understand, in detail, the molecular changes that are responsible for polymer orientation and crystallization.

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 apparent reaction kinetics between SO3 and polyethylene are investigated in various halogenated solvents using in situ Raman spectroscopy with an immersion Raman probe, demonstrating the power of in situ Raman spectroscopy to monitor hazardous reactions.

This study explores the use of a novel SERS substrate that can enhance the Raman signals of explosives that are present in picogram quantities in neat solutions using a visible laser wavelength and a compact Raman instrument.

The in situ combination of rheometry and Raman spectroscopy allows for real-time, synchronized measurement of both physical and chemical material properties.

A simple SERS-based method was used to identify low doses of the APIs alprazolam, codeine, oxycodone, and hydrocodone using a handheld Raman spectrometer.

A procedure was developed to calibrate the wavenumber (energy shift) axis in Raman spectrometers, and it was tested in both portable and laboratory-based instruments.

Interference from background fluorescence is a common challenge in Raman analysis. A study of three different types of biological samples was made to compare the ability of 785-nm and 1064-nm excitation to deal with this problem.

The resonance Raman spectra of carotenoids vary with subtle changes on the functional side groups, making these spectra useful for identifying and characterizing carotenoids.

A straightforward numerical approach to estimate the performance of a spatial filter in Raman backscattering spectroscopy has been developed. This approach enabled the authors to determine an optimal hole diameter that balances spatial resolution and signal intensity.

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.

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.

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.

Heinz W. Siesler, Emeritus Professor at University of Duisburg-Essen, reviews Jerry Workman’s new book, The Concise Handbook of Analytical Spectroscopy Theory, Applications, and Reference Materials

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.

When characterizing microscale objects using a Raman microscope, certain basic practical aspects of analytical instrument performance and experimental design should be taken into consideration.

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.

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.

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.

Raman spectroscopy is a well-suited spectroscopic technique for process development and control within development labs in chemical, pharmaceutical, and other industries. This article demonstrates the utility of portable Raman spectroscopy as a simple and versatile tool for in-situ monitoring of reactions using univariate analysis such as peak trending, as well as multivariate analysis approaches to predict the end point of chemical reactions. Using portable Raman systems allows users to make measurements in the lab, but also serves as a proof of concept for the Raman measurements to be implemented at-line or on-line in small pilot plants or large scale production sites. For known reactions that are repetitively performed, or for continuous online process monitoring of reactions, the present approach provides a convenient solution for process understanding and the basis for future implementation.

The availability of quality drugs is crucial in the event of a pandemic. Here, we report our pilot efforts to perform rapid screening of anti-infective drugs for confirmation of drug product quality using near infrared and Raman library methods. The methods reported are nondestructive towards the sample and are designed to facilitate rapid physical testing of drugs at the point of use or in a field setting. We built a representative library through voluntary collaboration with six different manufacturers of antibiotic and antiviral drugs. The drugs supplied by these manufacturers are representative of imported U.S. FDA approved finished products. We successfully transferred the spectral libraries from laboratory-based instruments to field-deployable handheld near infrared and Raman instruments and challenged the library methods using independent samples from different batches.

In this paper, we examine the relative performance of 532 and 785 nm portable Raman systems, as well as demonstrate an automated analytical methodology applicable for carbon nanotube (CNT) characterization and quality control applications. Both 532 and 785 nm Raman spectra were used to directly analyze and compare important CNT structural parameters and properties including CNT diameters, diameter distributions, CNT structural quality (% of defects), CNT types, and other properties. The data indicate advantages in a number of areas for using 532 versus 785 nm excitation for CNT Raman measurements.

This article verified the Brill transition in nylon 6,6 by Raman spectroscopy through heating and cooling processes of the sample. When nylon is heated at around 160 C a crystalline phase transition occurs from a triclinic structure at room temperature to a pseudohexagonal structure above that temperature. This phase transition is known as the Brill Transition. With temperature-dependent Raman scattering measurements, it was possible to determine the vibrational behavior of nylon 6,6 during the Brill transition, and consequently to identify the main Raman bands associated with the Brill transition.

Raman spectroscopy is particularly useful for identification of contaminant materials in pharmaceuticals because it can very clearly and nondestructively identify materials. Raman spectroscopy can be used to identify foreign matter on tablets as well as the individual tablet materials to confirm the material’s legitimacy. For injectable drug vials, Raman spectroscopy can be used with microscopy to count, size, and identify particulate contamination found in such vials. Spectral interpretation is key to the value of Raman spectroscopy, and it is important for accuracy of identification not to simply rely on library match values.

Cosmetic preparations are common consumer products that consist of various organic and inorganic materials. In this paper, a method for the identification and spatial discrimination of the components in eye shadow samples using laser Raman microspectroscopy is described. The use of a multivariate curve resolution (MCR) is utilized during the analysis of the cosmetic preparation mapping data to develop the spatial discrimination information presented within this note.

Analytical quality control (AQC) is an established application of Raman spectroscopy in many industrial fields. The extension of Raman spectroscopy as an AQC method in hospital environments imparts the benefits of a noninvasive and nondestructive analysis. The literature in using Raman spectroscopy as an AQC method for chemotherapy preparation and anesthesia gas monitoring is reviewed. Future applications in tissue engineering and incorporating new Raman techniques into AQC are also discussed.