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Intra-operative Raman spectroscopy and ex vivo Raman mapping for assessment of cartilage degradation

Gaifulina, Riana; Nunn, Abigail D G; Draper, Edward R C; Strachan, Robin K; Blake, Nathan; Firth, Steven; Thomas, Geraint M H; Mcmillan, Paul F; Dudhia, Jayesh; 6ap, U K


Riana Gaifulina

Abigail D G Nunn

Edward R C Draper

Robin K Strachan

Nathan Blake

Steven Firth

Geraint M H Thomas

Paul F Mcmillan

Jayesh Dudhia

U K 6ap


The development of a label-free, non-destructive and safe analytical method such as Raman spectroscopy for assessing cartilage degradation is highly desirable. Compared to non-optical imaging modalities, Raman mapping offers a more sensitive means of directly assessing the chemical composition of cartilage in three-dimensional space and the potential to monitor cartilage degeneration to inform intervention and treatment strategies. Herein, we report the application of Raman spectroscopic methods ex vivo and at arthroscopy to identify molecular alterations in cartilage specimens containing minor focal lesions characteristic of the early disease phase. Our initial ex vivo analysis, obtained by single-point Raman spectroscopy of cartilage samples, supports previous findings based on S-O stretching vibration bands associated with sulphated glycosaminoglycans (sGAGs). We extended the analyses to the high-wavenumber region where we observed that vibrational bands assigned to C-H and O-H stretching modes discriminated early cartilage alterations from healthy cartilage samples. Furthermore, we performed a proof-of-concept in-clinic study using a custom-built optical probe to acquire Raman spectral measurements for the first time in patients undergoing arthroscopy of knee joints. Spectra were obtained with adequate signal-to-noise ratios that similarly discriminated between lesion and adjacent cartilage sites and identified reductions in sGAGs in apparently healthy cartilage. Building on this, we present initial results from Raman mapping to spatially resolve the molecular constituents of cartilage through its depth and across a lesion. Mapping revealed a non-uniform and reduced sGAG distribution within the lesion and peripheral cartilage that was otherwise visually normal, similar to the in-clinic observations, showing that the degradative influence of the lesion extended beyond its border. This was accompanied by a decreased fluorescence signal intensity, which suggests that fluorescence may provide valuable information as an adjunct to the Raman signal in discriminating normal and degenerating cartilage. This work demonstrates the value of Raman mapping over single-point Raman measurements for the analysis of the anisotropy of articular cartilage and highlights the potential of the technology for in vivo articular joint arthroscopy applications.


Gaifulina, R., Nunn, A. D. G., Draper, E. R. C., Strachan, R. K., Blake, N., Firth, S., …6ap, U. K. (2021). Intra-operative Raman spectroscopy and ex vivo Raman mapping for assessment of cartilage degradation. Applied Spectroscopy,

Journal Article Type Article
Acceptance Date Jun 5, 2021
Publication Date Jun 7, 2021
Deposit Date Mar 22, 2021
Publicly Available Date Jun 18, 2021
Journal Clinical Spectroscopy
Print ISSN 0003-7028
Publisher Optical Society of America
Peer Reviewed Peer Reviewed
Keywords Articular cartilage, osteoarthritis, Raman spectroscopy, Raman mapping, arthroscopy
Public URL
Additional Information This manuscript was assigned RVC manuscript approval number CSS_01962 through the previous submission process. The manuscript was not accepted at the time by the journal but has since been revised and I will be submitting to a different journal. Please let me know if I can use the same approval number.


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