Development of spectroscopic methods for assessing polymorphic content of efavirenz

Authors

  • Talita Atanazio Rosa Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil
  • Marcos Victor Gregório de Oliveira Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil
  • Maria Joanellys dos Santos Lima Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil https://orcid.org/0000-0002-1880-5267
  • Leandro de Moura França Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil
  • Pollyne Amorim Silva Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil
  • Rosali Maria Ferreira da Silva Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil https://orcid.org/0000-0002-4139-6035
  • Larissa Araújo Rolim Collegiate of Pharmaceutical Sciences, Federal University of Vale do São Francisco, Petrolina, Pernambuco, Brazil
  • Maria Fernanda Pimentel Department of Chemical Engineering, Federal University of Pernambuco, Recife, Pernambuco, Brazil
  • Pedro José Rolim Neto Department of Pharmacy, Federal University of Pernambuco, Recife, Pernambuco, Brazil

DOI:

https://doi.org/10.1590/

Keywords:

Efavirenz, Infrared spectroscopy, Near-infrared spectroscopy, Partial least squares, Polymorph(s), Raman spectroscopy

Abstract

The present work aimed to develop a new method for assessing the content of mixtures of polymorphic forms I and II of the drug Efavirenz (EFV) by vibrational spectroscopic techniques such as Middle (MIR) and Near (NIR) infrared and Raman, using multivariate calibration models. Benchtop and handheld instruments were used for NIR and Raman and a benchtop instrument for MIR. In addition, VIP scores and iPLS, variable selection methods were employed. The infrared techniques showed the best models, with Root Mean Squares Error (RMSE) around 5% (w/w). When MIR and portable NIR instruments were used, this value was lowered to 4% (w/w) with selection of variables by iPLS. Raman spectroscopy showed higher error, even with selection of variables, possibly due to the spot laser size used by instruments and the lack of uniformity of the particle size in the samples. The infrared methods developed were shown to be effective in quantifying polymorphic mixtures of EFV. Given the ease of use of handheld instruments, they may be applied as tools of process analytical technology for monitoring quality control during industrial processing.

Downloads

Download data is not yet available.

References

Andersen CM, Bro R. Variable selection in regression-a tutorial. J Chemom, 2010;24:728–737. https://doi.org/10.1002/cem.1360

» https://doi.org/10.1002/cem.1360.

Antonio M, Maggio RM. Assessment of mefenamic acid polymorphs in commercial tablets using chemometric coupled to MIR and NIR spectroscopies. Prediction of dissolution performance. J Pharm Biomed Anal, 2018;149:603–611. https://doi.org/10.1016/j.jpba.2017.11.053 .

» https://doi.org/10.1016/j.jpba.2017.11.053

ASTM Standard E1655. Standard practices for infrared multivariate quantitative analysis. ASTM Internacional, West Conshohocken, PA, 2017.

Bastos MM, Costa CCP, Bezerra TC, Silva FC, Boechat N. Efavirenz a nonnucleoside reverse transcriptase inhibitor of first-generation: Approaches based on its medicinal chemistry. Eur J Med Chem, 2016; 108:455–465.

Brittain H. On the physical characterization of pharmaceutical solids. United States: Informa Healthcare USA, Inc. 2007

Chong I, Jun C. Performance of some variable selection methods when multicollinearity is present. Chemom Intell Lab Syst, 2005; 78:103–112. https://doi.org/10.1016/j.chemolab.2004.12.011 .

» https://doi.org/10.1016/j.chemolab.2004.12.011

Costa B, Vale N. Efavirenz: History, Development and Future. Biomolecules. 2023;13(1):88. https://doi.org/10.3390/biom13010088 .

» https://doi.org/https://doi.org/10.3390/biom13010088

Eilers PHC, Boelens HFM. Baseline Correction with Asymmetric Least Squares Smoothing. Life Sci, 2005:1–24. https://doi.org/10.1021/ac034173t .

» https://doi.org/10.1021/ac034173t.

Esclusa-Diaz MT, Guimaraens-Méndez M, Pérez-Marcos MB, Vila-Jato JL, Torres-Labandeira JJ. Characterization and in vitro dissolution behaviour of ketoconazole/β- and 2-hydroxypropyl-β-cyclodextrin inclusion compounds. Int J Pharm, 1996; 143:203–210. https://doi.org/10.1016/S0378-5173(96)04704-7 .

» https://doi.org/10.1016/S0378-5173(96)04704-7

Fandaruff C, Rauber GS, Araya-Sibaja AM, Pereira RN, Campos CEM, Rocha HVA, et al. Polymorphism of anti- HIV drug efavirenz: Investigations on thermodynamic and dissolution properties. Cryst Growth Des, 2014; 14:4968– 4975. https://doi.org/10.1021/cg500509c .

» https://doi.org/10.1021/cg500509c

Farias MAS, Carneiro RL. Simultaneous Quantification of Three Polymorphic Forms of Carbamazepine using Raman Spectroscopy and Multivariate Calibration. Anal Lett, 2014; 47:6. https://doi.org/10.1080/00032719.2013.860537 .

» https://doi.org/10.1080/00032719.2013.860537

FDA - Food and Drug Administration. 2007. Draft Guidance for Industry. ANDAs: Pharmaceutical Solid Polymorphism. Chemistry, Manufacturing and Controls Information.

Fearn T, Riccioli C, Garrido-Varo C, Guerrero-Ginel JE. On the geometry of SNV and MSC. Chemom. Intell Lab Syst, 2009; 96:22–26. https://doi.org/10.1016/j.chemolab.2008.11.006 .

» https://doi.org/10.1016/j.chemolab.2008.11.006.

Galvão RKH, Araujo MCU, José GE, Pontes MJC, Silva EC, Saldanha TCB. A method for calibration and validation subset partitioning. Talanta. 2005; 67:736–740. https://doi.org/10.1016/j.talanta.2005.03.025 .

» https://doi.org/10.1016/j.talanta.2005.03.025

Gómez DA, Coello J, Maspoch S. The influence of particle size on the intensity and reproducibility of Raman spectra of compacted samples. Vib Spectrosc. 2019;100:48–56. https://doi.org/10.1016/j.vibspec.2018.10.011

» https://doi.org/10.1016/j.vibspec.2018.10.011

Guo C, Luo X, Zhou X, Shi B, Wang J, Zhao J, Zhang X, et al. Quantitative analysis of binary polymorphs mixtures of fusidic acid by diffuse reflectance FTIR spectroscopy, diffuse reflectance FT-NIR spectroscopy, Raman spectroscopy and multivariate calibration. J Pharm Biomed Anal. 2017;140:130–136. https://doi.org/10.1016/j.jpba.2017.02.053 .

» https://doi.org/10.1016/j.jpba.2017.02.053

ICH - International Council for Harmonization, Specifications: Test procedures and aceptance Criteria for New Drug Substances and New Drug Products: Chemical Substances Q6A, in: Intergovernmental Panel on Climate Change (Ed.), ICH Harmon Tripart Guidel, Cambridge: Cambridge University Press;1999:1–30.

Kang Y, Shao Z, Wang Q, Hu X, Yu D. Quantitation of polymorphic impurity in entecavir polymorphic mixtures using powder X-ray diffractometry and Raman spectroscopy. J Pharm Biomed Anal. 2018;158:28–37. https://doi.org/10.1016/j.jpba.2018.05.026 .

» https://doi.org/10.1016/j.jpba.2018.05.026

Kim EJ, Kim JH, Kim M-S, Jeong SH, Choi DH. Process Analytical Technology Tools for Monitoring Pharmaceutical Unit Operations: A Control Strategy for Continuous Process Verification. Pharmaceutics. 2021;13(6):919. https://doi.org/10.3390/pharmaceutics13060919

» https://doi.org/10.3390/pharmaceutics13060919

Lindon JC, Tranter GE, Koppenaal D. 2017. Encyclopedia of Spectroscopy and Spectrometry. Elsevier ltd.

Luo J, Ying K, Bai J. Savitzky-Golay smoothing and differentiation filter for even number data. Signal Processing. 2005;85:1429–1434. https://doi.org/10.1016/j.sigpro.2005.02.002 .

» https://doi.org/10.1016/j.sigpro.2005.02.002

Mahapatra S, Thakur TS, Joseph S, Varughese S, Desiraju GR. New solid state forms of the anti-HIV drug efavirenz. Conformational flexibility and high Z′ issues. Cryst Growth Des, 2010;10:3191–3202. https://doi.org/10.1021/cg100342k .

» https://doi.org/10.1021/cg100342k.

Marques MM, Rezende CA, Lima GC, Marques ACS, Prado LD, Leal KZ, et al. New solid forms of efavirenz: Synthesis, vibrational spectroscopy and quantum chemical calculations. J Mol Struct, 2017;1137:476–484. https://doi.org/10.1016/j.molstruc.2017.02.061 .

» https://doi.org/10.1016/j.molstruc.2017.02.061

Mbuagbaw L, Mursleen S, Irlam JH, Spaulding AB, Rutherford GW, Siegfried N. Efavirenz or nevirapine in three- drug combination therapy with two nucleoside or nucleotide- reverse transcriptase inhibitors for initial treatment of HIV infection in antiretroviral-naïve individuals. Cochrane Database Syst Rev. 2016;12(12):CD004246. https://doi/10.1002/14651858.CD004246.pub4 .

» https://doi.org/10.1002/14651858.CD004246.pub4.

Mishra S, Tandon P, Ayala AP 2012. Study on the structure and vibrational spectra of efavirenz conformers using DFT: Comparison to experimental data. Spectrochim Acta - Part A Mol Biomol Spectrosc, 2012; 88:116–123. https://doi.org/10.1016/j.saa.2011.12.010 .

» https://doi.org/10.1016/j.saa.2011.12.010

Nørgaard L, Saudland A, Wagner J, Nielsen JP, Munck L, Engelsen SB. Interval Partial Least-Squares Regression (iPLS): A Comparative Chemometric Study with an Example from Near-Infrared Spectroscopy. Appl Spectrosc, 2000; 54:413–419. https://doi.org/10.1366/0003702001949500 .

» https://doi.org/10.1366/0003702001949500

Paiva EM, Silva VH, Poppi RJ, Pereira CF, Rohwedder JJR. Comparison of macro and micro Raman measurement for reliable quantitative analysis of pharmaceutical polymorphs. J Pharm Biomed Anal, 2018; 157:107–115. https://doi.org/10.1016/j.jpba.2018.05.010 .

» https://doi.org/10.1016/j.jpba.2018.05.010

Qiu J, Li G, Sheng Y, Zhu M. Quantification of febuxostat polymorphs using powder X-ray diffraction technique. J Pharm Biomed Anal, 2015;107:298–303. https://doi.org/10.1016/j.jpba.2015.01.005 .

» https://doi.org/10.1016/j.jpba.2015.01.005

Radesca LA, Maurin MB, Rabel SR, Moore JR, inventors. Bristol Myers Squibb Pharma Co, assignee. Crystalline Efavirenz. US Patent 6673372B1. [ONLINE] 2004-01-06. Avaiable at: https://patents.google.com/patent/US6673372B1/en?q=Crystalline&q=Efavirenz&oq=Crystalline+Efavirenz [Accessed on March 25, 2024].

» https://patents.google.com/patent/US6673372B1/en?q=Crystalline&q=Efavirenz&oq=Crystalline+Efavirenz

Ravikumar K, Sridhar B. Molecular and crystal structure of efavirenz, a potent and specific inhibitor of HIV-1 reverse transcriptase, and its monohydrate. Mol Cryst Liq Cryst, 2009;515:190–198.

Reddy BP, Reddy KR, Reddy RR, Reddy DM, Reddy KSC, inventors. Hetero Drugs Ltd, assignee. Polymorphs of efavirenz. US patent 8466279B2. 2013-06-18. [ONLINE] Avaiable at: https://patents.google.com/patent/US8466279 [Accessed on March 25, 2024].

» https://patents.google.com/patent/US8466279

Rinnan Å, Van Den Berg F, Engelsen SB. Review of the most common pre-processing techniques for near-infrared spectra. TrAC - Trends Anal Chem, 2009; 28:1201–1222. https://doi.org/10.1016/j.trac.2009.07.007 .

» https://doi.org/10.1016/j.trac.2009.07.007

Eigenvector. Advanced Preprocessing: Noise, Offset, and Baseline Filtering. 2019. Avaiable at: http://wiki.eigenvector.com/index.php?title=Advanced_Preprocessing:_Noise,_Offset,_and_Baseline_Filtering [Accessed on March 25, 2024].

» http://wiki.eigenvector.com/index.php?title=Advanced_Preprocessing:_Noise,_Offset,_and_Baseline_Filtering

Sankoh O, Arthur S, Nyide B, et al. Prevention, treatment and future challenges of HIV/AIDS: A decade of INDEPTH research. HIV AIDS Rev, 2014;14:1–8.

Siddiqui A, Rahman Z, Sayeed VA, et al. Chemometric evaluation of near infrared, fourier transform infrared, and raman spectroscopic models for the prediction of nimodipine polymorphs. J Pharm Sci, 2013; 102:4024–4035. https://doi.org/10.1002/jps.23712

» https://doi.org/10.1002/jps.23712

Silva VH, Gonçalves JL, Vasconcelos FVC, et al. Quantitative analysis of mebendazole polymorphs in pharmaceutical raw materials using near-infrared spectroscopy. J Pharm Biomed Anal, 2015;115:587–593. https://doi.org/10.1016/j.jpba.2015.08.018

» https://doi.org/10.1016/j.jpba.2015.08.018

Silva VH, Silva JJ, Pereira CF. Portable near-infrared instruments: Application for quality control of polymorphs in pharmaceutical raw materials and calibration transfer. J Pharm Biomed Anal, 2017;134:287–294. https://doi.org/10.1016/j.jpba.2016.11.036

» https://doi.org/10.1016/j.jpba.2016.11.036

Silverstein KD, Webster RM, Silverstein FX. Spectrometric Identification of Organic Compounds. New York: John Wiley & Sons, Inc. 2005.

Stuart BH. Infrared Spectroscopy: Fundamentals and Applications. John Wiley & Sons. 2004.

Vrouenraets SM, Wit FW, Van Tongeren J, Lange JMA. Efavirenz: a review. Expert Opin Pharmacother, 2007; 8:851–871. https://doi.org/10.1517/14656566.8.6.851 .

» https://doi.org/10.1517/14656566.8.6.851

Downloads

Published

2024-11-05

Issue

Vol. 60 (2024)

Section

Article

License

Copyright (c) 2024 Brazilian Journal of Pharmaceutical Sciences

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

All content of the journal, except where identified, is licensed under a Creative Commons attribution-type BY.

The on-line journal has open and free access.

How to Cite

Development of spectroscopic methods for assessing polymorphic content of efavirenz. (2024). Brazilian Journal of Pharmaceutical Sciences, 60. https://doi.org/10.1590/

Funding data