Abstract
Purpose
The concept of molecular factor computing (MFC)-based predictive spectroscopy was demonstrated here with quantitative analysis of ethanol-in-water mixtures in a MFC-based prototype instrument.
Methods
Molecular computing of vectors for transformation matrices enabled spectra to be represented in a desired coordinate system. New coordinate systems were selected to reduce the dimensionality of the spectral hyperspace and simplify the mechanical/electrical/computational construction of a new MFC spectrometer employing transmission MFC filters. A library search algorithm was developed to calculate the chemical constituents of the MFC filters. The prototype instrument was used to collect data from 39 ethanol-in-water mixtures (range 0–14%). For each sample, four different voltage outputs from the detector (forming two factor scores) were measured by using four different MFC filters. Twenty samples were used to calibrate the instrument and build a multivariate linear regression prediction model, and the remaining samples were used to validate the predictive ability of the model.
Results
In engineering simulations, four MFC filters gave an adequate calibration model (r2 = 0.995, RMSEC = 0.229%, RMSECV = 0.339%, p = 0.05 by f test). This result is slightly better than a corresponding PCR calibration model based on corrected transmission spectra (r2 = 0.993, RMSEC = 0.359%, RMSECV = 0.551%, p = 0.05 by f test). The first actual MFC prototype gave an RMSECV = 0.735%.
Conclusion
MFC was a viable alternative to conventional spectrometry with the potential to be more simply implemented and more rapid and accurate.
Similar content being viewed by others
References
R. J. Dempsey, D. G. Davis, R. G. Buice, and R. A. Lodder. Biological and medical applications of near-infrared spectroscopy. Appl. Spectrosc. 50:18A–34A (1996).
J. K. Drennen and R. A. Lodder. Nondestructive near-infrared analysis of intact tablets for determination of degradation products. J. Pharm. Sci. 79:622–627 (1990).
A. S. El-Hagrasy, H. R. Morris, F. D’Amico, R. A. Lodder, and J. K. Drennen, 3rd. Near-infrared spectroscopy and imaging for the monitoring of powder blend homogeneity. J. Pharm. Sci. 90:1298–1307 (2001).
A. Urbas, M. W. Manning, A. Daugherty, L. A. Cassis, and R. A. Lodder. Near-infrared spectrometry of abdominal aortic aneurysm in the ApoE−/− mouse. Anal. Chem. 75:3318–3323 (2003).
T. D. Ridder, S. P. Hendee, and C. D. Brown. Noninvasive alcohol testing using diffuse reflectance near-infrared spectroscopy. Appl. Spectrosc. 59:181–189 (2005).
J. C. Soto, C. P. Meza, W. Caraballo, C. Conde, T. Li, K. R. Morris, and R. J. Romanach. On line non-destructive determination of drug content in moving tablets using near infrared spectroscopy. Journal of Process Analytical Technology 2(5):8–14 (2005).
Guidance for Industry PAT—A Framework for Innovative Pharmaceutical Manufacturing and Quality Assurance, U.S. Department of Health and Human Services, Food and Drug Administration, Center for Drug Evaluation (CDER), and Research (CDER),Center for Veterinary Medicine (CVM), Office of Regulatory Affairs (ORA), September 2004.
A. S. Hussain. Process analytical technology: a first step in a jouney towards the desired state. Journal of Process Analytical Technology 2(1):8–13 (2005).
S. R. Byrn, J. K. Liang, S. Bates, and A. W. Newman. PAT—process understanding and control of active pharmaceutical ingredients. Journal of Process Analytical Technology 3(6):14–19 (2006).
M. R. Fischer and G. M. Hieftje. Near-IR multiplex bandpass spectrometer utilizing polymer filters. Appl. Spectrosc. 50:1246–1252 (1996).
A. Fong and M. G. Hieftje. Near-IR multiplex bandpass spectrometer using liquid molecular filters. Appl. Spectrosc. 49:493–498 (1995).
K. R. Beebe and B. R. Kowalski. Introduction to multivariate calibration & analysis. Anal. Chem. 59:1007A–1017A (1987).
H. Martens and M. Martens. Multivariate analysis of quality an introduction. Wiley, Chicester (2001).
H. Martens and T. Naes. Multivariate calibration. Chapman and Hall, London (1989).
R. Leardi. Application of genetic algorithm-PLS for feature selection in spectral data sets. J. Chemom. 14:643–655 (2000).
R. Leardi. Genetic algorithm-PLS as a tool for wavelength selection in spectral data sets. Data Handl. Sci. Technol. 23:169–196 (2003).
C. Schwartz. Integrated Sensing and Processing http://www.darpa.mil/dso/thrust/math/isp.htm.
O. Soyemi, D. Eastwood, L. Zhang, H. Li, J. Karunamuni, P. Gemperline, R. A. Synowicki, and M. L. Myrick. Design and testing of a multivariate optical element: The first demonstration of multivariate optical computing for predictive spectroscopy. Anal. Chem. 73:1069–1079 (2001).
S. E. Bialkowski. Species discrimination and quantitative estimation using incoherent linear optical signal processing of emission signals. Anal. Chem. 58:2561–2563 (1986).
A. M. C. Prakash, C. M. Stellman, and K. S. Booksh. Optical regression: a method for improving quantitative precision of multivariate prediction with single channel spectrometers. Chemometr. Intell. Lab. Syst. 46:265–274 (1999).
F. G. Haibach, A. E. Greer, M. V. Schiza, R. J. Priore, O. O. Soysmi, and M. L. Myrick. On-line reoptimization of filter designs for multivariate optical elements. Appl. Opt. 42:1833–1838 (2003).
F. G. Haibach and M. L. Myrick. Precision in multivariate optical computing. Appl. Opt. 43:2130–2140 (2004).
M. L. Myrick, O. Soyemi, J. Karunamuni, D. Eastwood, H. Li, L. Zhang, A. E. Greer, and P. Gemperline. A single-element all-optical approach to chemometric prediction. Vibr. Spectrosc. 28:73–81 (2002).
M. L. Myrick, O. Soyemi, H. Li, L. Zhang, and D. Eastwood. Spectral tolerance determination for multivariate optical element design. Fresenius’ J. Anal. Chem. 369:351–355 (2001).
M. L. Myrick, O. O. Soyemi, F. Haibach, L. Zhang, A. Greer, H. Li, R. Priore, M. V. Schiza, and J. R. Farr. Application of multivariate optical computing to near-infrared imaging. Proc. SPIE Int. Soc. Opt. Eng. 4577:148–157 (2002).
M. L. Myrick, O. O. Soyemi, M. V. Schiza, J. R. Farr, F. Haibach, A. Greer, H. Li, and R. Priore. Application of multivariate optical computing to simple near-infrared point measurements. Proc. SPIE Int. Soc. Opt. Eng. 4574:208–215 (2002).
O. O. Soyemi, F. G. Haibach, P. J. Gemperline, and M. L. Myrick. Nonlinear optimization algorithm for multivariate optical element design. Appl. Spectrosc. 56:477–487 (2002).
O. O. Soyemi, F. G. Haibach, P. J. Gemperline, and M. L. Myrick. Design of angle-tolerant multivariate optical elements for chemical imaging. Appl. Opt. 41:1936–1941 (2002).
L. A. Cassis, B. Dai, A. Urbas, and R. A. Lodder. In vivo applications of a molecular computing-based high-throughput NIR spectrometer. Proc. SPIE-Int. Soc. Opt. Eng. 5329:239–253 (2004).
L. A. Cassis, A. Urbas, and R. A. Lodder. Hyperspectral integrated computational imaging. Anal. Bioanal. Chem. 382:868–872 (2005).
P. Geladi and B. Kowalski. Partial least-squares regression: a tutorial. Anal. Chim. Acta 185:1–17 (1986).
E. Huang, S. H. Cheng, H. Dressman, J. Pittman, M.-H. Tsou, C.-F. Horng, A. B. E. S. Iversen, M. Liao, C.-M. Chen, M. West, J. R. Nevins, and A. T. Huang. Gene expression predictors of breast cancer outcomes. Lancet 361:1590–1596 (2003).
R. A. Lodder and G. A. Hieftje. Detection of subpopulations in near-infrared reflectance analysis. Appl. Spectrosc. 42:1500–1512 (1988).
Y. Zou, et al. Making your best case—near-IR spectral identification of soil. Anal. Chem. 65:A434–A439 (1993).
Acknowledgement
This work was supported in part by the National Science Foundation through CNS-0540178, the Kentucky Science and Education Fund, and by the National Institutes of Health through N01AA 33003 and T32 HL072743.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Dai, B., Urbas, A., Douglas, C.C. et al. Molecular Factor Computing for Predictive Spectroscopy. Pharm Res 24, 1441–1449 (2007). https://doi.org/10.1007/s11095-007-9260-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11095-007-9260-1