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Applied Spectroscopy Reviews


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FTIR Spectrophotometric Methods Used for Antioxidant Activity Assay in Medicinal Plants
Andrei A. Bunaciu , Hassan Y. Aboul-Enein & Serban Fleschin
a a b c

SC HOFIGAL SA, Research & Development Department, Bucharest, Romania


b

Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries Research Division, Dokki, Cairo, Egypt
c

Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Bucharest, Romania Available online: 17 Apr 2012

To cite this article: Andrei A. Bunaciu, Hassan Y. Aboul-Enein & Serban Fleschin (2012): FTIR Spectrophotometric Methods Used for Antioxidant Activity Assay in Medicinal Plants, Applied Spectroscopy Reviews, 47:4, 245-255 To link to this article: http://dx.doi.org/10.1080/05704928.2011.645260

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Applied Spectroscopy Reviews, 47:245255, 2012 Copyright Taylor & Francis Group, LLC ISSN: 0570-4928 print / 1520-569X online DOI: 10.1080/05704928.2011.645260

FTIR Spectrophotometric Methods Used for Antioxidant Activity Assay in Medicinal Plants
ANDREI A. BUNACIU,1 HASSAN Y. ABOUL-ENEIN,2 AND SERBAN FLESCHIN3
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SC HOFIGAL SA, Research & Development Department, Bucharest, Romania Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries Research Division, Dokki, Cairo, Egypt 3 Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Bucharest, Romania
Abstract: Fourier transform infrared spectroscopy (FTIR) is a fast and nondestructive analytical method. Associated with chemometrics, it is a powerful tool for research and industry. The present review discusses the antioxidant activities assay of some plants (fruits, leaves, aerian part) with medicinal properties using an FTIR spectrophotometric method in comparison with other ultraviolet-visible (UV-Vis) spectrophotometric methods. A good correlation was found between the different methods used for measuring the antioxidant capacity of some of these herbs. Keywords: Antioxidant activity, FTIR spectrophotometric methods, medicinal plants

Introduction
Medicinal plants constitute a major source of phytopharmaceutical products and dietary supplements. A whole range of natural products derived from plants, phytochemicals, and provitamins, which help to maintain health and ght disease, are now described as food supplements. The products derived from plants become more and more accepted and used in the cosmetics industry. In 1987, the World Health Organization (WHO) stated the importance of scientic research on herbal supplements, and there is sufcient evidence that such products may have benecial effects. Without doubt, herbal drug use is one of the oldest forms of health care, so the WHO has estimated that 80% of the world population still relies on botanic medication (1). National ora are remarkable for their diversity and richness; many species of plants are known for their therapeutic role. However, more research is still needed to explore their utility in modern therapy. In recent years, antioxidants have gained a lot of importance due to their potential as prophylactic and therapeutic agents in many diseases (2, 3). Traditionally, herbal medicines

This article is in memory of Magda Carmen Bunaciu (19552011). Address correspondence to Professor Hassan Y. Aboul-Enein, Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries Research Division, Tahrir Street, Dokki, Cairo12311, Egypt. E-mail: haboulenein@yahoo.com

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with antioxidant properties have been used for various purposes, and epidemiological data also point to widespread acceptance and use of these agents. Presently, the active constituents from these herbal sources are extracted, puried, and tested for their activities. Infrared (IR) spectrometry provides a useful method for herbal analysis (4, 5) as well as for quantitative analysis of drugs (6), and the help of Fourier transform infrared (FTIR) permits continuous monitoring of the spectral baseline and simultaneous analysis of different components of the same sample. There are numerous studies related to evaluation of antioxidant capacity of plant materials. Methods that measure the antioxidants radical scavenging ability include total peroxyl radical trapping parameter (TRAP) (7), oxygen radical absorbance capacity (ORAC) (8), Trolox equivalent antioxidant capacity (TEAC) (9), 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) (10), and N,N-dimethyl-p-phenylenediamine (DMPD) radical (11) assays. The reducing ability of plasma in the presence of antioxidant was determined by the ferric ionreducing antioxidant parameter (FRAP) assay (12). Other commonly used antioxidant activity methods include cupric reducing antioxidant capacity (CUPRAC) (13), cerium (IV) reduction (14), phosphomolybdenum complex (15), and inhibited oxygen uptake (IOU) (16). The present review discusses the antioxidant activities of some plants (fruits, leaves, and/or aerial part) with medicinal properties using FTIR spectrophotometric methods in comparison with other methods. Prior to the review on this subject, it is useful to provide a short introduction to the concept of the antioxidant activity and substances involved in this mechanism. Furthermore, the quantitative and qualitative determinations of antioxidant activity in different plants are presented.

Antioxidant Activity
Antioxidants are a class of compounds of great interest for the pharmaceutical industry and biochemists and other health professionals because they are designed to reduce damage caused by reactive oxygen species (ROS), nitrogen (RNS), or even chlorine (RCS). The discovery of the role of free radicals in cancer, diabetes, cardiovascular diseases, autoimmune diseases, neurodegenerative disorders, aging, and other diseases has led to a medical revolution that is promising a new paradigm of health care. There is also great interest in trying to achieve partial or total replacement of synthetic antioxidants with natural ingredients, in view of concerns about possible side effectsincluding cancerof some synthetic antioxidants in food. The importance of the mechanism of oxidation in the body as well as in food is widely accepted. Oxidative metabolism is an essential process for cell survival. A side effect of this metabolism is that excess production of free radicals and other ROS can cause undesirable oxidative changes. There is increasing evidence for the involvement of high reactivity of these species in a variety of diseases. Antioxidants are substances that counteract free radicals and prevent damage caused by them. These can greatly reduce the adverse damage due to oxidants by crumbling them before they react with biologic targets, preventing chain reactions or preventing the activation of oxygen to highly reactive products (17). Antioxidants can be classied into two major groups; that is, enzymatic and nonenzymatic antioxidants. Some of these antioxidants are endogenously produced, including enzymes, low-molecular-weight molecules, and enzyme cofactors. Many nonenzymatic antioxidants are obtained from dietary sources. Dietary antioxidants can be classied into

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Figure 1. Classication of antioxidants.

various classes (18), of which polyphenols is the largest class. Polyphenols consist of phenolic acids and avonoids. The other classes of dietary antioxidants include vitamins, carotenoids, organosulfural compounds, and minerals (Figure 1). Many methods reported for determination of antioxidant activity (19). Table 1 lists the major methods involved in antioxidant activity assays.

Applications
A large number of publications are available in the literature that are dedicated to antioxidant activity assays using FTIR spectrometry. Most of these papers are related to the qualitative and quantitative assays of active compounds. In this section, new methods for quantitative determinations of antioxidant activity will be presented followed by examples for the utilization of FTIR spectroscopy in studying the relationship between the chemical structure and antioxidant activity. The antioxidant content of fruits has made them a desirable component of the human diet. Several wet chemistry techniques, including the ORACFL assay, have been reported for measuring the antioxidant activities of fruit. Lam et al. (20) investigated the use of FTIR to measure fruits antioxidant activity. This study shows that an FTIR technique is suitable for rapidly measuring fruit extract antioxidant activity. A good calibration model (R2 = 0.97) for antioxidant activity was obtained with satisfactory predictive ability (root mean square error [RMSE] = 5.35) using the spectral region 2000 to 900 cm1.

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Assays involving hydrogen atom transfer reactions (HATs): ROO + AH ROOH + A ROO + LH ROOH + L Assays involving electron transfer (ET): Men + e (din AH) Me(n1) + AH

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Other methods

TRAP (7) ORAC (8) Crocin method IOU (16) Inhibition of linoleic acid oxidation TEAC (9) DPPH (10) FRAP (12) CUPRAC (13) Ce(IV) ions reduction (14) Mo(VI) ions reduction (15) Folin-Ciocalteu Total oxidant scavenging capacity (TOSC) (54) Briggs-Rauscher reaction (55) Chemiluminiscence (56) Electrochemiluminscence (57) FTIR

In other paper, Lam et al. (21) investigated the use of FTIR for measuring the changes in human low-density lipoproteins (LDL) primary and secondary lipid oxidation products and modication of the apolipoprotein B-100s (apoB-100) secondary structures during Cu2+mediated oxidation in the presence of catechin, quercetin, and -tocopherol at physiological concentrations. Relationships between peroxide formation, carbonyl products, and LDL protein denaturation were shown by the FTIR approach. The FTIR technique provided a simple new tool for a comprehensive evaluation of antioxidant performance in protecting LDL during in vitro oxidation. An FTIR spectroscopic method was developed for the determination of -tocopherol in rened, bleached, and deodorized (RBD) palm olein (22). The calibration and validation samples were prepared by spiking a known amount of -tocopherol to produce a wide range of -tocopherol up to 2,000 ppm. The partial least squares (PLS) calibration models for predicting -tocopherol were developed using the FTIR spectral region at 31002750 cm1. The accuracy of the method was comparable to that of high-performance liquid chromatography (HPLC) (23), with coefcients of determination (R2) from calibration samples of 0.9922. A simple, rapid, and direct FTIR spectroscopic method was developed for the determination of butylated hydroxytoluene (BHT) content in RBD palm olein and RBD palm oil (24). The method used sodium chloride windows with a 50-mm transmission path. FTIR results for both oils correlated well with results obtained by the IUPAC HPLC-based method. Due to the signicant decrease in analysis time and reduction in solvent usage, this FTIR method for BHT is especially well suited for routine quality control applications in the palm oil industry. Phycocolloids present in three brown seaweeds (Himanthalia elongata, Bifurcaria bifurcata, Saccharina latissima) and ve red edible seaweeds (Mastocarpus stellatus,

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Gigartina pistillata, Chondracanthus acicularis, Nemalion helminthoides, and Dumontia contorta) were studied by Fourier transform infraredattenuated total reectance (FTIRATR) spectroscopy. Infrared spectra of polysaccharide standards (alginate, agar, and iota-, kappa-, and lambda-carrageenan) were obtained for comparison (25). Therefore, FTIRATR spectroscopy is proposed as a useful tool for the food, pharmaceutical, and cosmetics industries to check the phycocolloid quality of a raw seaweed material by a quick and nondestructive method. Total phenolic content (TPC) and total antioxidant capacity (TAC) of four onion varieties (red, white, yellow, and sweet) and shallot from selected locations (Washington, Idaho, Oregon, Texas, and Georgia) were determined using FTIR spectroscopy (4000400 cm1) (26). The Folin-Ciocalteu (FC) assay was used to quantify TPC and three different methods were used to determine TAC, including 2,2-diphenyl-picrylhydrazyl (DPPH) (10), TEAC (9) and FRAP (12) assays. A correlation of r > 0.95 was obtained between FTIR-predicted and reference values (by FC, DPPH, TEAC, and FRAP assay) with standard errors of calibration (SEC) and standard errors of cross-validation (SECV) less than 2.85, 0.35, and 0.45 mol Trolox/g fresh weight (FW) of extracts for TEAC, FRAP, and DPPH assays, respectively, and 0.36 mg gallic acid/g FW of extracts for the FC assay. The determination of sweet cherry anthocyanins in crude material of three varieties using diffuse reectance infrared Fourier transform spectroscopy (DRIFTS) and the curvetting deconvolution method was described in Pappas et al. (27). A linear relationship between the sweet anthocyanins content and the peak area at 16401630 cm1 was established with a high correlation coefcient (0.990). The deconvolution analysis using the curve-tting method allowed elimination of spectral interferences from other cell wall components. The proposed methodology was compared with a reference ultraviolet-visible (UV-Vis) spectrophotometric method (28) and found equivalent in reproducibility and accuracy. FTIR spectroscopy provides rapid and nondestructive analysis of wine, with almost no sample preparation (29). Versari et al. (29) studied the use of FTIR measurement for the prediction of red wine TAC. PLS regression was chosen for evaluation of the FTIR spectra. A plot of the full cross-validated PLS-predicted TAC values showed a good correlation (r = 0.85), and the slope of 0.74 and the prediction error provided by the PLS model were consistent with the uncertainty derived from the reference method. Rapid FTIR spectroscopy combined with ATR was applied for quantitative analysis of virgin coconut oil (VCO) in binary mixtures with olive oil (OO) and palm oil (PO) (30). The spectral bands correlated with VCO, OO, PO; blends of VCO and OO; and VCO and PO were scanned, interpreted, and identied. Two multivariate calibration methods, PLS and principal component regression (PCR), were used to construct calibration models that correlate between actual and FTIR-predicted values of VCO contents in the mixtures at the FTIR spectral frequencies of 11201105 and 965960 cm1. In general, FTIR spectroscopy serves as a suitable technique for determination of VCO in mixtures with the other oils. A rapid FTIR-ATR spectroscopic method was applied to the determination of water content (WC), total phenol amount (TP), and antioxidant activity (ABTS+) of virgin olive oils (VOOs) and olive oils (31). Calibration models were constructed using partial least squares regression. The FTIR-ATR method provided results that were comparable to conventional procedures. Moreover, the ATR-FTIR-PLS method developed herein was faster; the complete determination takes only a few minutes compared to the long time required for both the WC analysis (approximately 30 min) by titrimetric analysis and TP and ABTS+ spectrophotometric determinations (several hours taking into consideration phenol extraction, reactive preparation, and the long wait for the complete reaction).

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Vegetable oils (e.g., soybean oil) are the main biodegradable lubricant base stocks used worldwide. Castro et al. (32) compared the oxidative and wear performance of oils to better understand how the chemical composition of the base stock affects these properties. Oxidation products from the micro-oxidation test were analyzed by FTIR and gel permeation chromatography. All oils were evaluated neat, without additives. Soybean oil (SBO) was blended with 1040% palm kernel olein (PKO) to obtain SBO:PKO blends with different degrees of unsaturation. These blends can be determined using an FTIR method (33). Oil-in-water (O/W) emulsions were prepared with 70 wt% of SBO or SBO:PKO blends and monitored for their chemical destabilization after an accelerated oxidation process up to 12 days at 60 C. The formation rate of hydroperoxides, as demonstrated by peroxide value (PV) evolution, throughout the oxidation period was relatively high for a fully SBO-based emulsion compared to those with PKO incorporation. An FTIR spectroscopic method was also performed in parallel with PV determination, providing further information on structural changes of the functional groups due to lipid oxidation in the emulsions. By using a PLS chemometric method, a developed calibration model that was based on the spectral region between 1800 and 1480 cm1 was shown to be able to predict the PV in oxidized emulsions over the range of 445 meq/kg. The calibration model provides a good coefcient of determination of 0.98 and a root mean standard error of cross-validation of 2.09. FTIR spectroscopy was investigated as a method for analysis of acesulfame-K content after a simple extraction procedure for certain commercial diet food samples (34). Partial least squares models were developed for prediction of acesulfame-K using select spectral ranges on the basis of relevant IR absorption bands associated with acesulfame-K. The acesulfame-K content of test food samples was predicted accurately in the ngerprint region between 1100 and 1300 cm1 with a maximum prediction error of 9.82% when compared with conventional HPLC methods. The PLS was found to be a consistently better predictor when both PLS and PCR analyses were used for quantication of acesulfame-K. Peridural scarring, or the excessive formation of scar tissue following spinal surgery, is one of the important contributing factors that result in persistent pain and disability in many individuals who have undergone elective back surgery. Treatment with anti-inammatory agents following surgery may reduce oxidative stress and scarring, leading to a reduction in postoperative pain. Wiens et al. (35) used a surgical rat model to test the hypothesis that postsurgical inammation and oxidative stress following laminectomy can be reduced by systemic administration of l-2-oxothiazolidine-4-carboxylate (OTC) and quercetin. OTC is a cysteine precursor required for the synthesis of glutathione, an important antioxidant. Quercetin is a avonoid with antioxidant properties found in fruits and vegetables. Synchrotron FTIR microspectroscopy data have been collected on OTC, quercetin, and saline (control)-treated postsurgery animals, sacriced at 3 and 21 days (n = 6 per age and treatment group). Preliminary IR results were presented, supported by immunocytochemistry, on the heterogenous distribution of biological components present in the healing tissue. Thermal and mechanical degradation of natural rubber (NR) mixed with N-(1,3dimethylbutyl)-N -phenyl-p-phenylenediamine (6PPD), polymerized 1,2-dihydro-2,2,4trimethyl-quinoline (TMQ), and 50/50 weight basis mixture under high-temperature and shearing conditions were investigated using a moving die processability test and FTIR spectroscopy (36). The antioxidative capability of those antioxidants on NR was ordered based on their effectiveness as follows: 6PPD > (6PPD mixed with TMQ) > TMQ. It was also found that the moving die processability test and FTIR spectroscopy are efcient routes to estimate the oxidative degradation of NR molecules. Therefore, the techniques

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could be applied to assess or compare antioxidative capability of various types and amounts of antioxidants used in the rubber formulation within a reasonable testing time. The relationship between dynamic properties in terms of tan value and chemical changes of NR molecules during degradation were correlated. A PLS regression model based on ATR-FTIR spectra of heated olive oil samples has been developed for determination of polymerized triacylglycerides (PTGs) generated during thermal treatment of oil (37). Three different approaches for selection of the spectral regions used to build the PLS model were tested and compared: (1) variable selection based on expert knowledge, (2) uninformative variable elimination PLS, and (3) interval PLS. Each of the three variable selection methods provided PLS models from heated olive oil samples with excellent performance for the prediction of PTGs in fried olive oils with comparable model statistics. Furthermore, it was veried that the determination of PTGs was not inuenced by the type of foodstuff fried in the olive oil. A rapid FTIR-ATR spectroscopic method coupled with PLS was developed to estimate the oxidation degree of extra virgin olive oil (EVOO) (38). The reference values of EVOO oxidation for the FTIR calibration were obtained by the specic absorptions at 232 and 270 nm, due to the presence of conjugated diene (CD) and conjugated triene (CT) groups, as monitored by the UV spectrophotometric determination. The results of the study indicated that a strong correlation existed between FTIR and UV-Vis peak intensities. A fast, versatile, inexpensive, and environmentally safe analytical method was developed to quantify simple sugars, malic acid, and total phenolic compounds in apple pomace, considering its potential use as a raw material with value instead of as an industrial waste (39). DRIFTS measurements of 26 samples of apple pomace were analyzed by PLS regression using several signal preprocessing methods. Multivariate models developed with four to ve latent variables (LVs) and based in the mid-infrared (MIR) region had good prediction for the determination of sucrose, fructose, malic acid, and total phenolic compounds, with average errors between 3.9 and 6.6%. By contrast, glucose was better determined by models developed in the near-infrared (NIR) region and using six LVs, yielding an average error lower than 7.4%. Red fruit (Pandanus conoideus Lam) is an endemic plant of Papua, Indonesia, and Papua New Guinea. The price of its oil (red fruit oil, RFO) is 1015 times higher than that of common vegetable oils; consequently, RFO is subjected to adulteration with lower price oils (40). Among common vegetable oils, canola oil (CaO) and rice bran oil (RBO) have similar fatty acid proles to RFO as indicated by the score plot of principal component analysis; therefore, CaO and RBO are potential adulterants in RFO. An FTIR spectroscopy method was developed in combination with chemometrics of PLS regression and discriminant analysis (DA) for authentication of RFO from CaO and RBO. FTIR spectroscopy combined with PLSR and DA can be successfully used for quantication and classication of oil adulterants in RFO. Quality characteristics of wheat are determined by different physiochemical and rheological analyses using different American Association of Clinical Chemists (AACC) methods (41). AACC methods are expensive, time consuming, and cause destruction of samples. FTIR spectroscopy is one of the most important and emerging tools used for analyzing wheat for different quality parameters. This technique is rapid and sensitive, with a great variety of sampling techniques. Amir et al. (41) used different wheat varieties for quality assessment and were characterized using AACC methods and FTIR techniques. FTIR works on the basis of functional groups and provides information in the form of peaks. On the basis of the peaks the values of moisture, protein, fat, ash, carbohydrates, and hardness of grain were determined.

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FTIR spectrometry was used also in order to study the relationship between chemical structure and properties of modied substances versus antioxidant activity. -Carrageenan oligosaccharides prepared through mild hydrochloric acid hydrolysis of the polysaccharide (42), polysaccharides extracted from Ulva pertusa Kjellm (Chlorophyta) (43), melanin produced by Hypoxylon archeri, a companion fungus of Tremella fuciformis, and puried from the submerged culture medium (44), chestnut (Castanea sativa) shell and eucalyptus (Eucalyptus globulus) bark, waste products of the food and wood industries, respectively (45), where FTIR spectroscopy conrmed the higher content of phenolic compounds in chestnut shell extracts compared to chestnut shell and eucalyptus bark and waste products of the food and wood industries, respectively. A water-soluble polysaccharide from the seeds of Plantago asiatica L. was extracted with hot water and puried by gel ltration chromatography (46), the nutrient and chemical contents of two Korean teas: traditional Chungtaejeon tea (CTJ) and green tea (GT) (47), fresh and stored maize (white and blue) tortillas (48), the structural change of the degraded -carrageenans, by an oxidative method involving hydrogen peroxide (H2 O2 ), was characterized (49), propolis extracts (50), the bioactive metabolites from a benthic, mat-forming strain dominating a polluted wastewater canal in Egypt (51), the water and acetone extracts of raw and boiled for 10, 20, 40, and 60 min Korean lotus roots (KLR) and Polish white onion (PWO) (52), as well was different extra virgin olive oils (EVOOs) (53).

Conclusions
In conclusion, FTIR spectroscopy is a promising technique to rapidly provide information on the TAC of products of interest and has a high potential to be implemented for the rapid screening of several TAC methods concurrently. The use of MIR spectroscopy to predict the total antioxidant capacity of vegetables provides a rapid and precise alternative to traditional wet chemistry analysis. With its speed and ease of data manipulation by computer software, FTIR spectroscopy is advantageous as a simple and rapid quantitative determining analytical tool for antioxidant activity assays in herbal medicine.

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