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Article Cite This: ACS Omega 2019, 4, 3839−3849

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Application of Molecularly Imprinted Biomembrane for Advancement of Matrix Solid-Phase Dispersion for Clean Enrichment of Parabens from Powder Sunscreen Samples: Optimization of Chromatographic Conditions and Green Approach Habibeh Gholami,† Mehrorang Ghaedi,*,† Maryam Arabi,† Abbas Ostovan,† Ahmad Reza Bagheri,† and Hadi Mohamedian‡ †

Chemistry Department, Yasouj University, Yasouj 75918-74831, Iran Chemistry and Chemical Engineering Research Centre of Iran, Tehran, Iran

ACS Omega 2019.4:3839-3849. Downloaded from pubs.acs.org by 31.40.211.109 on 02/21/19. For personal use only.

‡

S Supporting Information *

ABSTRACT: In this research work, molecularly imprinted biomembranes (MI-BMs) were fabricated by using the natural substance as a multifunctional monomer and methyl paraben as the template in a one-pot and green condition. Subsequently, the application of resulting MI-BMs as a dispersant sorbent in matrix solid-phase dispersion (MSPD) was evaluated, which exhibited supreme performance for cleanup and isolation of paraben’s family from complicated matrices. More importantly, the chromatographic conditions that affect resolution, band spreading, and peak symmetry were studied and optimized. Also, the effects of individual parameters and their significant interactions on extraction efficiency were concurrently optimized by a multivariate optimization methodology. Under an optimized condition, the developed MI-BM−MSPD method exhibited wide linear ranges of 40.0−10 000.0, 40.0−10 000.0, and 50.0−10 000.0 μg kg−1 with satisfactory recoveries ranging from 92.5 to 102.5, 88.8 to 101.5, and 92.0 to 102.8%, for methylparaben, ethylparaben, and propylparaben, respectively. Low detection limits close to 11.1 μg kg−1 and excellent repeatability (relative standard deviation ≤ 4.6%) imply that an innovative MI-BM−MSPD approach is qualified for simultaneous quantitative detection of parabens in complex samples along with simplicity in the line of green and sustainable chemistry. extraction procedures.6,7 Diverse kinds of dispersant sorbents (e.g., C18, diatomaceous earth, SiO2, Florisil) were used in MSPD for trapping the target analyte during grounding and blending in a mortar, which is selected based on polarity, functionality, and compatibility with the sample matrix. It should be pointed out that most of the biological and environmental samples have complex matrices, in which the concentration of the analyte is very low. Because in MSPD the sample is in direct contact with the sorbent, interferent compounds could be easily adsorbed on the surface of sorbent and subsequently led to the high detection limit, inaccurate analysis, and also pollute chromatography column (in a chromatographic-based analysis). Hence, using a selective dispersant sorbent with supreme anti-interference ability could overcome the mentioned drawbacks, which enhances the applicability of MSPD approach for cleanup and extraction of the analyte. Molecularly imprinted polymers (MIPs) are man-made artificial materials with predetermined recognition sites

1. INTRODUCTION Analytical chemistry is a branch of chemistry whose main purpose is to identify and quantitatively analyze target compounds (harmful and/or beneficial) in various complicated matrices. In this regard, scientists have been devoted their efforts to the design and development of analytical instruments to achieve high sensitivity and selectivity, low detection limit, as well as ease of operation. Despite the impressive advances of instrumental technology, namely, the hyphenated technique, it suffers from the vital limitation that needs to be overcome by influential sample pretreatment prior to instrumental analysis.1,2 The principal goals of sample pretreatment step are a clean separation of the analyte of interest from sample matrices and preconcentration of the analyte to the extent that it is recognizable for an instrument. Among the well-known sample preparation techniques that have been applied for different samples, matrix solid-phase dispersion (MSPD) is an enforceable sample preparation strategy for concurrent extraction and purification of the analyte from a different solid, semisolid, and/or highly viscous samples.3−5 The MSPD benefits from unique advantages viz. simplicity of the procedure and low amount of sample, reagents, glassware, time, and cost consumption, which distinguish it from other © 2019 American Chemical Society

Received: October 26, 2018 Accepted: February 11, 2019 Published: February 21, 2019 3839

DOI: 10.1021/acsomega.8b02963 ACS Omega 2019, 4, 3839−3849

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inspired from biological receptors.8,9 The polymerization process is carried out by pre-assembly of functional monomer and the template molecule, which are subsequently imprinted in the 3D dimensional polymer network by using cross-linking agents that finally create specific recognition cavities.10,11 These specific cavities can distinguish the target molecule from analog compounds based on size, shape, and functional groups.12 Depending on the application of MIPs, they can be fabricated in various morphologies, such as bulk, monolithic, nanoparticles, and microsphere beads. Albeit the traditional synthesis route for the preparation of mentioned MIPs have been popular owing to their significant properties, such as convenient synthesis, cheapness, low consumption, and sophisticated instrumentation, and provide pure MIPs products, they usually suffer from limitations in other aspects, such as being time consuming, irregularity in the size and shape of particles, template leakage, and also decrease in mass transfer and binding capacity.13,14 Specifically, although MIPs were used as a dispersant sorbent in MSPD, the crushing and grounding of particles were carried out two times: one during the synthesis step and another in MSPD for mass transfer of the analyte. Consecutive rubbing of MIPs caused destruction and deformation of binding sites that significantly reduced the MIP’s selectivity and efficiency. These remarkable reasons cheer researchers to use innovative methods for the preparation of MIPs to improve and develop them, for minimizing restrictions on their use. Molecularly imprinted membrane (MIM) materials, which are the combination of imprinted and membrane separation technique, is one solution to prevent drawbacks.15,16 Unlike MIPs, MIMs do not need crushing, which leads them to show unrivaled advantages, including easy removal of the template, faster binding kinetics, larger adsorption areas, higher adsorption capacity, less energy consumption, higher selectivity, and convenient detection.17,18 An important point to note is that MIMs, which have been synthesized based on traditional approaches, suffer from some limitations in terms of consumption of a large volume of toxic organic solvents, the need to control synthesis conditions, high cost, multi-step synthesis, and waste generation. For instance, Zhang et al.19 prepared acrylic-based MIMs based on cold plasma-induced grafting polymerization for membrane-assisted solvent extraction for the isolation of pyrethroid insecticides. Despite high performance of the membrane, a high amount of organic solvents, hazardous chemicals, and expensive accessories were required. Fan et al.20 synthesized a flexible organic membrane in a radical polymerization approach by using methacrylic acid, 2-hydroxyethyl acrylate, and ionic liquid for the separation of synephrine. Although by adding 2hydroxyethyl acrylate the flexibly improved obviously, different kinds of toxic reagents and proficiency of operator were the requirements that made their method costly and laborious. Du et al.21 immersed poly(vinylidene difluoride) (PVDF) membrane in MIP solution containing organic-based MIP’s precursor followed by photopolymerization. A thin layer of MIPs anchored on the PVDF membrane could selectivity adsorb cloxacillin. In the reported work, a prerequisite of MIM preparation was the usage of toxic monomer and other dangerous organic polymerization components. In the mentioned MIMs and majority of reported MIMs, toxic functional monomers, organic solvents, and/or complex accessories in several steps were used.22−24 To overcome the mentioned obstacles in the line of green chemistry, we persuade to use chitosan as a cheap versatile natural precursor

for the preparation of molecularly imprinted biomembrane (MI-BM) in one pot, with lower toxicity, and facile synthesis approach under mild condition. Chitosan has a multifunctional structure that could conveniently convert to the polymeric structure by phase inversion and owing to simple foaming condition and flexible structure, and it also benefits from unique features of structure predictability. Subsequently, the MI-BM has been used as dispersant sorbent in the MSPD method for purification and extraction of parabens as model compounds from powder sunscreen samples prior to highperformance liquid chromatography (HPLC) analysis. On the basis of four main reasons, we selected parabens as the analyte of interest: (I) parabens or p-hydroxybenzoic acid esters are widely used as an antimicrobial preservative in pharmaceutical, food, and cosmetic industries for enhancing the quality and longevity. Although, the Final Report on Safety Assessment of Parabens concluded that the concentrations of parabens preservative used in cosmetic products are not hazardous for human health,25 the threshold limit of parabens in cosmetic products in European Union (EU) countries and United States of America (USA) is 0.4% for each single ester and 0.8% for mixtures of parabens.26,27 On the other hand, several papers reported that human exposure to parabens increased the risk of breast cancer, altering hormone signaling and gene expression, causing the endocrine-disrupting effect on thyroid and reproductive hormones during pregnancy.28,29 Hence, monitoring and determination of parabens in cosmetic products have been a matter of concern. (II) Generally, two or more parabens are combined to enhance antimicrobial properties.30,31 Therefore, in cosmetic products, the family of parabens might have existed (especially methyl and propyl parabens32) so that a validated chromatography method is required for their identification and determination at trace level with acceptable resolution and sensitivity. (III) The affinity and ability of the prepared MI-BM for the simultaneous enrichment of the paraben family in the presence of matrix impurities. (IV) There are several papers that reported the application of different kinds of MIPs for the determination of parabens. Therefore, we could compare our results with the previous literature and evaluate the applicability of the proposed method.

2. EXPERIMENTAL SECTION 2.1. Materials and Instruments. Chitosan powder (low molecular weight, with ≥75.0% degree of deacetylation and 20−30 caps of viscosity), ethanol, methanol, and sulfuric acid (98%) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Deionized water used throughout the work with the specific resistance of 18.2 MΩ cm was produced from a MilliQ gradient water purification system (Merck, Germany). Methylparaben, ethylparaben, propylparaben, acetic acid, hexane, acetonitrile, and sodium hydroxide were purchased from Merck (Darmstadt, Germany). All chemicals were analytical reagent grade. For the evaluated morphology of MI-BM, scanning electron microscope (SEM) images were recorded on a Quanta 200 microscope (FEI Company of USA). For the identification of functional groups, Fourier transform infrared spectroscopy (FT-IR-8300, Shimadzu) using KBr pellet was employed. Parabens were determined by an Agilent 1260 liquid chromatography (Wilmington, DE, USA) equipped with a micro-vacuum degasser (model G1379A), a quaternary pump (model G1311A), a diode array detector (DAD, model 3840


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Figure 1. MI-BM-based MSPD procedure for parabens extraction.

Figure 2. Basic preparation procedure of MI-BM.

G13658), a sample injection valve with a 20 μL sample loop, and an Agilent C18 column (4.6 mm i.d. 250 mm, 5 μm). Different ratios of mobile phase consists of deionized water− methanol, which was filtered through a 0.45 μm filter, degassed under vacuum, and passed with the flow rate of 1.0 mL min−1. Separation process was carried out at different temperatures, and wavelength-switching program was used to enhance sensitivity. 2.2. Preparation of MI-BM and Non-Imprinted Biomembrane. Methylparaben (0.125 g) as template was dissolved in minimum amount of methanol. 1.25 g of chitosan was dissolved in 50 mL acetic acid solution (2%, v/v), followed by the addition of methylparaben solution. Subsequently, the mixture reacted under stirring at 60 °C for 6 h to get a clear suspension. The mixture was filtered for the removal of impurities, poured into a clean glass plate, and dried at 60 °C for 12 h and the MI-BM with a thickness of approximately 40 μm was obtained. Then, the prepared membrane was immersed in 0.5 mol L−1 sulfuric acid for the cross linking of chitosan membrane. In order to eliminate the template from the membrane network, the membrane was washed several times with methanol/acetic acid (9:1, v/v) until the template molecules were removed completely. The non-imprinted biomembrane (NI-BM) was prepared in the same manner in the absence of template. 2.3. Adsorption Test. To assay the binding capacity of parabens by the prepared MI-BM/NI-BM, 40 mg of MI-BM or

NI-BM was suspended into 15 mL aqueous solution of parabens at varied initial concentrations (40.0−500.0 mg L−1 individually). The mixture was mechanically stirred at 25 °C for 12 h in order to ensure complete adsorption process, and then the sorbents were separated from the original solution, and residual (non-sorbed) concentrations of parabens were determined by HPLC. 2.4. MI-BM−MSPD Procedure of Parabens from Powder Sunscreen Samples. Powder sunscreen samples were purchased from a local market (Shiraz, Iran). For MSPD procedure, 0.05 g of powder sunscreen samples, 0.15 g of MIBMs, and 0.1 g of sea sand were added to a small glass mortar and mixed together finely to obtain a homogeneous mixture. After that, the mixture was transferred to a polypropylene solid-phase extraction (SPE) cartridge, packed with plugs and retained by porous frits at both ends. The cartridge was washed with 3.0 mL hexane to eliminate hydrophobic interferences, and parabens were desorbed from the cartridge by 2.0 mL methanol/acetic acid (90/10 v/v). Finally, the eluent was evaporated under a nitrogen stream at 35 °C to attain dryness, and the residue was reconstituted with 50 μL mobile phase, whereas 20 μm of it was analyzed by HPLC−UV (Figure 1).

3. RESULTS AND DISCUSSION 3.1. MI-BM Synthesis and Characterization. To date, some researchers have reported the preparation of diverse kinds of chitosan-based imprinted membranes.33−35 There are 3841


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shape, and functional groups of template were created in the MI-BM structure. For approving the qualification of the fabricated MI-BM as a dispersant sorbent in the MSPD approach, the MI-BM was characterized well, as discussed below. SEM images of MI-BM and NI-BM demonstrate that the prepared membrane has a uniform surface containing a few slim interstices (Figure 3). The rough surface of the membrane

well-known strategies for the synthesis of these materials viz. (I) Porous chitosan membrane could be used as a versatile support owing to proper permeability and high functionality. Zhang et al.36 synthesized selective membrane by employing the ATRP method to construct MIP layers on the porous chitosan membrane substrate for the recognition of artemisinin. (II) In some other works, chitosan acted as a backbone of the 3D imprinted membrane at the attendance of functional monomer and template. 37 Di Bello and co-workers 38 constructed a new membrane with a multi-reagents procedure. The print molecule (4-nitrophenol) and synthesized functional monomer (4-[(4-hydroxy)phenylazo]benzenesulfonic acid) were trapped to the chitosan network in polyethylene glycol media. (III) Moreover, chitosan combines and links with different kinds of precursors to form hybrid imprinted membranes.39 In this regard, Zheng et al. fabricated the chitosan−gelatin membrane in a polyethylene glycol phase followed by chemical cross linking with glutaraldehyde. Despite remarkable benefits of the mentioned chitosan-based imprinted membranes, high-volume organic solvents and toxic precursor were required during the synthesis step. Therefore, we focused on a facile and green synthesis of MI-BM to further improve the simplicity and eco-friendliness of the proposed method. The schematic synthesis route of MI-BM based on phase inversion method is shown in Figure 2. Chitosan biosubstance was used as the natural multifunctional monomer owing to its versatile properties viz. easy availability, nontoxicity, biocompatibility, biodegradability as well as possess inherent ability to form a polymeric chemical and physical 3D network, in which print molecule is enmeshed in polymer skeleton and interact by non-covalent bonds. Among methylparaben, ethylparaben, and propylparaben, methylparaben has the shortest chain of ester group that leads to rising water solubility. By considering the geometry, size, functionality, as well as solubility of parabens, methylparaben was selected as a print molecule. The −OH, −NH2, and −O− groups of chitosan make it qualify to easily interact with ester and hydroxyl groups of methylparaben via hydrogen bonds without the adverse effect of water on the formation of hydrogen bonds and form a sustainable preassembled complex.40 Before drying of the membrane, the MI-BM precursor was a viscose liquid that could be spread on a wide surface or on a smaller surface of a glass plate in order to control the thickness of the membrane. In other words, if MIBM precursor is spread in a large space, the thickness of the prepared membrane will be thin; if the MI-BM precursor is spread in a small space, the thickness of the membrane increases as desired (the expanse of MI-BM precursor on a glass plate determines the thickness of the membrane). Then, the membrane was cross linked by an inexpensive and nontoxic inorganic cross-linking agent (sulfuric acid 0.5 mol L−1) in mild condition, in order to enhance the mechanical stability of chitosan membrane and reduce the degree of swelling in aqueous media. The cross-linking process occurs via Coulomb interaction between the SO22− ions in sulfuric acid and the NH3+ group in chitosan easily. The prepared MI-BM is significantly flexible; that is, it has remarkable superiority compared with traditional membrane, especially while the membrane is used in filtration or membrane extraction. Interestingly, in the proposed synthesis route, no organic solvent was used and all steps were done in one pot under mild condition. After template elimination by washing with methanol/acetic acid, the specific cavities based on size,

Figure 3. SEM image of (a) MI-BM and (b) NI-BM.

would provide much more contact area that can facilitate mass transfer of analytes and enhance the adsorption capacity. Moreover, the similarity between MI-BM and NI-BM structures reveals that imprinting of the molecular template does not have a significant effect on the morphology of membranes. FT-IR spectra of MI-BM containing a template, MI-BM after template removal, and NI-BM are shown in Figure 4. In Figure 4a, characteristic peaks observed at 1273 and 1157 cm−1 are asymmetrical and symmetrical stretching vibrations of ether-oxy groups (C−O−C) in ester groups, whereas the peak at 1735 cm−1 comes from stretching vibration of CO that is related to functional groups of methylparaben. After removal of the template from the MI-BM network, the characteristic peaks of methylparaben disappeared (Figure 4b). Moreover, all three samples have broadband at about 3422 cm−1 corresponding to the stretching vibration of N−H and O−H. The characteristic peaks of the bending vibration of NH2 appears at 1630 cm−1, whereas 1154 cm−1 could be attributed to the C−N stretching vibration (Figure 4c). The above results demonstrate that imprinted cavities were formed in MI-BM, which could be used to selectively extract parabens. 3.2. Binding Study of the MI-BM and NI-BM for Parabens. The adsorption isotherm is a significant factor that shows the recognition ability and adsorption capacity of MIBM and NI-BM toward the analytes. The adsorption isotherms 3842


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the MI-BM skeleton. Furthermore, in order to obtain a deep understanding of the binding affinity of MI-BM and its theoretical number of binding sites for the templates, the Scatchard equation was adopted to evaluate the binding ability of MI-BM, which can be defined as follows Q /Ce = (Q max − Q )Kd

where Q and Qmax are the amounts of parabens bound to the MI-BM at equilibrium and the apparent maximum binding amount, Ce is the concentration of parabens in solution at equilibrium, and Kd is the dissociation constant of the binding sites. According to Table S2, the Scatchard plot for MI-BM has two straight lines for parabens, which demonstrate that there are two binding sites in MI-BM: the high-affinity (specific) (left side) and the low-affinity (nonspecific) (right side) binding sites (Figure S1c−e). On the basis of the slopes and intercepts of straight lines, Kd values for methylparaben, ethylparaben, and propylparaben were obtained as 55.24, 69.90, and 80.00 mg L−1 for the high-affinity binding sites and 76.90, 86.70, and 149.2 for the low-affinity binding sites, respectively. On the other hand, corresponding affinity constants were calculated as 0.0181, 0.0143, and 0.0125 for the high-affinity binding sites and 0.0130, 0.0115, and 0.0067 mg L−1 for the low-affinity binding sites, respectively. Also, the Qmax was calculated as 23.26, 21.90, and 20.41 for the highaffinity binding sites and 18.47, 19.20, and 19.40 mg g−1 for the low-affinity binding sites. These results proved the high affinity of MI-BM to methylparaben, ethylparaben, and propylparaben, respectively, which is in good agreement with Freundlich isotherm. 3.3. Variable Optimization for MI-BM-Based MSPD. In order to obtain maximum extraction yield of parabens in powder sunscreen samples, the elementary effects of qualitative factors viz. kind of washing and desorption solvents were assayed, at the spiked concentration level of 200.0 μg kg−1 for each paraben individually. As much as matrix contaminations always compromise the cleanliness of the effluent that contains target analyte, there is a crucial line between washing the sorbent enough to remove interferents and not decreasing the recovery of the analyte of interest at the same time. Because powder sunscreen sample is complex and contains different kinds of matrix interferences, especially long chain fatty acids and other nonpolar compounds that could detrimentally pollute/block HPLC C18 column or give interference peaks overlapping with the peak of parabens. In this regard, different washing solvents with diverse polarity, including deionized water, acetone, acetonitrile, hexane, and ethyl acetate, were assayed. Among the selected solvent, hexane could rinse most of the hydrophobic impurities and provide the cleanest extract, whereas the interactions among analytes and MI-BM remained. Therefore, hexane was chosen as the washing solvent for further experiments. According to the polarity of desorption solvent and solubility of the target analyte, which is generally expressed as “elution strength,” and also compatibility with chromatographic system, different solvents and their mixture viz. methanol, ethanol, acetonitrile, methanol/ethanol (50:50, v/ v), methanol/acetic acid (90:10, v/v), and ethanol/acetic acid (90:10, v/v) were tested as eluent. Experimental results showed that methanol/acetic acid (90:10, v/v) could desorb most of the analytes that retained on MI-BM. This fact might be owing to the resemblance between the polarity of parabens

Figure 4. FT-IR spectra of (a) MI-BM contain template, (b) MI-BM after template removal, and (c) NI-BM.

of parabens onto MI-BM and NI-BM were determined in the concentration range of 40−500 mg L−1 (Figure S1a), which revealed that the adsorption capacities of polymers enhanced by the increasing initial concentration of parabens and subsequently specific cavities became saturated at 360 mg L−1. The Langmuir and Freundlich adsorption isotherm models were carried out to estimate the binding properties of MI-BM and NI-BM. The Langmuir model assumes monolayer adsorption of the analyte species onto a homogeneous surface, whereas the Freundlich model demonstrates multilayer adsorption of the analyte species onto a heterogeneous surface. The results obtained from isotherms (Table S1) showed that the Freundlich model was more suitable than the Langmuir model in terms of correlation coefficients. Freundlich model is described by the following equation log Q = m log C + log α

(2)

(1)

−1

where Q (mg g ) is the amount of parabens adsorbed at the equilibrium state; C (mg L−1) is the equilibrium concentration of parabens in sample solution; α is Freundlich constant, which is related to binding parameters; and m is the heterogeneity index, which reveals the intensity of the adsorption and can take values between 0 and 1, where these values refer to system heterogeneity and homogeneity, respectively. The Freundlich isotherms of parabens on MI-BM and NI-BM are shown in Figure S1b. According to Table S1, the correlation coefficients for MI-BM in Freundlich model were higher than for NI-BM, which could strongly support the presence of heterogeneous binding sites in MI-BM. On the other hand, the correlation coefficients for NI-BM in Langmuir model were higher than for MI-BM, which proved the monolayer adsorption of parabens onto NI-BM. Moreover, the m values for MI-BM are less than those for NI-BM, which indicated that the structure of MI-BM had more heterogeneous binding sites than NI-BM, which is due to a substantial role of template molecule during polymerization. The maximum adsorption capacities for methylparaben, ethylparaben, and propylparaben were 25.20, 21.60, and 19.00 mg g−1 by MI-BM and 8.00, 7.30, and 6.50 mg g−1 by NI-BM, respectively. In all cases, the maximum adsorption capacities for MI-BM were higher than for NI-BM, which exposed the presence of specific cavities in 3843


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and methanol and their high solubility in methanol, whereas acetic acid facilitates the breakdown of hydrogen bonds between the trapped analyte and MI-BM. 3.4. Variable Effects Evaluation by CCD and Response Surface Methodology. Optimization approaches as prominent tools have been widely performed in analytical methods to improve the efficiency of the systems, increment the yield of the processes without increasing the time and cost, and obtain conditions at which a procedure or model has the best possible response. The one-factor-at-a-time (OFAT) optimization technique is a simple and applicable optimization approach, which has been conventionally applied. In this method, one factor changes at a time in the general practice of determining the optimal operating conditions while keeping the others fixed. In spite of its simplicity and accessibility, OFAT suffers from fundamental defects, such as time, chemicals, experiments, and effort consuming. Most importantly, the major drawback of OFAT is that it can’t completely consider the effect of each factor or collaboration effects among the factors and subsequently is incapable of attaining the true optimum level. Therefore, to overcome these impressive problems, alternative approaches, such as response surface methodology (RSM), have been extensively applied.41,42 RSM is a set of statistical and mathematical techniques useful for developing, improving, and optimizing processes in which a response of interest is influenced by several variables and the objective is to optimize this response. Moreover, it assesses the effects of multiple parameters and their interactions, optimizes multifaceted processes, and sets empirically polynomial relationships between target response and independent parameters.43 Accordingly, to investigate the effect of operative factors and their interactions on paraben extraction, three experimental factors, including sample-to-MIBM ratio (A: 1/3−3/1), washing solvent volume (B: 2.0−4.0 mL), and eluent solvent volume (C: 2.0−4.0 mL), were assessed based on a fivelevel (−2, −1, 0, 1, 2) rotatable model containing 15 experimental runs (Table S3). Factors and their levels were chosen based on background knowledge and experimental experiences. After experimental runs, in order to understand the significance of the model/main factors, their interactions analysis of variances (ANOVA) was done in accordance with suggested quadratic model at a certain confidence level (α = 0.05) (Table S4). Suitability, dependability, and statistical significance of the fitted quadratic model were evaluated via a collection of standards, including p and F values, lack-of-fit test, and determination of coefficients (R2 and adjusted R2). The terms with higher values of F and p values less than 0.05 can be approved and strongly support their significant contribution to the extraction process, whereas the terms with p values more than 0.05 are not significant. The F value of the model (34.81) implies the significance of the model. In this case, A, B, C, AB, BC, B2, C2 with p values less than 0.05 are significant model terms. The lack-of-fit value more than 0.05 (0.6614) and correlation coefficient with high value (0.9843) confirm the accuracy and reliability of the suggested model. The acceptable quality of the polynomial model fit is expressed with the coefficient of determination values (R2 = 0.9843 and adjusted R2 = 0.9560), indicating that 98.43% of the variability can be revealed by the model. Figure S2 shows good agreement between experimental extraction recovery percentages (ER (%)) and calculated values. Further, the effect of variables and their interactions on ER (%) are shown in eq 3.

ER % = + 86.16 − 4.30A − 2.38B − 6.17C − 4.35AB − 5.13BC − 4.03B2 − 1.25C 2

(3)

These significant interactions between variables were demonstrated via response surface diagrams (Figure S3). Figure S3a,b show the effect of sample-to-MI-BM ratio on ER (%), which reveals that ER (%) of methylparaben declines with the enhancement of sample-to-MI-BM ratio. In lower sampleto-MI-BM ratio, the analyte can completely be extracted from sample to MI-BM, whereas in higher sample-to-MI-BM ratio, it could have a contrary effect. This can be because of the retention of the analyte onto the sample in a higher sample-toMI-BM ratio. Therefore, the best results were obtained at the lowest sample-to-MI-BM ratio (1/3). Powder sunscreen sample contains very fine particles and can easily block frit’s pores that lead to decreasing permeably of solvent and high backpressure. To overcome this problem, low amount of sea sand was added to the sample/sorbent mixture before homogenization, which caused minimized frit blocking and also increased the collision of the sample to MI-BM. The effect of washing solvent volume (B) is shown in Figure S3a,c. Proper volume of washing solvent reduces interfering species and accumulated matrix interferences. On the other hand, inadequate volume of washing solvent may not be able to eliminate impurities from the sample. Hence, the washing solvent volumes were studied over the range of 2.0−4.0 mL and the results showed that the 3.0 mL of hexane was suitable to obtain the cleanest extract. Also, Figure S3b,c illustrate the effect of eluent solvent volumes on ER (%). The proper volume of eluent solvent can effectively elute the trapped analyte from the sample. Thus, the volumes of the eluent in the range of 2.0−4.0 mL were investigated, and results showed that 3.0 mL of the eluent was enough to desorb analytes completely. After RSM assessment, desirability function (DF) was examined for simultaneous optimization of the analyzed variables, which is shown in Figure S4. DF is a useful and conventional approach to determine the global optimum conditions, which transform the predicted and experimental response of each variable into a desirability score. DF takes values between 0.0 and 1.0 for a completely undesirable and fully desired response, respectively. On the basis of the desirability score of 1.0, maximum recovery (98.56%) was achieved at optimum conditions set as the sample-to-MI-BM ratio (1/3), washing solvent volume (3 mL), and eluent solvent volume (3 mL). 3.5. Optimization of HPLC Chromatographic Conditions. During multi-analyte determination, optimization of chromatographic conditions leads to improved accuracy and reliable results. Perversion from optimal HPLC conditions causes unfavorable resolution and/or long analysis time or, more importantly, significant discrepancies of the results from true values. Hence, the influence of chromatographic conditions, namely, mobile phase composition, column temperature, and wavelength of detection on resolution and retention time as well as band spreading and peak symmetry, was investigated. In this regard, the mobile phase containing deionized water and methanol with different ratios was tested. As seen in Figure S5, by increasing organic phase percentage, the retention time of all analytes and subsequently the time of analysis were decreased. Although deionized water/methanol (30:70 and 40:60 v/v) were selected as the mobile phase, the resolution was not satisfactory (Figure S5a,b). Moreover, by considering the peak area, which is the criterion of the analyte’s 3844


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92.0 93.8 102.8 96.5 3.1 3.4 2.2 2.2 1.4 6.5 22.2 104.1 ± ± ± ± 46.0 187.5 1027.5 4825.0 50.0 200.0 1000.0 5000.0 propylparaben 88.8 93.5 96.3 95.8 3.6 2.1 1.4 2.0 1.3 4.0 13.2 97.8 ± ± ± ± 35.5 187.0 963.0 4792.5 40.0 200.0 1000.0 5000.0 ethylparaben 3.4 2.0 1.2 2.7 methylparaben

40.0 200.0 1000.0 5000.0

37.5 205.0 962.0 4825.0

1.3 4.2 11.8 132.3 ± ± ± ±

93.8 102.5 96.2 96.5

recovery (%) RSD (%) found (μg kg−1) ± SD add (μg kg−1) analyte recovery (%) RSD (%) found (μg kg−1) ± SD add (μg kg−1) analyte recovery (%) RSD (%) found (μg kg−1) ± SD add (μg kg−1) analyte

2.2 1.2 2.0 1.9 ± 1.1 ± 2.2 ± 20.8 ± 94.3 interday 48.02 186.3 1025.0 4965.0 50.0 200.0 1000.0 5000.0 propylparaben 90.0 95.0 101.5 98.7 3.1 1.4 2.6 1.6 ± 1.1 ± 2.7 ± 26.5 ± 78.9 interday 36.0 190.0 1015.0 4935.0 40.0 200.0 1000.0 5000.0 ethylparaben 2.7 1.8 1.3 1.9 methylparaben

40.0 200.0 1000.0 5000.0

37.0 191.0 946.0 5065.0

± 1.0 ± 3.4 ± 12.1 ± 94.3 interday

92.5 95.5 94.6 101.3

found (μg kg−1) ± SD found (μg kg−1) ± SD analyte recovery (%) RSD (%) found (μg kg−1) ± SD add (μg kg−1) analyte

intraday

Table 1. Precision of the MI-BM−MSPD−HPLC−UV Method (n = 4)

add (μg kg−1)

intraday

RSD (%)

recovery (%)

analyte

add (μg kg−1)

intraday

RSD (%)

recovery (%)

concentration, deionized water/methanol (50:50 v/v) provide the highest peak area at a constant concentration for all analytes (Figure S5c). Whenever high-percent deionized water was used in the mobile phase, the time of analysis was too long and the propylparaben’s peak was broadened that causes undesirable separation (Figure S5d,e). Subsequently, in order to decrease the time of analysis, the temperature was increased and results confirm that highest peak area, supreme resolution, and lowest analysis time were achieved at 35 °C (Figure S5f,g). It should be pointed out that in all selected conditions, tailing factors for three analytes were lower than 2.000, which were in accordance with the U.S. pharmacopeia version 41. Owing to differences in the structure of methylparaben, ethylparaben, and propylparaben, the maximum absorption wavelength may not be uniform, and slight deviation about a few nanometers from maximum wavelength lead to nondetected or inaccurate results in trace analysis. DAD could scan the analyte at multiple wavelengths concurrently, and this remarkable feature encourages us to overcome the mentioned pitfalls that enhance accuracy and sensitivity. Accordingly, the efficacy of wavelengths variation in the range of 248−263 nm with 1 nm spacing on the peak area was studied. As shown in Table S5, the optimized wavelength for methylparaben, ethylparaben, and propylparaben was 257 nm. By exploiting true maximum wavelengths, more peak area was achieved, whereas the signal of interferences from solvents was minimized. 3.6. Method Validation and Real Sample Analysis. The developed MI-BM−MSPD−HPLC−UV was exhaustively validated by analytical performance characteristics, including the calibration, recovery, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision using powder sunscreen sample. The powder sunscreen standard calibration curves were obtained over the range of 40.0−10 000.0 μg kg−1 for methylparaben, 40.0−10 000.0 μg kg−1 for ethylparaben, and 50.0−10 000.0 μg kg−1 for propylparaben under optimized conditions. Each calibration curve comprised seven points, whereas all correlation coefficients were higher than 0.998, which certified supreme linear responsivity of the method. The LODs and LOQs were found to be 11.1 and 37.2 μg kg−1 for methylparaben, 11.0 and 36.3 μg kg−1 for ethylparaben, and 13.5 and 45.1 μg kg−1 for propylparaben using 3σ/slope and 10σ/slope ratios, respectively, where σ is the standard deviation for chromatograms obtained from the blank according to IUPAC recommendation.44 Low LODs demonstrate qualified operational conditions and merit of the proposed method. Method precision was investigated by the relative standard deviation (RSD) of the intra-day and interday measurement variations at four different concentration levels (40.0, 200.0, 1000.0, 5000.0 for methylparaben and ethylparaben and 50.0, 200.0, 1000.0, 5000.0 μg kg−1 for propylparaben) of the quality control sample, which is the criterion of the repeatability and reproducibility. As seen in Table 1, for four repeated assays, extraction recoveries and intra-day precisions were found to be 92.5−101.3 and 1.3− 2.7% for methylparaben, 90.0−101.5 and 1.4−3.1% for ethylparaben, and 93.1−102.5 and 1.2−2.2% for propylparaben, respectively, whereas that of inter-day recoveries and precision were 93.8−102.5 and 1.2−3.4% for methylparaben, 88.8−96.3 and 1.4−3.6% for ethylparaben, and 92.0−102.8 and 2.2−3.4% for propylparaben, respectively, which confirm competent precision of the present method. The selectivity of the proposed method was affirmed by comparing chromato-

96.0 93.1 102.5 99.3

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grams of blank powder sunscreen sample and spiked powder sunscreen sample pretreatment by the MI-BM−MSPD. Figure 5 shows no interference peak in overlapping with the analyte’s

Because sample pretreatment is an inevitable step during analytical analysis, different sample preparation methods have been applied for extraction of parabens, including SPE,45 liquid−liquid microextraction (LLME),46 solid-phase microextraction (SPME),47 ultrasound-assisted extraction.48 SPE suffers from impediments like high amount of solvents and flow rate controlling consumption, several steps, long time waste (in sample loading), cartridge blockage/channeling and requirement of extraction of the analyte in a proper solvent before loading step (for solid and semisolid samples). Developed LLME requires a high amount of toxic organic solvents/reagents for extraction/derivatization and also the method lacks from selectivity. SPME needs high-cost accessory and operator skill, as well as the proposed method couldn’t be applied for solid samples. The defects of all mentioned techniques can be conveniently prevailed by the MSPD method.49−52 On the other hand, MIP-based methods have been frequently used for trapping parabens in different samples. However, to the best of our knowledge, all reported MIPs were prepared by toxic precursors and organic solvents. In the current work, we tried to utilize eco-friendly biosubstances as the service of molecular imprinting technology, which is completely in agreement with the principle of green chemistry. A typical comparison in terms of analytical figures of merits between proposed MI-BM−MSPD−HPLC−UV and previously reported literature for the determination of parabens in different samples is summarized in Table 3.46,47,50,53−56 As seen, the linear ranges of current work are remarkably wide. More excitingly, the LODs of the developed MI-BM−MSPD− HPLC−UV method are lower than those of all HPLC−UV methods and higher than those of mass spectrometry (MS)based methods that are because of quiddity of the MS detector, which is highly sensitive, complex, and expensive. Emphasis should be put in the current work on the sample preparation step in the line of sustainable and green chemistry with at least the consumption of organic solvents and reagents in the mild condition, which is unique in terms of feasibility, natural origin, full biodegradability, and eco-friendliness for simultaneous determination of parabens.

Figure 5. Typical chromatograms of (a) blank powder sunscreen sample and (b) spiked powder sunscreen sample after DMIP-MSPE procedure.

peaks, which is because of influential cleanup of the MI-BM− MSPD. Meanwhile, the accuracy and applicability of the method were examined via the analysis of real samples. As seen in Table 2, all samples contain paraben with RSD lower than 4.6% for three continuous measurements. These superior results imply that the developed MI-BM−MSPD is highly qualified for the clean enrichment of parabens family from the complicated powder sunscreen sample. 3.7. Method Comparison. On the one hand, the high consumption of cosmetic products by women and, on the other hand, the addition of parabens as an illegal additive in these products extend the exposure to parabens and subsequently enhance its perilous side effects, which cheers researchers to develop accurate and facile analytical methods for quantitative determination of parabens in different samples.

4. CONCLUSIONS In summary, a biocompatible and cheap molecularly imprinted a membrane form was fabricated in a one pot under mild condition. The synthesis procedure benefits from impressive merits of available and safe reagents, waste elimination, and least amount of glassware consumption, which is in accordance with the principle of green chemistry. The MI-BM was used as a dispersant sorbent in MSPD for simultaneous trapping of three parabens in a powder sunscreen sample. In order to attain the highest sensitivity and lowest LODs, the chromatographic conditions, including mobile phase composition, column temperature, and detector wavelength, were optimized.

Table 2. Accuracy of the MI-BM−MSPD−HPLC−UV Method (n = 3) methylparaben ± SD sample sample sample sample

1 2 3 4

1182.0 1620.0 894.0 596.0

± ± ± ±

13.1 20.0 10.0 10.6

RSD (%)

ethylparaben ± SD

RSD (%)

propylparaben ± SD

RSD (%)

1.1 1.2 1.1 1.8

N.D.a 488.0 ± 10.6 190.0 ± 8.7 326.0 ± 6.0

N.D. 2.2 4.6 1.8

606.0 ± 16.4 260.0 ± 4.0 156.0 ± 2.0 N.D.

2.7 1.5 1.3 N.D.

a

Not detected. 3846


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Table 3. Comparison of Different Analytical Techniques for the Determination of Parabens method FSALLM−GCa

sample cosmetic and aqueous sample solutions

UHPLC−MS/MSb

milk samples

GC−MSc

seafood

LVSS−NACE−DADd

aqueous samples

UHSLC−DADe

cosmetic products

LC−UVf

milk samples

LC−MS−MSg

environmental solid samples

HPLC−UVh

powder sunscreen samples

analyte

linear range

LOD

RSD (%)

methylparaben

2−5000 μg L−1

0.5 μg L−1

≤9.2

ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben ethylparaben propylparaben methylparaben

2−5000 μg L−1 2−5000 μg L−1 10−400 μg L−1 10−400 μg L−1 10−400 μg L−1 4−500 μg kg−1 4−500 μg kg−1 4−500 μg kg−1 5−1000 μg L−1 5−1000 μg L−1 5−1000 μg L−1 500−160000 μg L−1 500−160000 μg L−1 500−160000 μg L−1 50−4000 μg L−1 50−4000 μg L−1 50−4000 μg L−1

1.0 μg L−1 0.5 μg L−1

≤7.8 ≤9.4 ≤11.4 ≤8.7

40−10000 μg kg−1

0.06 μg kg−1 0.12 μg kg−1 0.12 μg kg−1 2.2 μg L−1 2.3 μg L−1 1.9 μg L−1 120 μg L−1 140 μg L−1 150 μg L−1 25 μg L−1 25 μg L−1 25 μg L−1 0.14 μg kg−1 0.09 μg kg−1 0.08 μg kg−1 11.1 μg kg−1

ethylparaben propylparaben

40−10000 μg kg−1 50−10000 μg kg−1

11.0 μg kg−1 13.5 μg kg−1

recovery (%)

ref 39

40

43

≤3.9 ≤4.4 ≤5.7

≤11.3 ≤10.5 ≤10.4 ≤8.9 ≤10.3 ≤9.8 ≤3.4

93.7−104.5 95.5−105.2 100.7−104.6 92.3−96.1 92.2−96.8 90.9−94.6 87 92 83 91.5−105.0 94.1−102.5 97.1−110.2 92.5−102.5

≤4.6 ≤3.4

88.8−101.5 92.0−102.8

46

47

48

49

this work

a

Fast syringe-assisted liquid−liquid microextraction gas chromatography. bUltra-high-performance liquid chromatography−tandem mass spectrometry. cGas chromatography−mass spectrometry. dLarge-volume sample stacking non-aqueous capillary electrophoresis coupled with diode array detection. eUltra-high-speed liquid chromatography with diode array detector. fLiquid chromatography−ultraviolet detector. gLiquid chromatography with triple quadrupole mass spectrometry. hHigh-performance liquid chromatography−ultraviolet detector.

■

Furthermore, multivariate optimization was employed for evaluating impacts of individual variables and their interactions on the extraction efficiency to find the true optimum level. Credible analytical features, namely, satisfactory LODs, broad linear ranges, worthy recoveries, and proper precisions, which are because of accurate optimization of both sample preparation and instrumental analysis steps, imply that the proposed method can contribute to increasing the performances of MSPD for the analysis of parabens in complex matrices and promote simplicity and short analysis time. Owing to cost-effectiveness, flexibility, eco-friendliness, and high throughput of MI-BM, it be expected that the prepared MI-BM is considered as a worthy platform for selective concurrent separation of analytes of interest from different matrices to satisfy green and sustainable development.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone/Fax: +98-7412223048 (M.G.). ORCID

Maryam Arabi: 0000-0002-2028-9572 Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was financially supported by the Graduate School and Research Council of Yasouj University.

■

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.8b02963. Adsorption isotherms and Scatchard plots curves; the experimental data versus predicted data of CCD; response surface diagrams; DF; typical HPLC chromatograms at different conditions; adsorption isotherm parameters; Scatchard parameters; CCD with experimental results; analysis of variance (PDF) 3847


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