GC-FID based analysis of trace phthalates with a novel nanocomposite by polar-nonpolar properties in plastic bottled water

doi:10.21203/rs.3.rs-2741303/v1

Download PDF

Research Article

GC-FID based analysis of trace phthalates with a novel nanocomposite by polar-nonpolar properties in plastic bottled water

https://doi.org/10.21203/rs.3.rs-2741303/v1

This work is licensed under a CC BY 4.0 License

Version 1

posted

You are reading this latest preprint version

Risk of emerging contaminants such as phthalates in drinking water and food are concerned due to adverse effect of these chemicals. Release of phthalates as a plastics additive from bottles to drinking water is a source of risk. On the other hand, trace level determination of phthalates in plastic bottled samples is a hurdle in risk assessment. A dispersive solid phase extraction (DSPE) with polar-nonpolar properties adsorbent was prepared for trace analysis of di (2-ethylhexyl) phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP).

Adsorbent consisted of magnetic nano silica aerogel (MSi) coated by CuO ROD (CuR) which was supported ionic liquid (IL). Produced MSi@CuR@IL was characterized by SEM, VSM, BET, EDS, FTIR, C/H/N elemental analysis and TGA. In DSPE method, the effect of adsorbent amount, time of sample absorption and suspension speed were optimized based on the central composite design (CCD).

Optimized condition was evaluated in 24 mg MSi@CuR@IL, sample absorption time of 14 min at pH = 6.2 by suspension speed of 700 RPMI. Using optimized method suitable performance was presented including detection limit of 0.78 to 1.25 µg/L, phthalate recovery of 92.21 to 102.12, linear rage of 3 to 200 µg/L and repeatability by RSD% of < 10%. Evaluated DSPE was performed in 10 plastic bottled water between 8.9 to 195.3 µg/L.

In conclusion application of a potent adsorbent prepare a simple, sensitive and rapid DSPE for phthalate detection by gas chromatography with flame ionization detector (GC-FID) as a commercial technique.

Dispersive solid phase extraction

Phthalates

Silica aerogel

CuO ROD

Ionic liquid

Bottled water

Modern lifestyle and population growth cause emerging contaminants into the food, drinking water and environments [1–3]. Pharmaceuticals, phthalates, micro plastics and surfactants are some of major emerging contaminants in different media [4]. These chemicals are defined as new chemicals with considerable potential for human health by Environmental Protection Agency (EPA) [5]. Emerging contaminants are found in trace level, but accumulation of them in the environment is a hurdle of chemical risks [6]. Phthalates are a group of polymer plasticizer which applied to improve the flexibility of products. These reagents are characterized by endocrine disruption and estrogenic effects in human health [7–8]. Di-(2- Ethyl hexyl) phthalate has been classified as a possible carcinogen to human by International Agency for Research on Cancer [9]. Phthalates commonly used in food packaging, plastic bottle of juice and water bottle [10–11].

Low molecular weight of phthalates cause wide release of these component in plastic packaging materials [12]. Because of this, a lot of attention are for the presence of phthalates in drinking and bottled water. Therefore, proposing a method for trace determination of phthalates could be interested in these years. To determine low concentration of phthalates, various solid phases have been suggested, including microsphere, polyaniline coated chitosan nanocomposite, poly m-aminophenol /nylon 6/graphene oxide and ZIF-8 in different samples [13–16]. However a potent sample preparation for phthalate extraction are needed. The aim of this study is developing an efficient adsorbent for the sample preparation of dimethyl phthalate (DMP), diethyl phthalate (DEP) and di-2ethylhexyl phthalate (DEHP) in water sample.

One-dimensional materials such as rods and tubes as a functional material with super properties is intended [17]. These structures are specified by high mechanical strength, exorbitant surface area and suitable electron transportation [18]. Carbon tube and metal oxides rods are the most intensively one-dimensional materials which improved in these years [19–20]. Growing of the rods on the surface of material is a unique property to produce heterogenic structure and improve surface area for efficient extraction [21]. CuO is specified by great surface area, physiochemical stability and low cost of preparation [18]. So the study of CuO ROD (CuR) has received wide attention recently [22–23].

Ionic liquids (IL) are a new solvents mainly used to improve the characteristic of solid phase. These materials are attractive due to dual nature of their structure including low polarity properties and powerful proton donor groups [24]. Hydrophilicity and hydrophobicity potential of IL are increased reports for the application of these component in adsorption process. This behavior cause the application of IL in the sample preparation techniques [25–27]. Determination of phthalates in trace level released from plastic bottle in aqueous samples are great applicability in health risk assessment. In this work, additive properties of three adsorbent in magnetic silica aerogel-CuO rods nanocomposite supported by an ionic liquid (MSi@CuR@IL) is employed for unique sample preparation of phthalates.

2.1. Chemicals

Nano silica aerogel prepared by Vakonesh Sanate Part Co., Ltd (Esfahan, Iran). Di (2-ethylhexyl) phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP), 1-butyl-3-metylimidazolium tetrafluooroborate, hexamethylenetetramine, ferric chloride hexahydrate, ferrous chloride tetra hydrate, copper sulphate, ammonium nitrate,chloroform, ethanol and methanol were used. All chemicals were purchased from Merck and Sigma Company with extra pure selection.

2.2. Chromatographic instrument

A Shimadzu 17A gas chromatography system equipped with split less injector and flame ionization detector (FID). Injector was applied in split ration of 10:1 at 300°C.Column was 30m×0.25mmid,0.25µm HP-5 which was programed from 60°C to 270°C at 20°C/min and remained at 270°C for 2 minutes and then to 290°C at 50°C/min by 7 min staining. High purity nitrogen was used as carrier gas at flow rate of 0.29 mL/min.

2.3. Preparation of MSi@CuR@IL adsorbent

Magnetic nano silica aerogel (MSi) was synthetized by 0.1 g silica aerogel and 1.6 g FeCl3.6H2O, 0.6 g FeCl2.4H2O in 150 mL distilled water at room temperature in ultrasonic bath for 30 min. 25 mL of 30% ammonia in a 250 mL three-necked flask under stirring at 25°C for 30 min. Ammonia solution by the amount of 25 mL was dropped to the solution. Suspension was stirred for 30 min in the N₂ atmosphere to prevent an oxidative reaction and then temperature was elevated to 80°C for 1 h. Sediment was washed by distilled water and ethanol. Collected MSi nanoparticles were dried at room temperature after 24 h.

To prepare MSi@CuR@IL adsorbent, 0.1 g MSi nanoparticles and 1.248 g of copper sulphate were stirred in 25 mL distilled water. The amount of 1 mL IL was dropped to the solution by striation for 10 min and stirred at 100°C for 5 min. Then 0.35 g of hexamine was stirred for 10 min and heated at 80°C for 20 min.Sediment was washed by distilled water and ethanol. Collected MSi@CuR@IL nanoparticles were dried 80°C for 20 min.

2.4. Characterization of MSi@CuR@IL nanocomposite

Morphology of MSi@CuR@IL adsorbent was obtained by scanning electron microscope (TESCAN MIRA3, Czech Republic). Elemental character in micro meter scale was evaluated by EDS system. Chemical structure was studied by Fourier transform infrared (FTIR) spectra (WQF-510A) in 400–4000 cm^− 1.Elemental analysis of C/H/N was used for ILs confirmation (Vario El III analyzer). Thermal gravimetric analysis (TGA) was conducted by the STA504 instrument (Bahr, Germany) and BET surface area measurement was recorded using BELSORP-mini II analyser (BEL Japan). AGFM vibrating sample magnetometer (VSM) was applied in the fields up to 10 kOe (magnetic Kavir Kashan, Iran).

2.5. Phthalates extraction optimizing

To optimize DEHP, DMP, DEP extraction central composite design (CCD) version 16 was performed by the variables of X1: MSi@CuR@IL amount (20–40 mg), X2: pH (4–10), X3: time of sample absorption (5–20 min) and X4: suspension speed (100–1000 rpm). By triplet experiment design in each variable, 19 tests was considered in the concentration of 200 µg/L of phthalates (Table 1). Analysis of variance (ANOVA) was used to evaluate the significance of parameters. Based on the best model of CCD, Optimised level of MSi@CuR@IL amount, pH, time of sample absorption and suspension speed was selected. Eluent potency of samples was evaluated for methanol, chloroform and acetonitrile. Moreover solvent volume extraction was studied in the level of 1, 2 and 3 mL.

Table 1

Experimental design matrix and the response.
Run	X1	X2	X3	X4	Mean of Response for phthalates
1	7	30	550	12.5	71.02
2	7	30	550	12.5	42.69
3	7	30	550	12.5	57.92
4	7	30	550	12.5	48.09
5	1.5	30	550	12.5	41.59
6	12.5	30	550	12.5	42.97
7	10	20	100	20	49.66
8	4	20	100	5	46.79
9	10	40	1000	5	81.6
10	4	20	1000	20	64.89
11	7	30	550	12.5	22.25
12	7	30	1370	12.5	34.37
13	7	48	550	12.5	57.17
14	7	30	550	12.5	23.55
15	7	30	550	26	59.41
16	4	40	100	20	49.28
17	4	40	1000	20	50.3
18	10	40	100	5	82.39
19	10	40	100	20	65.02

2.6. MSi@CuR@IL dispersive solid-phase extraction (DSPE)

Standard solution of DEHP, DMP, DEP in the concentration between 5 to 200µg/L were prepared daily. Based on the optimized parameters in the CCD model 34 mg of MSi@CuR@IL dispersed in 10 mL aqueous samples by the pH = 6.2. The suspension vigorously stirred in 700 RPM for 14 min. Extracted phthalates are eluted from solid phase using 2 mL methanol as the best solvent. Desorbed samples was dried over the nitrogen gas and then extracted DEHP, DMP, DEP dissolved in 200µL methanol. Finally the concentration of phthalates were evaluated by GC-FID method.

2.7. Evaluation of DSPE

Performance of MSi@CuR@IL DSPE was evaluated according to calibration plots, inter- and intra-day assays, Limit of quantification (LOQ), limit of detection (LOD) and recovery assessment. Inter-day and intra-day parameters were estimated by relative standard deviations. LOD was performed by Eq. 1 equation while SA is standard deviation of blank samples, and M is slop of the calibration curve.

Eq1: LOD=\(\frac{3\text{S}\text{A}}{\text{M}}\)

LOQ was evaluated based on the 3.3 LOD.However recovery of samples were characterized based on the Eq. 2:

Recovery %= \(\frac{\text{E}\text{s}\text{t}\text{i}\text{m}\text{a}\text{t}\text{e}\text{d} \text{l}\text{e}\text{v}\text{e}\text{l} \text{o}\text{f} \text{a}\text{n}\text{a}\text{l}\text{y}\text{t}\text{e}}{\text{A}\text{c}\text{t}\text{u}\text{a}\text{l} \text{l}\text{e}\text{v}\text{e}\text{l} \text{o}\text{f} \text{a}\text{n}\text{a}\text{l}\text{y}\text{t}\text{e}}\) ×100

Finally developed method was validated by 10 plastic bottled water samples prepared from three company.

3.1. Nanocomposite characterization

As presented in Fig. 1 magnetic properties of silica aerogel was performed through chemical co-precipitation reaction. Moreover, hydrothermal strategy in the presence of copper sulphate, MSi and IL was used for MSi@CuR@IL production.

Figure 2 specified the SEM, Elemental analysis of C/H/N, VSM, TGA, BET and FTIR character of synthetized nanocomposite. The morphology of prepared MSi@CuR@IL was characterized by SEM technique. Image in Fig. 2a, 2b show the tetrahedral structure shape of CuO nanorods by diameter between 69.88 to 311.3 nm.However nanostructure of silica aerogel was confirmed by the size of 38.88 and 44.67nm.

FT-IR spectra of two synthetize steps for production of MSi and MSi@CuR@IL are depicted in Fig. 2c, 2d. The peaks at 457 cm^− 1, 3210 cm^− 1 and 3180 cm^− 1 are specified in these components. The FTIR band at 457 cm^− 1 in Fig. 2c is associated to the Cu-O stretching band [28]. Peaks in the region between 3100 cm^− 1 to 3200 cm^− 1 in (Fig. 2d) are related to quaternary amine groups of IL component [29]. Moreover bands at 3440 cm^− 1 were related to stretching vibrations of N-H groups.

Results of N₂ absorption/desorption in BET for MSi@CuR@IL was obtained at 77 K (Fig. 2f ) with the type V isotherm. The slow adsorption at low pressure and hysteresis loop at high level confirmed presence of mesoporous structure. Surface area of nanocomposite was measured 29.6 m²/g by total pores volume of 0.08cm³/g and porosity size of 11.44 nm.

Presence of IL in the MSi@CuR@IL nanocomposite was determined by C/H/N elemental analyser (Fig. 2g). According to C/H/N analysis 0.172% wt. nitrogen, 0.235% wt. C, 1.296% wt. H, and C/N ratio, 1.3 was found in the nanocomposite. EDS analysis also confirmed MSi@CuR@IL synthesis by the existence of C, N, Fe, O and Si (Table 2) in their structure.

Table 2

EDS Analysis of adsorbent
Chemical	Element	Weight %
MSi@CuR@IL	C	1.97
	N	1.25
	O	47.18
	Cu	47.71
	Si	1.7
	Fe	0.19

The Magnetic properties of MSi@CuR@IL are presented in Fig. 2h. S- Shape of Magnetic loops by the saturation of 6.2 emu/g was seen. Figure 2e.presented the results of TGA test for MSi@CuR@IL component. Weight loss of about 50% in the TGA curve occurred at 350°C.

3.2. DSPE method optimization

Significant factors such as pH, MSi@CuR@IL amount, and suspension speed, time of absorption, type and volume of elution were optimized in DSPE method. Between methanol, chloroform and acetonitrile solvents, phthalates extraction was optimized by methanol based on the Fig. 3a.

Moreover elution volume is an important parameter for successful extraction process. Large volumes of eluent is time-consuming due to nitrogen drying of extraction and analyte extraction is not completed in the little amount of solvent. Figure 3b shows 2 mL of methanol is sufficient for DEHP, DMP, and DEP extraction.

The mean GC response of DEHP, DMP, DEP chemicals(R) in DSPE method were fitted to X1, X2, X3 and X4 by linear model. Following equation predict the mean of GC response in phthalates to independent variables.

R = 91.03130-0.229781 X1-3.62090 X2 + 1.57520 X3-0.051071 X4

ANOVA analysis of CCD-RSM method presented in Table 3. F-value of 55.22 and the p-value of 0.0001 confirmed significance of linear model. R² coefficients of 0.94 and adjusted R² of 0.75 with predicted R² of 0.89 indicated suitable describing of phthalate extraction.

Table 3

ANOVA analysis of linear model.
Source	Sum of squares	Degree freedom	Mean Square	F-value	p-value Prob > F
Model	3813.85	4	953.46	55.22	0.0001
X1	19.92	1	19.92	1.15	0.3
X2	569.75	1	569.75	33	0.0001
X3	673.91	1	673.91	39.03	0.0001
X4	2550.28	2550.28	147.71	12.5	0.0001
Residual	224.45	13	17.27
Lack of Fit	176.78	11	16.07	0.6742	0.7311
Pure Error	47.67	2	23.84
Cor Total	4038.30	17

The interaction between X2 (pH) with X3 (time of sample absorption) and X4 (suspension speed) represent higher phthalate extraction at lower pH. At down pH the functional groups of MSi@CuR@IL are increased due to protonation and production of positive charge in the surface of nanocomposite. In fact generation of interaction between phthalate polar site and MSi@CuR@IL is accelerate. However extraction potency increased by growing the time of sample absorption [30]. According to linear model, the best extraction was performed using 24 mg MSi@CuR@IL, sample absorption time of 14 min at pH = 6.2 by suspension speed of 700 RPMI.

3.3. Method Evaluation

Adsorbent potency of MSi, MSi@CuR and MSi@CuR@IL was compared in optimized DSPE method. The growth of extraction level presented in Fig. 5.

Phthalate chemicals has the reaction sites such as carbonyl group for electrostatic interaction and hydrogen bonding and the site of aromatic and alkyl group for van der Waals bonding. In this way phthalates could be interact with polar component by their carbonyl groups and nonpolar forces is created by aromatic and alkyl groups. The increase of polar groups from MSi@CuR than MSi developed the adsorption potency at one step and in the second stage polar and nonpolar sites of IL progress DEHP, DMP, DEP extraction in DSPE method with MSi@CuR@IL adsorbent.

To evaluate performance of optimized method, parameters of LOD, LOQ, intera-day and inter-day reproducibility (n = 3) were measured (Table 4).

Table 4

Validation parameters of the proposed method.
Sample	Calibration curve equation	R2		LOD (µg/L)		LOQ(µg/L)	Inter-day RSD%			Intera-day RSD%
Sample	Calibration curve equation	R2		LOD (µg/L)		LOQ(µg/L)	5	60 (µg/L)	200	5	60 (µg/L)	200
DMP	y = 0.093x + 0.6035	0.993		0.78		2.57	9.5	7	3.3	9.5	3.7	2.9
DEP	y = 0.008x + 0.2241	0.991		0.84		2.77	9.4	8.1	3.5	6.4	1.7	2.1
DEHP	y = 0.0151x + 4.3479		0.999		1.25	4.12	6.4	4.5	4.5	3.3	4.8	4.4

Calibration plots was performed in the range of 5 to 200 µg/L with regression ranging from 0.991 to 0.999. Extraction recovery for DEHP, DMP, and DEP was evaluated 100.22 ± 4.3, 92.21 ± 9.5 and 102.12 ± 4.5 respectively. The intra-day and inter-day %RSD as the precision of method were reported between 1.7 and 9.5. These results confirmed that DSPE containing MSi@CuR@IL nanocomposite is suitable for phthalate assessment in water samples. The results of phthalate contamination of plastic bottled water are presented in Table 5.

Table 5

DEHP, DMP, and DEP assessment in plastic bottled water samples
Sample number	DMP (ppb)	DEP(ppb)	DEHP(ppb)
1	90.4	74.8	74.8
2	44	125.4	125.4
3	91.4	115.8	115.8
4	79	170	170
5	171	138.6	138.6
6	106	170	170
7	119.3	188	188
8	54.3	195.3	195.3
9	8.9	187	187
10	34.7	161.5	161.5

We compare DSPE based MSi@CuR@IL with reported methods for phthalate in Table 6. The results show validation parameters of suggested method are competitive with other reports.

Table 6

Comparison between DSPE based MSi@CuR@IL and other reported methods for DEHP, DMP, and DEP assessment
Technique	Analyte	Sample Pretreatment	Matrix	Linear range (µg/L)	Limit of detection (µg/L)	RSD (%)	Reference
GC-FID	Phthalate Easers	solid-phase extraction	Beverages	5-750	0.85–1.38	2.54–6.33	[31]
GC-FID	DOP – DIBP-DEHA – DBP	dispersive micro solid phase extraction	Aqueous samples	-	0.88 − 1.04	-	[32]
GC-FID	DMP-DEP-DEHP-DBP-BBP	Solid-phase microextraction	cosmeceutical products	5-1000	3.65–4.91	< 5.5	[33]
GC-FID	DMP-DEP -DBP-BBP-DNOP	Solid-phase microextraction	aqueous samples	5-500	0.32–3.13	3.7–13.3	[34]
GC-FID	DMP-DEP-DEHP	dispersive solid phase extraction	Aqueous samples	5-200	0.78–1.25	1.7–9.5	This study

Based on the importance of phthalate release from plastic bottled water, we optimized the novel DSPE based on the new adsorbent in an accurate and repeatable method. However, Gas chromatography with electron capture detector (GC-ECD) was used in method 606 EPA followed by liquid-liquid extraction. In our study, gas chromatography with flame ionization detector (GC-FID) was suggested. FID is common detector and user friendly while ECD is expert dependent with uncertainty of multiple negative ions [30]. Although ECD determine has higher sensitivity than FID, we optimized the GC-FID based method by suitable LOD due to appropriate sample preparation with MSi@CuR@IL nanocomposite.

Trace analysis of emerging contaminants such as phthalates in drinking water is strong reason for this study. We synthetized an adsorbent by two-side properties for attraction of polar and nonpolar fragment of phthalates according to gas chromatography equipped by flame ionization detector as commercial detector. The co-application of Magnetic nano silica aerogel, CuO ROD and ionic liquid in MSi@CuR@IL increase the reaction site for phthalate absorption. In this way a simple, sensitive and rapid DSPE based method has been developed for the detection of DEHP, DMP, and DEP in plastic bottled water samples. LOQ of the evaluated method was in the trace level of consistent with the contamination of real samples. This established method could be performed as an alternative option instead of international method.

Conflicts of interest

There are no conflicts of interest to declare.

Acknowledgment

This study is supported by the department of occupational health and safety engineering, school of public health and safety, Shahid Beheshti University of medical sciences (Ethical code: IR.SBMU.PHNS.REC.1399.196).

Funding: This work was supported by the public health and safety school, Shahid Beheshti University of medical sciences, Tehran, Iran.

Lian L, Jiang X, Guan J, Qiu Z, Wang X, Lou D (2020) Dispersive solid-phase extraction of bisphenols migrated from plastic food packaging materials with cetyltrimethylammonium bromide-intercalated zinc oxide. Journal of Chromatography A 1612, 460666.
Wu Q, Song Y, Wang Q, Liu W, Hao L, Wang Z, Wang C (2021) Combination of magnetic solid-phase extraction and HPLC-UV for simultaneous determination of four phthalate esters in plastic bottled juice. Food Chemistry 339, 127855.
Gao X, Kang S, Xiong R, Chen M (2020) Environment-friendly removal methods for endocrine disrupting chemicals. Sustainability 12(18): 7615.
Herrero O, Martín J. P, Freire P. F, López L. C, Peropadre A, Hazen M (2012) Toxicological evaluation of three contaminants of emerging concern by use of the Allium cepa test. Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 743(1–2): 20–24.
Parlapiano M, Akyol Ç, Foglia A, Pisani M, Astolfi P, Eusebi A. L, Fatone F (2021) Selective removal of contaminants of emerging concern (CECs) from urban water cycle via Molecularly Imprinted Polymers (MIPs): Potential of upscaling and enabling reclaimed water reuse. Journal of Environmental Chemical Engineering, 9(1): 105051.
Pastorino P, Ginebreda A (2021) Contaminants of emerging concern (CECs): occurrence and fate in aquatic ecosystems 18(24):13401.
Dogaheh M. A, Behzadi M (2019) Preparation of polypyrrole/nanosilica composite for solid-phase microextraction of bisphenol and phthalates migrated from containers to eye drops and injection solutions. Journal of pharmaceutical analysis 9(3): 185–192.
Hadjmohammadi M. R, Ranjbari E (2012) Utilization of homogeneous liquid–liquid extraction followed by HPLC-UV as a sensitive method for the extraction and determination of phthalate esters in environmental water samples. International Journal of Environmental Analytical Chemistry 92(11): 1312–1324.
Abtahi M, Dobaradaran S, Torabbeigi M, Jorfi S, Gholamnia R, Koolivand A, Darabi H, Kavousi A, Saeedi R (2019) Health risk of phthalates in water environment: occurrence in water resources, bottled water, and tap water, and burden of disease from exposure through drinking water in Tehran, Iran. Environmental research 173:469–79.
Fierens T, Servaes K, Van Holderbeke M, Geerts L, De Henauw S, Sioen I, Vanermen G (2012) Analysis of phthalates in food products and packaging materials sold on the Belgian market. Food and Chemical Toxicology 50(7): 2575–2583.
Akhbarizadeh R, Dobaradaran S, Schmidt T. C, Nabipour I, Spitz J (2020) Worldwide bottled water occurrence of emerging contaminants: a review of the recent scientific literature. Journal of hazardous materials 392: 122271.
Paluselli A, Fauvelle V, Galgani F, & Sempere R (2018) Phthalate release from plastic fragments and degradation in seawater. Environmental science & technology 53(1): 166–175.
Liang Y, Li Z, Shi P, Ling C, Chen X, Zhou Q, Li A (2019) Performance of a novel magnetic solid-phase-extraction microsphere and its application in the detection of organic micropollutants in the Huai River, China. Environmental pollution 252: 196–204.
Razavi N, Es' haghi Z (2018) Employ of magnetic polyaniline coated chitosan nanocomposite for extraction and determination of phthalate esters in diapers and wipes using gas chromatography. Microchemical Journal 142: 359–366.
Mehrani Z, Ebrahimzadeh H, Moradi E (2019) Poly m-aminophenol/nylon 6/graphene oxide electrospun nanofiber as an efficient sorbent for thin film microextraction of phthalate esters in water and milk solutions preserved in baby bottle. Journal of Chromatography A 1600: 87–94.
Lu Y, Wang B, Yan Y, Liang H, Wu D (2019) Silica protection–sacrifice functionalization of magnetic graphene with a metal–organic framework (ZIF-8) to provide a solid-phase extraction composite for recognization of phthalate easers from human plasma samples. Chromatographia 82(2): 625–634.
Viswanathamurthi P, Bhattarai N, Kim H. Y, Lee D. R (2003) The photoluminescence properties of zinc oxide nanofibres prepared by electrospinning. Nanotechnology 15(3): 320.
Boddula R, Ahmer M. F, Asiri A. M (2019) Morphology design paradigms for supercapacitors: CRC Press.
Wang J, Gao L (2003) Synthesis and characterization of ZnO nanoparticles assembled in one-dimensional order. Inorganic Chemistry Communications 6(7): 877–881.
Yuan J, Müller A. H (2010) One-dimensional organic–inorganic hybrid nanomaterials. Polymer 51(18): 4015–4036.
Ilipronti T, de Campos S. D, Muller C. C, de Campos É. A (2019) SPME fiber coated by arrayed ZNRs for sampling and concentration of polar residual solvents for further analysis using GC FID. Journal of Pharmaceutical and Biomedical Analysis 174: 644–649.
Araghi M, Ghahari M, Afarani M. S (2017) Synthesis and investigation of antimicrobial properties of SiO2@ Cu rods with core–shell structure. Journal of Environmental Chemical Engineering 5(2): 1780–1790.
Pallela P. N. V. K, Ummey S, Ruddaraju L. K, Kollu P, Khan S, Pammi S (2019) Antibacterial activity assessment and characterization of green synthesized CuO nano rods using Asparagus racemosus roots extract. SN Applied Sciences 1(5): 1–7.
Vidal L, Riekkola M.-L, Canals A (2012) Ionic liquid-modified materials for solid-phase extraction and separation: a review. Analytica chimica acta 715: 19–41.
Liu X, Gao S, Li X, Wang H, Ji X, Zhang Z (2019) Determination of microcystins in environmental water samples with ionic liquid magnetic graphene. Ecotoxicology and Environmental Safety 176: 20–26.
Tian Y, Feng J, Wang X, Luo C, Sun M (2019) Ionic liquid-functionalized silica aerogel as coating for solid-phase microextraction. Journal of Chromatography A 1583: 48–54.
Wang N, Zhou X, Cui B (2019) Synthesis of a polymeric imidazolium-embedded octadecyl ionic liquid-grafted silica sorbent for extraction of flavonoids. Journal of Chromatography A 1606: 460376.
Sowri Babu K, Ramachandra Reddy A, Sujatha C, Venugopal Reddy K, Mallika A (2013) Synthesis and optical characterization of porous ZnO. Journal of Advanced Ceramics 2(3): 260–265.
Dharaskar S. A, Wasewar K. L, Varma M. N, Shende D. Z, Yoo C (2016) Synthesis, characterization and application of 1-butyl-3-methylimidazolium tetrafluoroborate for extractive desulfurization of liquid fuel. Arabian Journal of Chemistry 9(4): 578–587.
Chen E. S, Chen E. C (2002) Electron-capture detector and multiple negative ions of aromatic hydrocarbons. Journal of Chromatography A 952(1–2): 173–183.
Yan H, Cheng X, Yang G (2012) Dummy molecularly imprinted solid-phase extraction for selective determination of five phthalate esters in plastic bottled functional beverages. Journal of agricultural and food chemistry 60(22):5524–31.
Pezhhanfar S, Farajzadeh MA, Hosseini-Yazdi SA, Mogaddam MR (2021) An MOF-based dispersive micro solid phase extraction prior to dispersive liquid-liquid microextraction for analyzing plasticizers. Journal of Food Composition and Analysis104:104174.
Chunin N, Phooplub K, Kaewpet M, Wattanasin P, Kanatharana P, Thavarungkul P, Thammakhet-Buranachai C (2019) A novel 3D-printed solid phase microextraction device equipped with silver-polyaniline coated pencil lead for the extraction of phthalate esters in cosmeceutical products. Analytica Chimica Acta 1091:30–9.
Wu D, Chen X, Liu F, Wu JF, Zhao GC (2020) A carbon dots-based coating for the determination of phthalate esters by solid-phase microextraction coupled gas chromatography in water samples. Microchemical Journal 159:105563.

No competing interests reported.

Download PDF

Version 1

posted

You are reading this latest preprint version

GC-FID based analysis of trace phthalates with a novel nanocomposite by polar-nonpolar properties in plastic bottled water

Status:

Version 1

Abstract

Figures

1. Introduction

2. Experimental

2.1. Chemicals

2.2. Chromatographic instrument

2.3. Preparation of MSi@CuR@IL adsorbent

2.4. Characterization of MSi@CuR@IL nanocomposite

2.5. Phthalates extraction optimizing

2.6. MSi@CuR@IL dispersive solid-phase extraction (DSPE)

2.7. Evaluation of DSPE

3. Results And Discussion

3.1. Nanocomposite characterization

3.2. DSPE method optimization

3.3. Method Evaluation

Conclusion

Declarations

References

Additional Declarations

Status:

Version 1