Colorimetric Detection of Carcinogenic Alkylating Fumigants on a

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Functional Nanostructured Materials (including low-D carbon)

Colorimetric Detection of Carcinogenic Alkylating Fumigants on Nylon 6 Nanofibrous Membrane. Part II: Self-Catalysis of 2Diethylaminoethyl Modified Sensor Matrix for Improvement of Sensitivity Peixin Tang, Ngoc Thi-Hong Nguyen, Jeane Gladys Lo, and Gang Sun ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b03147 • Publication Date (Web): 20 Mar 2019 Downloaded from http://pubs.acs.org on March 22, 2019

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ACS Applied Materials & Interfaces

Colorimetric Detection of Carcinogenic Alkylating Fumigants on Nylon 6 Nanofibrous Membrane. Part II: Self-Catalysis of 2-Diethylaminoethyl Modified Sensor Matrix for Improvement of Sensitivity Peixin Tang †, Ngoc Thi-Hong Nguyen ‡, Jeane Gladys Lo ‡, Gang Sun *† †

Division of Textiles and Clothing, University of California Davis, CA, USA 95616

‡ Department

of Chemistry, University of California Davis, CA, USA 95616

ABSTRACT Nylon

6

nanofibrous

membrane

(N6NFM)

was

covalently

modified

with

2-

diethylaminoethylchloride (DEAE-Cl) to provide self-catalytic functions to facilitate the formation of color compounds in reactions of 4-(p-nitrobenzyl)pyridine with alkylating fumigants.

The

2-diethylaminoethyl

group

on

the

DEAE-Cl

modified

N6NFM

(DEAE@N6NFM) enables effective elimination of hydrohalogenic acids from intermediates that were formed from reactions between the alkylating fumigants and NBP, and consequently improve their detection sensitivities, especially for 1,3-dichloropropene at room temperature. Moreover, the DEAE@N6NFM can be recycled and reused multiple times without obvious loss in the sensing functions or any noticeable material damage. The naked-eye detection limits of the sensor to 1,3-dichloropropene, methyl iodide and methyl bromide on the DEAE@N6NFM are improved to 0.2 ppm, 0.1 ppm, and 0.1 ppm, respectively, which are much lower than their occupational exposure limits. The reaction mechanism is demonstrated through a computational method by analyzing the thermodynamics of the reaction. The modification of the DEAE@N6NFM also provides an insight into the development of functionalized materials with improved reactivities for versatile sensing applications. Keywords: self-catalysis, amine, colorimetric sensor, fumigant, nanomaterial. * Corresponding author: Tel.: +1 530 752 0840; [email protected] (G. Sun). 1. INTRODUCTION Air pollutions caused by small particles and toxic industrial and agricultural chemical vapors have become serious public concerns.1,2 Specifically, the poisonings of fumigants that are used in agricultural and household pest-control continuously occur elsewhere.2-5 The monitoring methods of fumigants and pesticides are still heavily relying on sophisticated instrumentations such as gas chromatography-mass spectroscopy,6-9 quartz crystal nano-balance,10,11 acoustic wave spectroscopy,12 other lab-instrument-based methods,13,14 and computational modeling to predict their distributions,15,16 which are not convenient or suitable for providing real-time 1

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monitoring results. With the intention of instant detection and on-site monitoring of toxicants in the environment, various naked-eye detectable colorimetric and fluorescent sensors have been designed and developed, including sensors for heavy metal ions,17,18 nerve agents,19-22 pesticides and fumigants,23,24 volatile organic compounds,25,26 and other medical and biological toxicants.27,28 Nylon 6 nanofibrous membrane (N6NFM) based sensors were developed for the detection of different fumigants including methyl isothiocyanate, chloropicrin, methyl iodide, and methyl bromide.29-31 The ultrahigh surface area and good mechanical and chemical strength of the N6NFM provide a good platform on the detection of toxic vapors of a concentration ranging from ppm to ppb level with a short exposure duration (1%) (Figure 3f), which is caused by the electrostatic force between the cationic quaternary ammonium salts on the membrane and the anionic dye. Therefore, 1.0% of DEAE-Cl was selected as the optimal concentration in further studies of the self-catalytic function of 10


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DEAE@N6NFM.

Figure 2. (a) Fabrication and modification procedures of N6NFM with DEAE-Cl. (b) The proposed mechanism of the modification reactions.

Figure 3. Characterizations of the sensor matrix. (a) FTIR of N6NFM before and after the modification with different concentrations of DEAE-Cl. (b) TGA and (c) DSC curves of N6NFM and DEAE@N6NFM. (d) Quantification of DEAE groups on the N6NFM and DEAE@N6NFM with BCA tests. (e) Catalysis function of DEAE@N6NFM in a liquid phase detection. (f) Results of dyeing test of N6NFM and different concentrations DEAE@N6NFM. The inserted figures are the optical pictures of dyed membranes. Water contact angles (WCAs) of the membranes can demonstrate the surface property changes after the DEAE-Cl modification. In Figure 4(a), N6NFM is more hydrophobic by showing a WCA of 101.98°, whereas, the addition of DEAE groups on the nylon 6 surface shows a dramatic increase of the hydrophilicity of the membrane, leading to a smaller WCA. Meanwhile, the WCA continuously decreased with an increase of the DEAE-Cl concentration in the reaction systems since more hydrophilic tertiary and quaternary amines have been incorporated on the membrane. Moreover, the DEAE@N6NFM becomes even more 11



hydrophilic after one and eight cycles of the detection uses (Figure 4a-viii and 4a-ix), which was a result of protonation of the tertiary amines on the membrane through the self-catalytic reaction. (Figure 1b). The morphologies and fiber diameters of the membranes were monitored with SEM, and the images are shown in Figure 4(b). Obviously, the ultrafine fibers in N6NFM were achieved through electrospinning with an average fiber diameter around 80 nm (Figure S7). The chemical modification did not show significant effects on the fiber diameter and the morphology of the membrane when DEAE-Cl concentration that used in the modification reaction was lower than 1.0%. Therefore, the membrane maintains an ultra-high specific surface area after the modification, which ensures the good adsorption of the fumigant vapor. However, some membrane morphology changes were noticed in 3.0% and 5.0% DEAE@N6NFM. Formation of nanorods on/between nylon 6 fibers was observed, which is caused by the self-nucleophilic substitution reaction (self-polymerization) of DEAE-Cl under a basic condition. It visually proves the occurrence of the interference reaction under a high DEAE-Cl concentration. Meanwhile, the higher concentrations of DEAE-Cl also lead to increases in the fiber diameter of 3.0% and 5.0% DEAE@N6NFM from ~80 nm to 98 nm and 123 nm, respectively (Figure S7).

Figure 4. (a) Water contact angels (WCA) of (i) N6NFM, (ii)-(vii) DEAE@N6NFM with a DEAE-Cl concentration of 0.2%, 0.5%, 0.8%, 1.0%, 3.0%, and 5.0%, and (viii) 1.0% DEAE@N6NFM after one cycle and (ix) eight cycles of the detection. (b) SEM images of (i) N6NFM, (ii)-(v) DEAE@N6NFM with a DEAE-Cl concentration of 0.2%, 0.5%, 0.8%, 1.0%, 3.0%, and 5.0%, and (viii) 1.0% DEAE@N6NFM after one cycle and (ix) eight cycles of the detection. The yellow bar refers to 500 nm. 3.3. Catalytic Property of DEAE@N6NFM in Gas Phase Detection. Four layers of 1.0% DEAE@N6NFM were piled up as one sensor matrix to be soaked in 100 12


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µL of the sensing agent (50% NBP in DMSO), which ensured complete wetting of surfaces of the nanofibers. The dynamic detection procedure (Scheme 1) was used for the vapor phase detection of different fumigants with various concentrations. As a comparison, the detection of 1,3-D on a N6NFM (four layers) was also performed at room temperature. As shown in Figure 5, the color differences (Diff2) are more significant on the DEAE@N6NFM system than that of the N6NFM, especially at a very low concentration of 1,3-D. The color change on the N6NFM was not obvious when the concentration of 1,3-D was lower than 2.0 ppm. Excitingly, the detection limit of the DEAE@N6NFM was easily improved to 0.2 ppm with a quantitative Diff2 of 23.61 ± 4.40, which is more than 10 times higher than the detection sensitivity of the N6NFM sensor. Furthermore, the color change caused by exposure to 1.0 ppm of 1,3-D (REL) at the room temperature can be unambiguously noticed, with a Diff2 of 61.07 ± 6.25. Linear color intensity changes in the detection of 1,3-D concentration from 0.4 ppm to 2.0 ppm could be achieved for both N6NFM and DEAE@N6NFM systems (Figure 5c). The detection sensitivities for MeBr and MeI were also performed on the DEAE@N6NFM sensors (Figure 6). Obviously, the color difference for detecting 0.5 ppm of MeBr and MeI increased about 85.0% compared with using the N6NFM as the sensor matrix.31 By using the DEAE@N6NFM as the self-catalytic sensor matrix, the naked eye detection limits of MeI and MeBr reached 0.1 ppm, which is five times more sensitive than the previous results (0.5 ppm). The detection property of the alkylating fumigants by using the NBPDEAE@N6NFM system is compared with other colorimetric methods and products, and the results are summarized in Table 2. Another advantage of incorporating the DEAE group onto a solid support is that the addition of the extra bases can be controlled, and the DEAE group can be regenerated and reused, which can meet the criteria for the development of reusable sensor materials. The regeneration of the used DEAE groups on the DEAE@N6NFM after exposed to 1,3-D was achieved by washing the membrane with 10 mL 0.1% triethylamine acetone solution with 5 min shaking at room temperature, and then the membrane was dried in the fume hood for the next detection cycle. As shown in Figure 7(a), the self-catalytic effect of the membrane in liquid phase reaction can be maintained at least for seven cycles of regenerations and reuses, whereas, the color intensity decreased on the eighth cycle. The recyclability and reusability of the DEAE@N6NFM were also achieved for seven cycles in the gas phase detection of 1,3-D (Figure 7b). The optical images of the tested sensors in the gas phase are shown in Figure 7(c), with the color intensity change undetectable to the naked eyes except for the eighth cycle one . Moreover, the catalytic effect was increased when the membrane layer was doubled in 13



the liquid system due to increased DEAE groups in the matrix, but the catalysis was not further increased when the membrane layer was increased to four times (Figure 7a and Figure S8). It means that the self-catalytic function of the DEAE@N6NFM is correlated to the amount of DEAE groups on the membrane. Too much of DEAE may make the tertiary amine more competitive than NBP in reaction with 1,3-D. In addition, a thicker membrane may also increase the color intensity.

Figure 5. (a) Optical and color images of tested sensors with DEAE@N6NFM and N6NFM after the sensor matrix exposing to different concentrations of 1,3-D. The operation time is 10 min, including 5 min for gas pumping and 5 min for incubation. The RGB values of each sample are shown in the supporting information in Figure S9. (b) The color differences of tested sensors by using different sensor matrices. (c) Relationships between color difference and 1,3D concentration.

14


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Figure 6. The detection results of low concentrations of MeBr and MeI on N6NFM and DEAE@N6NFM. The operation time is 5 min without extra incubation time. The bottom part of the figure shows the optical images of tested sensors by using DEAE@N6NFM as the sensor matrix. The RGB values of each sample are shown in the supporting information in Figure S9. Table 2. Summary of colorimetric sensors for alkylating fumigants. Fumigants

MeI

MeBr

1,3-D

Sensor/Product

Detection range

Detection time

Ref.

Sensidyne™ 176S

5-40 ppm

in minutes

47

Sol-gel

3 mg/L

14 hours

48

NBP/N6NFM

0.5-20 ppm

5 min

31

NBP/DEAE@N6NFM

0.1-20 ppm

5 min

This work

Sensidyne™ 157SB

0.4-80 ppm

1.5 min

47

Gastec™ 136H

10-600 ppm

45 s-3 min

49

Drager™ CH27301

0.2-8 ppm

4-8 min

50

NBP/N6NFM

0.5-20 ppm

5 min

31

NBP/DEAE@N6NFM

0.1-20 ppm

5 min

This work

Sensidyne™ 249S

0.5-10 ppm

1.5 min

47

NBP/N6NFM (65 °C)

0.8-20 ppm

10 min

31

NBP/DEAE@N6NFM

0.2-20 ppm

10 min

This work

15



Figure 7. (a) Reusability of one layer (1 cm × 1 cm) and two layers of DEAE@N6NFM in the liquid phase detection of 1,3-D (50 µL 5 mg/mL) with 50% NBP in DMSO. (b) Reusability of DEAE@N6NFM in the vapor phase detection of 1,3-D (20 ppm) with 50% NBP in DMSO. (c) The color images of vapor phase tested sensors during different detection cycles. The RGB values of each sample are shown in the supporting information in Figure S9. 4. CONCLUSION 2-Diethylaminoethyl (DEAE) groups were successfully incorporated onto surfaces of nylon 6 nanofibers in a microporous nanofibrous membrane (N6NFM) through a two-step reaction process. The DEAE groups on the modified membrane (DEAE@N6NFM) could provide a self-catalytic effect to accelerate color generations between different alkylating fumigants with 4-(p-nitrobenzyl)pyridine (NBP) at room temperature. The existence of DEAE groups and the N6NFM structure enabled the solid support with effective self-catalysis of color generation, low possibility of reaction interference, better hydrophilicity, and recyclable catalysis capability. The application of the DEAE@N6NFM as a novel sensor matrix highly improved the detection sensitivity of 1,3-dichloropropene with a naked-eye detection limit of 0.2 ppm under a room temperature operation, which is much lower than its safety requirement (1.0 ppm). And the detection sensitivity of MeBr and MeI was also increased, and their detection limits were improved to 0.1 ppm. More importantly, the modified membrane can be recycled and reused without significant loss in catalysis efficiency for seven cycles of the detection. The catalytic mechanism of the reactions was theoretically proved with computational methods. The successful functionalization of such material provides guidance for the design and development of other nanomaterials with the catalytic function for various sensing applications. ACKNOWLEDGMENT 16


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