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Durable Antibacterial Cotton Fabrics Containing Stable Acyclic N‑Halamine Groups Hongru Tian, Yongshai Zhai, Cheng Xu, and Jie Liang* The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, P. R. China ABSTRACT: Inexpensive and commercially available methylene-bis-acrylamide (MBA) was covalently bonded onto the cotton fabrics by an effective catalytic solid-state reaction in water. The as-prepared MBA grafted cotton fabric (cottonMBA) was characterized by field emission scanning electron microscopy image and Fourier transform infrared spectroscopy spectra. After a facile chlorination in diluted NaOCl solution, the amide functional groups in cotton-MBA were converted to N-halamine ones and durable antibacterial cotton fabric containing stable noncyclic N-halamine groups (cotton− MBA−Cl) was achieved. Antimicrobial testing showed that the cotton−MBA−Cl could effectively inactivate 5.78 × 107 CFU/mL of S. aureus and 7.58 × 108 CFU/mL of E. coli O157:H7 completely within 1 min of contact time. Washing durability testing indicated that the oxidative chlorine percentage of the cotton−MBA−Cl decreased from 0.43% to 0.06% after 50 washing cycles and was recovered to 0.30% via a simple rechlorination. It means that the N-halamine antimicrobial groups and the covalent bonds between MBA and cotton are very resistant to washing. Storage stability testing showed that the oxidative chlorine percentage of the cotton−MBA−Cl decreased from 0.43% to 0.32% after 30 day’s storage under room temperature, indicating that N-halamine functional groups are stable. Furthermore, it was found that the grafting and chlorination processes did not have any obvious bad effect on the tensile strength of cotton fabrics due to the mild grafting and chlorination conditions.

1. INTRODUCTION As a natural polymeric material, cotton fabric can be put into different applications in our daily life because of its many advantages such as nonirritating to human skin, warmth, high breathability, and so on. However, since cotton fabrics can provide ideal environments for survival and growth of bacteria, fungi, viruses, and yeasts causing damage of cotton fabrics and transmission of infectious diseases,1 much attention has been given to the development of antibacterial cotton fabrics in the past few decades.2−6 So far, a large quantity of antimicrobial agents, such as quaternary ammonium salts,7,8 metal ions,9,10 Nhalamines,11−17 have been incorporated into cotton fabrics to endue these cotton fabrics antibacterial properties. Among these mentioned biocides, N-halamines are good candidates because of their powerful antibacterial efficacies18−22 and regenerabilities.23−26 Cotton fabrics consist mainly of cellulose which is a macromolecular polysaccharide containing reactivable hydroxy groups.27 Therefore, many works about grafting N-halamine precursors on cotton fabrics through a reaction with the hydroxyl groups of cotton fabrics were reported. Grafting copolymerization was usually used to graft N-halamine precursors on cotton fabrics.28,29 Though the reaction mediums were water solvents, the grafting rates were usually relatively © XXXX American Chemical Society

low because of the great extent of unexpected secondary reactions. Bridging agents such as organosilane and epichlorohydrin were also used to connect the N-halamine precursors with the hydroxyl groups on cotton fabric.30−34 This method could increase the grafting rate, but the synthetic routes were usually too complicated and not favorable for industrial production. Many other reaction types were also used to graft N-halamine precursors on cotton fabrics; however, most of the reaction mediums were organic solvents and the reactants were expensive and unstable, which was not good for mass production.35−37 Therefore, a facile, highly efficient, economical, and environmentally benign grafting method remains highly desirable. In this paper, an Oxa-Michael addition was used to modify cotton with N-halamine precursor. Inexpensive and commercially available methylene-bis-acrylamide (MBA) was used to treat cotton fibers by the catalysis of aqueous sodium carbonate. The reaction condition was mild and the catalytic solid-state reaction occurred in water without any organic solvents Received: Revised: Accepted: Published: A

February 28, 2017 June 21, 2017 June 23, 2017 June 24, 2017 DOI: 10.1021/acs.iecr.7b00863 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Article

Industrial & Engineering Chemistry Research

Figure 1. Synthetic route for antimicrobial cotton−MBA−Cl.

the pH of the solution was adjusted to about 7 by adding sulfuric acid solution. The chlorinated cotton fabric (cotton− MBA−Cl) was washed thoroughly with distilled water to remove the free oxidative chlorine absorbed on the surface of the cotton fabric, then dried at 45 °C for 1 h to be used next time. The iodometric/thiosulfate titration method mentioned by other researches was used to measure the loaded oxidative chlorine concentration on the coated sample, and the weight percentage of oxidative chlorine was calculated according to the following equation:28−34

involved in the whole treatment, which favors practical application and industrial production. The antimicrobial efficacies of treated cotton swatches against Staphylococcus aureus and Escherichia coli O157:H7 were evaluated according to a modified American Association of Textile Chemist and Colorists (AATCC) test method. The stabilities and recharge abilities of the N−Cl bonds of the reactive N-halamine coatings were investigated.

2. EXPERIMENTAL SECTION 2.1. Materials. Methylene-bis-acrylamide (MBA) was purchased by Shanghai Macklin Biochemical Co., Ltd. Sodium carbonate; sulfuric acid, ethanol, potassium iodide (KI), and 10% NaClO solution were purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai. The cotton fabric, 100% bleached, was purchased from Zhejiang Guangong Printing & Dyeing Company, China. All chemicals were used without further purification unless otherwise stated. The bacteria used for the antibacterial test were Staphylococcus aureus ATCC 6538P (S. aureus) and Escherichia coli O157:H7 ATCC 25922 (E. coli) (Shanghai Institute of Materia Medica of the Chinese Academy of Sciences). 2.2. Instruments. Hitachi S4800 scanning electron microscope was used to obtain field emission scanning electron microscope (FE-SEM) images. PerkinElmer PHI 5000 ESCT System was used to obtain X-ray photoelectron spectroscopy (XPS) spectra. The Fourier transform infrared spectroscopy (FTIR) spectra were obtained using Thermo Scientific Nicolet iN10 infrared spectrometer. 2.3. Grafting MBA onto Cotton Fabrics. Sodium carbonate (1.00 g), cotton fabrics (3.00 g, 10 × 10 cm), and MBA (1.00 g) were added into 50 mL of deionized water in a three-necked flask. The mixture was stirred with a mechanical stirrer at 55 °C for 6 h. After the reaction was over, the achieved MBA-grafted cotton fabric (cotton-MBA) was washed several times with distilled water and then dried at 45 °C in an oven for 2 h. 2.4. Chlorination and Analytical Titration. The achieved cotton-MBA was soaked in a 0.10% aqueous sodium hypochlorite solution under room temperature for 1 h after

Cl+(%) =

N × V × 35.45 × 100 W×2

where N and V are the normality (equiv/L) and volume (L) of sodium thiosulfate solution, respectively, and W is the weight (g) of the cotton fabric sample. 2.5. Biocidal Efficacy Test. The bacterial concentrations chosen to do the antibacterial test of the modified cotton fabric were 5.78 × 107 CFU/mL, corresponding to S. aureus, and 7.58 × 108 CFU/mL, corresponding to E. coli. The method of the antimicrobial test has been mentioned by many other researchers.33−37 Briefly, 25 μL of the bacterial suspension prepared in advance was added to the center of a 2.54 cm × 2.54 cm cotton fabric, then the other piece of cotton fabric of the same size was placed upon the first one so the as-prepared cotton fabrics were in full contact with the bacterial suspension. After 1, 5, 10, and 30 min of contact time, the cotton fabrics were put into a centrifuge tube containing 5 mL of sterile 0.02 N sodium thiosulfate solution and the bacterial suspension on the cotton fabric was transferred into the solution by a vortex. Finally 100 μL of bacterial suspension was plated on Trypticase agar plates and incubated at 37 °C for 24 h. The biocidal efficacy of the cotton fabric was analyzed according to the quantity of the bacterial colonies. 2.6. Standard Washing Testing. The washing durability of the grafted cotton fabrics was evaluated by using AATCC Test Method 61-1996.33−37 Launder-Ometer (Darong Textile Instrument Co., Ltd., Zhejiang, China) with Stainless steel canisters (1 in. × 2 in.) containing 50 stainless steel balls and 150 mL of 0.15% AATCC detergent water solution was used to B

DOI: 10.1021/acs.iecr.7b00863 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Article


Figure 2. Effects of (a) reaction time (reaction temperature, 60 °C; mass of cotton fabric, 3.00 g; mass of MBA, 1.00 g; mass of Na2CO3, 1.00 g), (b) reaction temperature (reaction time, 12 h; mass of MBA, 1.00 g; mass of Na2CO3, 1.00 g), (c) mass of MBA (reaction time, 12 h; reaction temperature, 60 °C; mass of Na2CO3, 1.00 g), and (d) mass of catalyst (reaction time, 12 h; reaction temperature, 60 °C; mass of MBA, 1.00 g) on the mass-on of MBA grafted onto cellulose. Solvent: 50 mL of water. Each symbol indicates the means ± standard errors for three observations.

do the test. Stainless steel canisters rotated at 42 rpm and 49 °C for 45 min after the cotton fabric samples were put into the machines. Each cycle of washing is equivalent to five machine washings in this test, after 5, 10, 25, and 50 cycles of machine washing, the oxidative chlorine content of the as-prepared cotton−MBA−Cl was measured by titration as mentioned in section 2.4. 2.7. Tensile Strength Testing. The tensile strength of cotton fabrics and grafted ones were assessed using a GB/ T3923-1997 standard method. The samples (25 cm × 5 cm) were tested at room temperature in quintuplicate to obtain the average value. 2.8. Storage Stability Test. The as-prepared cotton− MBA−Cl was stored in a dark environment at room temperature and the oxidative chlorine contents of the sample were measured on day 1, 3, 7, 14, 21, and 30.

added amount of catalyst. After the cotton-MBA was obtained, 0.10% NaClO aqueous solution was used to chlorinate the cotton-MBA to form antimicrobial N-halamine functional groups on cellulose. The mass-on of MBA grafted onto cellulose can be estimated from the oxidative chlorine percentage (Cl+%) on the cotton fabric. Higher Cl+% indicates more MBA grafted on the cotton fabric. To investigate the relationship between the mass-on of MBA grafted onto cellulose and reaction time, 3.00 g of cotton fabric, 1.00 g of MBA, and 1.00 g of Na2CO3 were added to 50 mL of H2O, and then the mixture was stirred for different times under 60 °C. As shown in Figure 2a, when the time increased from 3 to 12 h, the Cl+% increased from 0.07 to 0.68%; times longer than 12 h did not cause any Cl+% increase, so 12 h could be the optimal reaction time for this Oxa-Michael addition reaction. The effect of reaction temperature on the mass-on of MBA grafted onto cellulose is shown in Figure 2b. It was found that higher reaction temperature leads to more MBA grafted onto the cotton fabric. The effects of the added MBA and catalyst amounts on the mass-on of MBA grafted onto cellulose are shown in Figure 2c,d. It was obvious that the mass-on of MBA grafted onto cellulose increased with the increase of the added MBA and catalyst amounts. From the results of Figure 2, we find that a higher mass-on of MBA grafted onto cellulose can be achieved under mild and environmentally friendly reaction conditions, leading to a higher Cl+ content after chlorination of the as-prepared cotton-

3. RESULTS AND DISCUSSION 3.1. Grafting MBA onto Cotton Fabric. Studies on OxaMichael addition have been widely reported.38−42 However, the Oxa-Michael addition of α,β-unsaturated amides in aqueous solutions has not yet been reported so far as we know. In this study, we tried to covalently bond MBA, a α,β-unsaturated amide, onto the surface of cotton fabrics via Oxa-Michael addition in aqueous solutions. For the Oxa-Michael addition between MBA and cellulose, the key parameters are reaction time, reaction temperature, the added amount of MBA, and the C


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Industrial & Engineering Chemistry Research MBA compared to those reported in the literature.27−37 For the mass of catalyst and the reaction temperature, since more Na2CO3 and higher reaction temperature may cause some damage to the cotton fabrics, we chose 0.80 g and 60 °C as the optimal amount of catalyst and reaction temperature. As for the mass of MBA, different masses of MBA could cause different contents of oxidative chlorine on the surface of cotton fabrics, so more choices are provided in practical applications. 3.2. Preparation and Characterization of the Cotton− MBA−Cl. The cotton−MBA−Cl was usually prepared by a chlorination process in dilute NaClO solution, which was very simple, so there is no need to further discuss it. An FE-SEM technique was used to investigate the surface morphology of untreated cotton and cotton−MBA−Cl. FESEM images of untreated cotton and the as-prepared cotton− MBA−Cl are shown in Figure 3. It can be observed that there

was not much difference between the cotton−MBA−Cl (Figure 3b) and the untreated cotton. This means that the grafting and chlorination processes did not damage the cotton fibers. FTIR spectroscopy in an attenuated total reflection (ATR) configuration was also used to characterize the as-prepared cotton−MBA−Cl. Figure 4 shows the collected FTIR spectra of the untreated cotton and cotton−MBA−Cl. In the spectrum of cotton−MBA−Cl, the peaks at 2926 and 2854 cm−1 (corresponding to the symmetric and asymmetric stretching vibration of the C−H bonds on −CH2−CH2−)43−45 became stronger because the −CHCH− double bonds in MBA became −CH2CH2− after it was grafted onto cotton (as we can see in Figure 1). The new peak at 1458 cm−1 corresponds to the in-plane bending vibration of the C−H bonds on −CH2− CH2−,46 which also demonstrated that the −CH2−CH2− became greater, and the new peak at 1281 cm−1 ascribes to the C−N vibrational bond.47 The SEM micrographs and FTIR spectra demonstrated that MBA was successfully grafted onto the surfaces of cotton fabrics. Further confirmation of the grafted fabrics was observed by XPS spectra, which are shown in Figure 5. Compared to the XPS spectrum of the untreated cotton, that of cotton−MBA− Cl shows the new peaks at a binding energy of 400.0 eV (corresponding to N 1s) and 200.3 eV (corresponding to Cl 2p),30−34 indicating the existence of nitrogen and chlorine atoms on the surface of treated cotton fabric. The N 1s corelevel spectrum (Figure 5c) shows two peaks at BEs of about 400.0 and 400.5 eV, which may be attributed to the nitrogen atom with a conjugated system nearby and a nitrogen atom

Figure 3. FE-SEM images of the untreated cotton (a) and cotton− MBA−Cl (b) at a magnification of 5000×.

Figure 4. FTIR spectra of untreated cotton and cotton−MBA−Cl. D


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Figure 5. XPS spectra of cotton and cotton−MBA−Cl (a), Cl2p core-level spectra of cotton and cotton−MBA−Cl (b), and N1s core-level spectra of cotton and cotton−MBA−Cl (c).

stable during washing. More interestingly, the percentages of Cl+ reached 0.40, 0.38, 0.35, and 0.30% by a simple rechlorination after 5, 10, 25, and 50 machine washing cycles. It clearly demonstrates that the lost N-halamine functional groups can be regenerated and the decrease of Cl+% on cotton−MBA−Cl fabrics during washing is mainly caused by the conversion of N−Cl to N−H groups. Also, after 50 washing cycles, the oxidative chlorine loading could be revived up to 0.30%, indicating that the chemical bonds between MBA and cotton fabric are resistant to washing. It can be concluded that the washing durability of the as-prepared cotton−MBA−Cl fabric in this paper is much better than that of the cyclic Nhalamine grafted cotton fabrics reported in the literature.29−33 The reason for the good washing durability is that MBA is grafted onto cellulose via ester bonds which are not easily hydrolyzed in water and have a good acid and basic resistance. This characteristic could give cotton−MBA−Cl fabrics a wide range of applications. 3.4. Tensile Strength. The tensile strength testing of untreated cotton fabrics, cotton-MBA, and cotton−MBA−Cl were performed, and the results are shown in Figure 6. Cellulose is unstable under alkaline conditions, which has been reported by many other researchers. Because the grafting reaction was performed under weak alkaline conditions, there is a small degree of loss of tensile strength when the cotton has been grafted. However, this grafting method has an advantage over the traditional coating process to produce antimicrobial Nhalamine fabrics in practical applications. The small degree loss of tensile strength between the cotton-MBA and the cotton− MBA−Cl was due to the oxidative sodium hypochlorite in the chlorination reaction, which was also reported in other researche.34−36

without that. The XPS spectra indicate that MBA was successfully grafted onto cotton, and the N-halamine functional groups formed after the chlorination process. 3.3. Washing Durability of the as-Prepared Cotton− MBA−Cl. The washing durability of the as-prepared cotton− MBA−Cl was evaluated using the method mentioned in the Experimental Section, and the results are shown in Table 1. Table 1. Washing Durability of Cotton−MBA−Cla Cl+ concentrationb (wt %) no. of washing cycles

X

Y

0 5 10 25 50

0.43 0.33 0.28 0.21 0.06

0.43 0.40 0.38 0.35 0.30

a

Conditions: X, oxidative chlorine content of the samples after different washing cycles; Y, oxidative chlorine content of the samples rechlorinated after washing. bThe error in the measured Cl+ wt % values was ±0.01.

The column marked X refers to the oxidative chlorine content of the samples after different washing cycles, which indicates the washing durability of the N-halamine functional groups on the cotton−MBA−Cl. And the column marked Y refers to oxidative chlorine content of the samples rechlorinated after washing, which indicates the washing durability of the newly formed bond between the cotton fabric and MBA. It was found from Table 1 that the Cl+% of cotton−MBA−Cl fabrics decreased from 0.43% to 0.33, 0.28, 0.21, and 0.06% after 5, 10, 25, 50 washing cycles, respectively. It means that the acyclic amide N−Cl bonds in cotton−MBA−Cl fabrics are relatively E


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cotton−MBA−Cl fabrics have excellent antibacterial efficacies against both kinds of bacteria. For the untreated cotton and cotton-MBA fabrics, it was found that the S. aureus reductions are 12 and 20% and E. coli O157:H7 reductions are 22 and 43% within a contact time of 30 min, respectively, probably due to the adhesion of bacteria to the cotton fabrics. To further investigate the bactericidal action, we also measured the inhibition zone of the as-prepared cotton− MBA−Cl fabrics. A solution containing both S. aureus and E. coli at 1 × 104 CFU/mL was used to perform the test. The cotton-MBAA-Cl fabrics, molded as discs with a diameter of 1.8 cm, were placed onto the surfaces of the bacteria containing agar cultural plate. The inhibition zones around the discs were measured after incubation at 37 °C for 12 h. In Figure 7, the

Figure 6. Tensile strength of the cotton fabrics.

3.5. Storage Stability. Table 2 shows the results of the storage stability of the as-prepared cotton−MBA−Cl. After 30 Table 2. Storage Stability of the as-Prepared Cotton−MBA− Cl Cl+ concentrationa (wt %)

a

time (day)

before rechlorination

after rechlorination

0 3 7 14 21 30

0.43 0.40 0.38 0.35 0.33 0.32

0.43

Figure 7. Photograph of the zone of inhibition against E. coli and S. aureus for cotton−MBA−Cl.

The error in the measured Cl wt % values was ±0.01.

days of storage in the dark at room temperature, over 74% of the oxidative chlorine was retained and the loss of oxidative chlorines was regained by 100% after rechlorination, which means the N-halamine groups and the new formed ether bond on the cotton−MBA−Cl was stable under the storage condition. 3.6. Biocidal Efficacy. The antibacterial test results of untreated cotton, cotton-MBA, and cotton−MBA−Cl against S. aureus and E. coli O157:H7 are shown in Table 3. As can be seen from Table 3, the as-prepared cotton−MBA−Cl fabric with a oxidative chlorine content of 0.43% completely inactivated S. aureus and E. coli O157:H7 in a contact time of less than or equal to 1 min, implying that the as-prepared

photographs give apparent inhibition zones with the radius of 2.3 cm for E. coli and S. aureus, indicating that the as-prepared cotton−MBA−Cl fabrics have excellent antibacterial activity toward both strains. As for the cause of the formation of inhibition zones, we can conclude that the oxidative chlorine was released to the agar medium and killed the bacterial in the zone.48,49

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CONCLUSIONS Inexpensive and commercially available methylene-bis-acrylamide was used to treat cotton fabrics by a facile, highly efficient, economical and environmentally benign grafting method. After exposure to a diluted aqueous solution of household bleach, the grafted cotton became biocidal. It is clear that the whole process can be easily scaled up for commercial applications. The as-prepared cotton−MBA−Cl fabrics exhibited powerful antimicrobial properties against S. aureus and E. coli O157:H7. The washing durability test indicated that 69.77% of MBA moieties remained on the surface of cotton−MBA−Cl fabrics after 50 washing cycles, and 0.30% of Cl+ could be reached by rechlorination which could still quickly kill bacteria. After grafting and chlorination processes, the tensile strength of cotton fabrics had no significant decline, indicating that the grafting and chlorination processes did not cause any significant damage to the structure of the cotton fabrics. With the above-mentioned advantages,

Table 3. Antibacterial Properties of Treated Cotton Swatches against S. aureus and E. coli O157:H7 bacterial reduction (%)

a b

sample

contact time (min)

S. aureusa

E.coli O157:H7b

cotton cotton−MBA cotton−MBA−Cl

30 30 1 5 10 30

12 20 100 100 100 100

22 43 100 100 100 100

Inoculum was 5.78 × 107 colony forming units (CFU) per sample. Inoculum was 7.58 × 108 CFU per sample. F


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the as-prepared cotton−MBA−Cl fabrics will have potential applications in the antimicrobial treatment of textiles.

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +86-21-64321045. Fax: +86-21-64322511. E-mail: [email protected]. ORCID

Jie Liang: 0000-0002-3870-4199 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors would like to acknowledge the financial support from Shanghai Pujiang Talent Project (11PJ1407600), the Research and Innovation Project of Municipal Education Commission of Shanghai (12YZ085), and the Shanghai Natural Science Foundation (10ZR1407700). This work is supported by PCSIRT (RT1269), the Program of Shanghai Normal University (DZL124).

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