Surface-Modified Graphene Oxide-Based Cotton Fabric by Ion

Mar 27, 2019 - ... analysis showed two facts: (1) ion bombardment damaged the original structure of GO-cotton, and some whirlpools structure was gener...
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Surface modified graphene oxide based cotton fabric by ion implantation for enhancing antibacterial activity Junhui Hu, Jian Liu, Lihui Gan, and Minnan Long ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06361 • Publication Date (Web): 27 Mar 2019 Downloaded from http://pubs.acs.org on March 27, 2019

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Surface modified graphene oxide based cotton fabric by ion implantation for enhancing antibacterial activity

Junhui Hu†, Jian Liu†,††,†††*, Lihui Gan†,††,†††*, Minnan Long†,††,††† .College of Energy, Xiamen University, Xiamen 361102, China



. Xiamen Key Laboratory of Clean and High-valued Applications of Biomass,

††

Xiamen University, Xiamen 361102, China; . Fujian Engineering and Research Center of Clean and High-valued

†††

Technologies for Biomass, Xiamen University, Xiamen 361102, China

* Corresponding author. E-mail: [email protected] (Jian Liu); [email protected] (Lihui Gan) Address: College of Energy, Xiang'an Campus of Xiamen University, Xiang'an South Road, Xiang'an District, Xiamen 361102, Fujian, China

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Abstract The graphene has been concerned as a promising antibacterial material. The antibacterial activity is proved to be related to the distinctive conformation. In this study, ion implantation is used to modify the surface property and structure of carbon-based materials as an effective technique. GO nanosheets was introduced on the cotton fabric by radiation-induced crosslinking under the domestic microwave and suffered with bombardment by different dose of Fe3+ ions. SEM showed GO nanosheets has appeared protuberances and nanopore after being treated by ion implantation. AFM and Raman analysis showed two facts: (1) ion bombardment has damaged the original structure of GO-cotton and some whirlpools structure generated. (2) The root mean square (RMS) value of the modified GO-cotton is higher than the controls. Compared with the untreated GO coated on cotton fabrics, the ion implanted GO-cotton showed higher antibacterial activity. In addition, the high thermal stability and washing durability are also investigated. In general, the prepared materials possess excellent mechanical, thermal, antibacterial and washing durability properties. Keywords Graphene

oxide

nanosheets,

Cotton

fabric,

GO-cotton,

Antibacterial.

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Ion

implantation,

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Introduction In recent years, antibacterial agents and materials play an important role in global public health. However, the wide use of antibiotics in killing or inhibiting bacterial growth leads to the rise of antibiotic resistance, resulting in poor treatment efficacy and significant economic losses

1, 2.

Clothing and other textile materials,

especially those made of natural fibers such as cotton, can act as the hot-bed of microorganisms. When in contact with the human body, cotton fabrics offer an ideal environment for microbial growth because of their large surface area and hydrophilicity. Therefore, with a rising interest in personal health and hygiene, textiles with antimicrobial properties are becoming an increasingly desirable aim of textile manufacturers 3,4. In the last few years, metal or metal oxide nanoparticles (e.g. Ag, TiO2 and ZnO) were applied to develop the antibacterial properties of textile materials. Typically, Ag nanoparticles are widely used as an effective antibacterial agent for its application on antibacterial textile 5-8. However, the risk in assessment of nanoparticles to human bodies should be considered 9,10. Since the nanoparticles are in very small size, they can easily access to skin and other organs and lead to potential problems

11, 12, 13.

Therefore, it makes sense to find new safe substitutes for metal

nanoparticles. Graphene is one of the most promising materials due to its outstanding mechanical, electrical and thermal properties

14,15

as well as its diverse potential

applications, such as biosensors, electronic devices, supercapacitor and so on

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16-18.

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Graphene oxide (GO), a material derived from graphene, produced through the chemical exfoliation of graphite, consists of single-layer or multi-layers of two-dimensional graphene sheet with oxygen-containing functional groups, which makes it readily dispersed in water 19. Recently, the antibacterial activity of graphene materials has been concerned 20-23. A systematic study compared antibacterial activity of graphite, graphite oxide, GO and reduced graphene oxide (rGO), respectively and showed GO and rGO exhibited high antibacterial activity against P.aeruginosa 24. The mechanism of antibacterial is presumed to be related to the sharp nanosheets of GO. Therefore, it is meaningful to investigate how the distinctive conformation of GO affects the antibacterial activity. Ion implantation is an effective technique in modifying the surface property, structure and morphology of carbon-based materials that utilizes implantation of various ions with different energy and doses in a controlled manner

25.

Carbon ion has been used to introduce defects into graphene

sheets 26. Implanting Ti ions in different doses deoxygenated and modified the surface of GO papers 27, while the implantation of Au ion led to the enhancement of Raman scattering 28. To date, ion implantation for GO antibacterial materials has been rarely reported. In this paper, we first prepared GO coated cotton fabric by a facile and rapid microwave-assisted method and then used different doses of ion implantation for material modification. The potential antibacterial activity against both Gram-negative and Gram-positive bacteria was evaluated. The results show that ion implantation is an effective way to modify the surface properties of GO and enhance the antibacterial activity. By ion implantation on the modified surface of GO, we can obtain more

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antibacterial activity and washing durability. Our study offers an advanced and effective method to produce antibacterial materials with a wide range of potential textile industrial and biomedical applications.

Experimental section Reagents and materials The bleached plain weave with 100% cotton fabrics (120 g/m2, 40 s, wrap/weft density 25/21 threads/cm, dip bleaching) were purchased from YongSheng Spinning & Weaving Company. Few-layer GO powder (Purity > 98%) was purchased from Suzhou Tanfeng Graphene Tech Co., Ltd. EDTA was purchased from Guangdong Xi long Chemical Co., Ltd. All chemical agents are of analytical grade. Preparation of GO-cotton 100 mg of GO powder was dispersed in 100 mL of deionized water under sonication for 1 h to prepare a stable GO colloid (1.0 mg/mL). The cotton fabric was cut into 5×5 cm2 and initially cleaned in acetone, ethanol and deionized water under sonication for 30 min, successively. Then it was dipped into the above dispersion solution and treated with a microwave oven (1000 W) for 10 min. The sample was turned over every minute to ensure uniform coating of GO nanosheets on the fabric. Lastly the GO-cotton was rinsed with deionized water and dried at 100℃ for 1 h. Preparation of ion implanted GO nanosheets and GO-cotton Ion implantation experiments were performed according to the literature 29 with the ion implanter (NEC company, America) in Xiamen University. The implantation doses for the as-prepared GO-cotton were set at a certain ion dose with an

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accelerating voltage of 60 kV. The ion beam current was kept approximately at 6 mA. ii-GO-c-1, ii-GO-c-2 and ii-GO-c-3 represent ion implanted GO coated cotton fabrics with the ion dose of 5×1014, 8×1014, 3×1015 ions/cm2, respectively. Antibacterial test The antibacterial activity of fabric was examined against Gram-positive bacteria S.aureus and Gram-negative bacteria E.coli. To prepare the seed, E.coli and S.aureus were cultured in LB medium and incubated in a shaking incubator at 37℃ and 200 rpm overnight. Then the bacteria were incubated into the fresh media in an inoculum dose of 1:100 and growing at 37℃and 200 rpm for 2.5 h (S.aureus) and 5.0 h (E.coli) till the optical density of 0.5 at 600 nm (OD600) was reached

30.

Shake flask test

method was used to evaluate the antibacterial activities. The tested cotton fabric was cut into square sheets in size of 1 cm × 1 cm and weighed 0.015 ± 0.005 g. The samples were first dipped in EDTA solution (50 mL, 0.5 mol/L) to remove the residual Fe ions and then sterilized at 121℃ for 20 min in an autoclave. Each sample was a 250-mL Erlenmeyer flask filled with 20 mL of LB medium and incubated with 0.2 mL of seed. The incubation conditions are 37℃ and 200 rpm for 2.5 h. The broth was diluted to a certain volume by 10-fold dilution. 0.1 mL of diluent transferred on LB agar plates in triplicate and incubated at 37℃ for 24 h. The antibacterial efficiency was obtained as follows: R (Rate of Bacteriostasis) = (A-B) /A×100%, where A and B are the colonies on the untreated and treated fabrics respectively. Therefore, the Cell viability, C = (1-R) ×100%. Washing test The effect of washing durability of antibacterial activity of the GO and ion

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implanted GO coated cotton fabrics were evaluated according to AATCC 61(2A)-1996 31. In this test, cotton fabric samples (5 cm × 5cm) were first immersed in the solution of WOB Standard detergent (50 mL, 1.5 mg/mL) and then washed for 10 min in the shaking incubator at 38℃ and 200 rpm. Afterwards, all the samples were washed 60 times with deionized water, every time for 5 min. Finally the samples were dried at 60 ℃ and the antibacterial activity was tested. Mechanical test The tensile strength properties of the control and modified cotton fabrics were conducted with a tensometer (ZHIQU) at a constant speed of 100 mm/min and ambient temperature. The as-prepared cotton fabric samples were in the size of 4 mm width, 20 mm length and 0.2 mm thickness. The tensile strength (σmax, kPa) is calculated as σmax = F/A, where F represents the load (kN), and A stands for the cross area (m2).

Material Characterizations Fourier-transform infrared (FTIR, Nicolet iS5 Thermo Fisher) spectra was used to confirm the presence of functional groups in as-prepared cotton fabric samples. The surface morphology of the untreated cotton fabrics, GO and ion implanted GO coated cotton fabrics were observed at an acceleration voltage of 5 kV by field emission scanning electron microscopy (FESEM, SUPRA 55 instrument). All the samples were sputtered with gold for 30 s. Atomic Force Microscopy (AFM, Nanoscope) were employed to investigate the surface morphology of GO-cotton which were implanted with Fe ions at the doses of 0, 5×1014, 8×1014, 3×1015 ions/cm2. The root mean square (RMS) and 3D images were made by NanoScope Analysis. Molecular structure was

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investigated using IDSpec ARCTIC Raman spectrometer at the excitation wavelength of 532 nm. Thermogravimetric analysis (TG) was conducted in a STA449F5 manufactured by NETZSCH of Germany. The samples approximate 5 mg were heated from 30 ℃ to 600 ℃ at a rate of 20 ℃/min under nitrogen atmosphere.

Results and discussion Material preparation and SEM analysis The photographs of untreated cotton fabric (UCF), GO-cotton and ii-GO-cotton (3×1015 ions/cm2) are shown in Figure 1. FESEM was employed to identify the morphology of the GO nanosheets coating cotton fibers before and after implantation of Fe ions at different doses (Figure 2). The UCF is made up of single fibers that twist spiral together or side by side in a cylindrical-like structure (Figure 2a) As we all known, GO has a two-dimension structure. By loading on the fibers, GO can act as the membrane to wrap them (Figure 2b). The GO distributes evenly on the fibers and attaches on the surface of GO by strong electrostatic interaction. The GO modified by ion implantation showed cracks due to the impact of high ion beam (Figure 2c-e). High dose of implantation caused severe crack and structure changes. Jagged fragments appeared on the both side of fibers at the dose of 3×1015 ions/cm2 (Figure 2e). It is interesting that the fibers seem like an axe at the magnification of ×2000. The fibers act as axe-handle and GO nanosheets act as axe-blade (Figure 2f). This structure may provide a good basis for subsequent antibacterial activity.

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Figure 1. Photographs of GO coated cotton fabrics. a-c are untreated cotton fabric (UCF), GO-cotton, and ii-GO-cotton(3×1015ions/cm2), respectively.

Figure 2. SEM images of UCF (a, ×1000), GO-cotton(b, ×1000), ii-GO-c-1 (c, ×1000), ii-GO-c-2 (d, ×1000) and ii-GO-c-3 (e, ×1000; f,×2000), respectively.

The mechanisms for modification of graphene nanostructures by ion implantation were investigated by atomic simulation 32, 33. The nanopore is caused by the direct sputtering from the collision of irradiated particle beam and the dragging of the adjacent carbon atoms

34.

Low energy ion beam irradiation method was

demonstrated to be capable to dope graphene efficiently while high energy ions could pass through the graphene plane instantaneously without inducing any sputtering effect 35. An ion beam irradiation with supposed level of energy contributes to the

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proper modification of graphene nanostructures. AFM analysis The GO-cotton exhibited a large smooth area and a few intrinsic ripples (Figure 3a). The implanted GO cotton showed surface topography changes in appearing many whirlpools and defects which could attribute to the etching by Fe ions, as shown in 3D and 2D images (Figure 3b-d). The height profile corresponding to the white line of 2D images were plot by NanoScope Analysis (Figure 3i-l). The untreated GO-cotton has uniform curve and the height values fluctuates between -50nm and 50nm (Figure 3i). With the increasing of ion implantation dose, the fluctuation frequency of curve increases, indicating more protuberances and concaves on its surface, which is presumed to be related to the antibacterial activity. Meanwhile, the depth of concaves increased from 58 nm to 208 nm. Moreover, more comprehensive surface topography can be seen from the corresponding 3D image (Figure 3a-d). The root mean square (RMS) and average deviation values are also calculated through the NanoScope Analysis (Table 1). It is observed that the RMS and its average deviation value relatively increased compared with the untreated GO cotton, due to the action by implantation of Fe ions on cotton fabrics.

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Figure 3. AFM surface morphology of GO-cotton showing (a-d) 3D, (e-h) 2D, (i-l) height distribution curve that marked with 1 μm white lines on 2D AFM images for (a,e,i) unimplanted, and ions implanted GO nanosheets at dose of (b,f,j) 5×1014 ions/cm2 , (c,g,k) 8×1014 ions/cm2 and (d,h,l) 3×1015 ions/cm2.

Table 1. The root mean square and average deviation values of 2D AFM images.

sample GO-cotton ii-GO-cotton-1 ii-GO-cotton-2 ii-GO-cotton-3

Roughness RMS 20.7 35.7 60.2 88.3

Average Deviation 15.8 25.5 43.0 55.3

Raman spectra of GO nanosheets Raman spectra is a powerful technique to study carbon-based materials due to the specific responses to the structural changes in carbon hybridization state. The Raman spectra of GO samples after Fe ion implantation of different doses are shown in Figure 4a-d. The original GO showed two obvious peaks at 1348 cm-1 and 1579

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cm-1 which can be attributed to the D and G band, respectively. The D band represents the defects induced in GO structure while the G band is resulted from the scattering of E2g mode in sp2 carbon domains

36.

We often use R (ID/IG, the intensity ratio of D

band to G band) as the measure of defect levels in graphene-based materials. The major changes are mainly in three aspects, G band center, width and R, as shown in Figure 4. In order to obtain the accurate parameters of the two peaks, Peak Analyzer is used to fit the Lorenz curves (Table 2).

Table 2. The Raman spectral parameters of GO nanosheets after being treated with different doses of Fe ions implantation.

D band/cm-1 center 1348 1349 1353 1348

sample GO ii-GO-1 ii-GO-2 ii-GO-3

width 147 131 132 92

G band/cm-1 center 1579 1583 1585 1589

R=ID/IG

width 76 73 76 92

0. 98 0. 91 0. 84 0. 59

G D 15

2

14

2

GO-2(8x1014ions/cm2)

b ii-GO-1 (5×10 ions/cm )

2

GO-1(5x1014ions/cm2)

a original GO nanosheets

pure GO

d ii-GO-3 (3×10 ions/cm )

Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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c ii-GO-2 (8×10 ions/cm )

14

1000

1500

2000

2500

GO-3(3x1015ions/cm2)

3000

-1

Raman shift (cm )

Figure 4. Raman spectra of original GO nanosheets (a) and ion implanted GO nanosheets at three difference doses (b-d).

According to Table 2, ID/IG ratios of ion implantation at difference doses were

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found to be within 0.59-0.91, which were lower than original GO nanosheets (0.98). The ratio decreased with the ion dose increasing. It indicated more defects on the GO nanostructure by stronger ion implantation. The G band of implanted GO nanosheets (1589 cm-1) up-shifted by 10 cm-1 compared to original GO (1579 cm-1), which is consistent with the G band shift and electron-phonon coupling previously observed after introduction of Fe ions in GO nanosheets

37.

The G band width at low dose of the implantation were also same as

the original GO (76 cm-1), while it broadened obviously (92cm-1) at the 3×1015 ions/cm2. This phenomenon showed the damage in the nanostructure after the high dose of ion implantation. 100 80

Weight (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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60 40 GO-cotton

20

ii-GO-cotton

UCF 0

0

100

200

300

400

500

600

Temperature (℃ )

Figure 5. TGA curves of UCF, GO-cotton and ii-GO-cotton.

Thermal properties The thermal stabilities of UCF, GO-cotton and ii-GO-cotton are shown in Figure 5. It is obvious that the process of weight loss in all the samples is divided into two steps. All the samples have a minor weight loss below 200 ℃ due to the removal of moisture content in the first step. The second step, a sharp weight loss ranging from 300 to 400℃ resulted from degradation of cellulose in cotton fabric. The residual

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weight of GO-cotton is 10.95% at 600℃, which is more than that of ii-GO (8.86%) due to its weight addition of Fe element in the ion implantation. 100

10

(a)

80

60

40

20

0

(b)

8 Elongation at break (mm)

Tensile strength (MPa)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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UCF

GO-cotton

ii-GO-c-1

ii-GO-c-2

ii-GO-c-3

6

4

2

0

UCF

GO-cotton

ii-GO-c-1

ii-GO-c-2

ii-GO-c-3

Figure 6. (a) Tensile strength and (b) elongation at break of UCF, GO-cotton and ii-GO-cotton.

Tensile properties The mechanical properties of cotton fabric are essential in textile industrial. The histogram of tensile strength (σmax) and elongation at break are shown in Figure 6. It is obvious that the addition of GO increased the tensile strength due to the contribution of GO nanosheets with well mechanical property. However, the ion implantation showed a negative effect on the tensile strength. Furthermore, the increase of ion dose reduced the tensile strength, attributing to the structural damage of GO nanosheet by the harsh ion implantation. In conclusion, the mechanical properties of cotton fabrics can be enhanced with the addition of GO, but reduced with ion implantation, relying on dose.

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ii-GO-cotton OH

C=O

C-C C-O

GO-cotton C=O

Transmittance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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C-C

OH

C-O

GO

C=O

C-OH

C=C UCF C=O COOH C-O

3000

2800

2600

2400

2200

2000

1800

1600

1400

1200

1000

-1

Wavenumber (cm )

Figure 7. FTIR spectra of UCF, GO, GO-cotton and ii-GO-cotton fabrics (3×1015 ions/cm2), respectively.

FT-IR As shown in Figure 7, the spectra generated for UCF, GO, GO-cotton and ii-GO-cotton fabrics (3×1015 ions/cm2) were different, indicating differences in their chemical groups. The spectra of GO-cotton and ii-GO-cotton fabrics showed wide absorption bands in the 2300-2400 cm-1 region corresponding to stretching vibrations of hydroxyl groups, which indicates hydrogen-bonding interactions in these materials. The band was more intense in the composites compared to UCF and GO, which could be attributed to the newly generated hydrogen bonds in the recombination. The characteristic peaks of GO observed at 1630 cm-1 correspond to C-C stretching was observed in the sample spectra of GO, GO-cotton and ii-GO-cotton fabrics, indicating a successful loading of GO. A band at 1040 cm-1 appeared in UCF, GO-cotton and ii-GO-cotton fabrics, indicating the presence of cellulose in the samples.

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120

160

(a)

(b) **

80

** **

60

**

40 20

S.aureus viability (%)

120

0

**

140

100 E.coli viability (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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*

*

100 80 60 40 20

UCF

GO-cotton

ii-GO-c-1

ii-GO-c-2

ii-GO-c-3

0

UCF

GO-cotton

ii-GO-c-1

ii-GO-c-2

ii-GO-c-3

Figure 8. Bacterial cell viability of E. coli (a) and S. aureus (b) treated with UCF, GO-cotton, ii-GO-cotton, respectively. Error bars represent the standard deviations (n=3). *p< 0.05, **p<0.01.

Antibacterial Activity The antibacterial activities of the samples were evaluated by CFU counting method against both S. aureus and E. coli, as shown in Figure 8. The UCF showed no antibacterial activities against both G+ and G- bacteria. In the case of E. coli, after treatment with GO coated cotton, the viability decreased. Moreover, the samples with implantation of high ion dose exhibit higher antibacterial activity than those with low ion dose. However, in the case of S. aureus, no antibacterial activity was detected. On the contrary, the GO coated cotton even cause a 12%~45% increase in S. aureus cells viability (Figure 8b. It is surprising that GO contributed to the proliferation of Gram-positive microbial cell. A potential reason is indicated by Ruiz et al. that GO acts as a scaffold for the surface attachment and proliferation of cells

38.

There are

some assumptions on the antibacterial mechanism of GO. GO nanosheet has sharp edges and oxygen-contained functional groups on the surface which makes it negatively charged, and easily bind to the bacterial cell wall and damage them. It

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serves as a blade to cut the cell membrane

39,40.

As we know, the cell wall of

Gram-positive bacteria is thicker than the Gram-negative bacteria and its high-strength peptidoglycan prevents cell membrane from the destruction by sharp GO. This statement explained why the cotton fabric coated GO exhibited higher antibacterial activity against E. coli than S. aureus. Furthermore, it is reasonable that the jagged fragments of GO nanosheets bring even more damage to E.coli. Therefore, the cotton fabric coated with ion implanted GO show higher antibacterial activity than the control. In order to further investigate the antibacterial property in liquid culture, the bacterial growth rate of E.coli was characterized by measuring optical density of LB medium and the curves are shown in Figure 9a. The growth curve of incubation with UCF need approximately 5 h to reach a tentative concentration (OD600=0.5) and the others under the antibacterial pressure need more time. It is obvious that E. coli growth rate decreased on the effects of GO coated cotton fabrics, especially the ion-implanted samples of higher dose. 0.7

(a)

(b)

UCF GO-cotton ii-GO-c-1 ii-GO-c-2 ii-GO-c-3

1.4 1.2 1.0

0.6 E.coli growth at 5h (O.D.600 nm)

1.6

E.coli growth (O.D.600 nm)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.8 0.6

OD600=0.5

Log phase

0.4 0.2 0.0

0.5 0.4 0.3

0.1 0.0

0

2

4

6 Time (h)

8

10

12

UCF GO-cotton ii-GO-1 ii-GO-2 ii-GO-3

0.2

0

15

30 washing times

45

60

Figure 9. (a) The E.coli growth curve of 12 h after being treated with UCF, GO-cotton and ii-GO-cotton, respectively. (b) The E.coli OD600 values at 5 h of UCF, GO-cotton and ii-GO-cotton, respectively after being washed for 0 to 60 times.

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Washing durability Washing durability is an important feature of in evaluating the antibacterial textile materials. The cell concentrations under the antibacterial pressure by prepared 5 samples were recorded in Figure 9b. The antibacterial efficiency of GO-cotton and ii-GO-cotton decreased slowly in the washing process, especially the GO-cotton retained original antibacterial efficiency even after being washed for 60 times. The mechanism probably attributed to large amounts of carboxyl groups on the surfaces of GO result in strong hydrogen bonds between GO and cotton fabrics 41.

Conclusion In summary, the result shows that the GO nanosheets can successfully combine with cotton fabrics under microwave irradiation. Subsequently GO coated on cotton fabrics were treated with ion implantation using varies dose of Fe ions in order to modify the surface and properties of GO nanosheets. Through the analysis of surface morphology by SEM and AFM, we can conclude that jagged fragments formed on GO nanosheets. Furthermore, some novel structure like whirlpools has been generated, which is presumed to be related to the antibacterial activity. The antibacterial test showed that GO coated on cotton fabrics exhibited higher antibacterial activity against E.coli than S.aureus. What’s more, ion implanted GO-cotton exhibited higher antibacterial activity than the controls. The increasing of ion dose also resulted in higher antibacterial activity. The proposed mechanism is that the size and geometry of GO nanosheets play an important role in its antibacterial

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activity. The composites have shown great washing durability even after being washed for 60 times. At the same time ion implantation provides a new method for the surface modification of GO materials, which may facilitate the development of GO based antimicrobial with respect to selective antibacterial field for Gram-negative bacteria.

Author Information Corresponding Author [email protected] [email protected] Present Addresses † College of Energy, Xiamen University, Xiamen 361102, China Acknowledgment This work was supported by the Energy development Foundation of College of Energy, Xiamen University (No. 2018NYFZ03 & 2017NYFZ02).

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Table of contents (TOC)

Synopsis After the ion implantation, GO coated cotton fabrics show better antibacterial activity, possessing excellent mechanical, thermal, antibacterial and washing durability properties.

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