Lasting superhydrophobicity and antibacterial activity of Cu nanoparticles immobilized on the surface of dopamine modified cotton fabrics

    Lasting superhydrophobicity and antibacterial activity of Cu nanoparticles immobilized on the surface of dopamine modified cotton fabrics Jiaying Yang, Hong Xu, Linping Zhang, Yi Zhong, Xiaofeng Sui, Zhiping Mao PII: DOI: Reference:

S0257-8972(16)31190-2 doi: 10.1016/j.surfcoat.2016.11.058 SCT 21804

To appear in:

Surface & Coatings Technology

Received date: Revised date: Accepted date:

18 April 2016 10 November 2016 15 November 2016

Please cite this article as: Jiaying Yang, Hong Xu, Linping Zhang, Yi Zhong, Xiaofeng Sui, Zhiping Mao, Lasting superhydrophobicity and antibacterial activity of Cu nanoparticles immobilized on the surface of dopamine modified cotton fabrics, Surface & Coatings Technology (2016), doi: 10.1016/j.surfcoat.2016.11.058

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ACCEPTED MANUSCRIPT Lasting superhydrophobicity and antibacterial activity of Cu nanoparticles immobilized

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on the surface of dopamine modified cotton fabrics

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Jiaying Yang, Hong Xu*, Linping Zhang, Yi Zhong, Xiaofeng Sui, Zhiping Mao*

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Key Lab of Science and Technology of Eco-textile, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620,

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People’s Republic of China.

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*E-mail: [email protected]. [email protected].

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Tel.: +86 21 67792720. Fax: +86 21 67792707.

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ACCEPTED MANUSCRIPT Abstract: A simple two-step impregnation method was used to prepare copper nanoparticles coated

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cotton fabric. In which, dopamine firstly self-polymerized to polydopamine membrane on the

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cotton fabric surface, then copper nanoparticles were obtained and bound onto the cotton

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fabric using polydopamine as a reductant and binder. Field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Inductively Coupled

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Plasma Optical Emission Spectrometer (ICP-OES) were used to observe the surface morphology and analyze the elemental composition as well as their surface chemical states of

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all samples. The results confirmed the formation of polydopamine film and copper

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nanoparticles. The results of contact angle measurements and antibacterial tests showed that

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antibacterial activity.

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the modified cotton fabrics had durable sticky superhydrophobicity and considerable

activity.

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Keywords: Polydopamine; Copper nanoparticles; Sticky superhydrophobicity; Antibacterial

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ACCEPTED MANUSCRIPT 1. Introduction Interest in functional textiles have been rapidly growing in the last few decades motivated by

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the need of extra properties such as antibacterial, waterproof, easy-clean and so on to improve

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life quality. Materials containing particles of metals such as silver, copper and zinc play an

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important role in antibacterial applications in the past decades. Compared to silver-based antibacterial agents, copper has its advantages of rich content and cheap in price. With an

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antibacterial property only second to silver, copper can fully meets the requirements of antibacterial fabrics in daily life, industrial and even medicine[1]. Besides, as materials

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presenting superhydrophobic property always contain several requirements including high

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roughness and low surface energy, nano copper is also reported to be used in

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superhydrophobic fields such as a superhydrophobic nanoribbon layer[2]. More and more attention is hence given to environmentally friendly modifiers and methods.

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Dopamine acting as a natural strong adhesive bonding agent has been widely used in various fields since it was discovered. The catechol structure of dopamine is the key to its outstanding

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crosslinking and adhesion property[3]. Polydopamine can act as a binder in two ways including covalent binding like a crosslinking agent or to react with some specific substrates that contain amine/ thiol groups and noncovalent binding such as metal coordination or chelating, hydrogen bonding, π−π stacking and so on[4]. As dopamine can form a thin film on substrate surface by self-assembled aggregation and produce a strong adhesive force, it was also applied on the surface modification of fabrics as a binder between fabrics and the surface modification materials. In the meanwhile, the use of dopamine greatly increased the durability of functional fabric[5-8]. Moreover, dopamine is a strong reducing agent, as the phenolic hydroxyl group can be easily oxidized to reactive o-quinone structure[9]. The hydroxyl 3

ACCEPTED MANUSCRIPT structure and quinone structure are expected to be in equilibrium state at aqueous condition, and the balance moves to the catechol group in a non-alkaline environment, which ensures the

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reduction reaction could be sustainably performed. Reduction property of dopamine in the

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performance of catechol structure can be greatly utilized simultaneously[10].

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The aim of this paper was to introduce a method of obtaining copper nanoparticles by in-situ reduction, and adhering the copper nanoparticles to cotton fabrics through polydopamine

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under mild conditions. Different from other methods like electroplating[11] and electroless plating[12], the use of dopamine as a binder and a reducing agent at the same time is not only

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environmentally friendly and energy saving, but also provides a good durability in its

2.1. Materials

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2. Experimental

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superhydrophobicity and antibacterial activity to the modified fabrics.

Fabrics are commercially available knitted cotton fabrics and cleaned by diethyl ether

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anhydrous before used. 3-Hydroxytyramine hydrochloride (Dopamine HCl) and tris (hydroxymethyl) methyl aminomethane (Tris) were purchased from Alfa Aesar (China) and used without further purification. Copper sulfate and hydrochloric acid were purchased from Hushi (China) and used as received. 2.2. Preparation of dopamine film on cotton fabric Dopa (Dopamine HCl) was dissolved in a Tris buffer solution at a concentration of 10mM. The pH value was adjusted to 8.5 by hydrochloric acid. Then the cleaned cotton fabric was immersed into the freshly prepared dopamine solution and stirred for 24 h at room temperature (30 oC). Then remove the fabric and rinse it with deionized water. The fabric was 4

ACCEPTED MANUSCRIPT dried in air dry oven at a temperature of 60 oC. The modified fabric will be called C-Dopa (short for Cotton-Dopamine fabric) in the subsequent discussion.

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2.3. In-situ reduction of copper on C-Dopa

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The C-Dopa fabric was dipped directly into a copper sulphate solution with a concentration of

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40 mM. The reaction was taken at room temperature and the fabric was stirred gently for 24 hours. Then it was taken out and rinsed with deionized water. The fabric was dried in air dry

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oven at a temperature of 60 oC. The modified fabric will be called C-Dopa-Cu (short for Cotton-Dopamine-Copper fabric) in the subsequent discussion.

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2.4. Washing fastness testing

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The washing fastness of C-Dopa-Cu fabric was followed by ISO 105-C10: 2006 (color

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fastness to washing with soap or soap and soda). The liquor ratio of solution was set at 50:1 with a temperature around 60 oC. 5 g/L soap and 2 g/L sodium carbonate were added to the

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solution and preheated to test temperature. The C-Dopa-Cu fabric was washed in this solution for 30 min before rinsed in deionized water 5 times and dried in air dry oven at a temperature

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of 60 oC in one washing cycle. 2.5. Dyeing method The C-Dopa-Cu fabric was dyed to light red color using reactive red dye with a concentration of in 10g/L. Then it was rinsed with deionized water and dried in air dry oven at a temperature of 60 oC for further test. 2.6. FE-SEM Surface morphology of the samples including cotton fabric, C-Dopa fabric, C-Dopa-Cu fabric and the C-Dopa-Cu fabric washed 50 circles was observed using field emission scanning electron microscopy (FE-SEM, S-4800, Hitachi) at an accelerating voltage of 10 kV. 5

ACCEPTED MANUSCRIPT 2.7. ICP-OES The elemental composition of the samples was analyzed using an Inductively Coupled Plasma

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Optical Emission Spectrometer (ICP-OES, Vario EL III, Elmentar) according to JY/T

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2.8. XPS

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017-1996 (general rules for elemental analyzer).

X-ray photoelectron spectroscopy experiments of samples were carried out on a XPS

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spectrometer (ESCALAB 250, Thermo) using a monochromatized Al Kα (1486.71 eV) X-ray source[13].

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2.9. Contact angle

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The static contact angle was measured by a drop shape analyzer (DSA30, Kruss). The fabric

3 μL in one drop[14].

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was placed on the sample stage smoothly, and the deionized water was used with a volume of

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2.10. Antibacterial activity

The antibacterial properties of treated samples were tested according to AATCC 100-2004

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standard, which provides a quantitative procedure for the evaluation of the degree of antibacterial activity[15]. Two circular swatches of the test fabrics 4.8 cm in diameter were prepared as one test sample, and three test samples were needed from each test fabrics for parallel test. All the samples, glassware, broth and medium were sterilized in an autoclave at 121 oC for 15 min. E. coli was cultured in 100 mL of broth containing 1% tryptone, 0.5% of yeast extract, and 1% of NaCl at 37 oC of 24 h. The pH was adjusted to 7.0 using NaOH solution. A direct contact method was used for the quantitative test of the antibacterial assay. Test samples were put into Erlenmeyer flask and 1 mL of the 24 h broth culture containing 106 colony forming units (CFU)/mL of the test organism was removed and placed onto the 6

ACCEPTED MANUSCRIPT sample. For the blank control sample, add 100 mL of PBS buffer solution to the Erlenmeyer flask and shake it vigorously for one minute as an elution at “0” contact time. For the

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untreated control sample and treated samples, an incubation at 37 oC for 18 h was taken

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before the elution.

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Inoculums were diluted appropriately in PBS buffer solution and 0.05 mL of the diluted inoculum was spread evenly on the surface of the agar plate on a petri dish. After culturing at

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37oC for 24 h, the CFU number was counted of which the colonies ranged from 30 to 300 CFU on one agar plate. And the reported data were the average value of three parallel runs.

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The percent reduction of bacteria was calculated by the specimen treatments by the following

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formula Eq. (1):

(1)

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100(C-A)/C = R

Where A (CFU) is the number of bacteria recovered from the samples incubated over 18 h,

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time.

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and C (CFU) is the number of bacteria recovered from the blank control sample at “0” contact

3. Results and discussion 3.1. Formation of dopamine film on the cotton fabric surface FE-SEM images of initial cotton (Fig. 1a) and C-Dopa (Fig. 1b) revealed that on the contrary to the smooth surface of cotton fiber, a rough coating was formed after 24h reaction. The well-defined thin film was believed to be a polydopamine film, to prove which, an X-Ray Photoelectron Spectroscopy (XPS) was used to analyze the elemental composition difference between cotton fabrics and dopamine modified cotton fabrics as shown in Fig. 2. In comparison to the XPS wide-scan spectrum of the initial cotton surface and that of C-Dopa 7

ACCEPTED MANUSCRIPT surface, the characteristic signal of nitrogen 1 s (N 1s) with respective binding energies (BEs) at 400 eV was appeared in the later one, and the coating thickness was above the 8-nm

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probing depth of the XPS technique in sample indicate matrices[8, 16]. The theoretical N/C

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and N/O atomic ratios of pure dopamine are 0.125 and 0.5. In our XPS test as showed in

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Table 1, we achieved values of N/C=0.107 and N/O=0.290 in C-Dopa surface, proving that a

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large amount of dopamine was aggregated and deposited on the surface of cotton fabric.

Fig. 1. FE-SEM images of (a) initial cotton fabric, (b) C-Dopa, (c) C-Dopa-Cu, (d) C-Dopa-Cu washed 50 cycles.

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Fig. 2. XPS spectra of (a) initial cotton, (b) C-Dopa, (c) C-Dopa-Cu and the Cu2p region of

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the XPS spectrum of C-Dopa-Cu.

XPS.

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Table 1. Surface chemical composition of initial cotton and C-Dopa surface determined by

dopamine

cotton

C-Dopa

C 1s

72.7%

59.91%

67.72%

O 1s

18.2%

38.42%

25.02%

N 1s

9.1%

1.67%

7.26%

N/C

0.125

0.043

0.107

N/O

0.5

0.028

0.290

In order to study the strength of C-Dopa, the bursting strength of samples were tested 9

ACCEPTED MANUSCRIPT according to the ISO 13938-1:1999 standard method and the results were summarized in Table 2. Based on the bursting strength of initial cotton and C-Dope, the strength loss can be

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calculated. The negative strength loss may result from two reasons including the strong

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adhesion of polydopamine and the fabric shrinkage after 24h bath treatment.

Table 2. Bursting strength of samples according to the ISO 13938-1:1999 standard method. Bursting Strength(N)

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Sample

385.17

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Cotton C-Dopa

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C-Dopa-Cu

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C-Dopa-Cu washed 5 cycles

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C-Dopa-Cu washed 30 cycles C-Dopa-Cu washed 50 cycles

Strength Loss -

416.68

-8.18%

394.45

-2.42%

398.17

-3.38%

374.5

2.77%

355.5

7.70%

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3.2. The in-situ reduction of copper ions and the loading of copper nanoparticles on C-Dopa

According to our previous researches[8], polydopamine was likely to be conjectured to adsorb copper ions near the reaction sites (catechol group) by metal chelating (noncovalent binding) firstly, and then deposit the nanometer copper particles on the surface of polydopamine by in-situ reduction. XPS was used to determine the chemical states of copper atoms. Fig. 2c shows a copper (Cu) (933 eV) peak of C-Dopa-Cu indicating the deposition of copper on the surface of C-Dopa fabrics. As can be seen from the Cu2p region in the XPS spectrum in Fig. 2d, the copper atom is mostly in its metallic state (Cu0) (933 eV), which confirmed that the 10

ACCEPTED MANUSCRIPT in-situ reduction of copper was succeed. There is an additional Cux+ peak showed at 940 eV, which is believed to be the signal of copper oxide CuOx in light of the oxide satellite structure

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showed around 943eV. The formation of copper oxide might have taken place during the

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storage. While the surface of copper particles was oxidized, the internal part remained.

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According to the method of deconvolution analysis, the amount of copper in different states can be calculated. It was found that about 89.9% of copper atoms were considered to be in the

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metallic state (Cu0), while the rest part (about 10.1%) were perceived as copper oxide, respectively. The XPS results mentioned above gave conclusive evidence to the deposition of

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copper gain after modification.

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copper particles on dopamine modified cotton surface. ICP-OES test also suggests a 5mg/g

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FE-SEM was used to characterize the surface morphology of copper deposited C-Dopa fabrics and C-Dopa-Cu washed 50 cycles. Comparing to the dopamine modified cotton

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surface in Fig. 1b, we can clearly recognize the appearance of particles sizing from 400 nm to 500 nm on the surface of C-Dopa fabrics (Fig. 1c), which was advised to be the aggregated

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copper nanoparticles. Relative to the unevenly distributed copper particles with large size on processed fabrics in Fig. 1c, the difference was obviously figured out on the C-Dopa-Cu fabrics surface after 50 washing cycles as shown in Fig. 1d. The copper aggregates with large size (400-500 nm) was disappeared and replaced by a great quantity of copper nanoparticles with a smaller size (around 50-100 nm) and a uniform distribution. After the reduction, the larger copper particles are recognized to be formed by the aggregation of small copper nanoparticles (Fig.1c). The larger particles may be eluted or broken up into small particles and adhered to the surface of polydopamine film after several standard washing cycles. And due to the strong adhesion between the copper particles and polydopamine film, the surface layer of 11

ACCEPTED MANUSCRIPT large particles might be eluted and leaving inners with small size as well. Therefore, the size of copper particles on the surface became smaller and the number increased significantly.

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The FE-SEM images also demonstrated the formation of copper nanoparticles and the success

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of in-situ reduction[17, 18]. Moreover, the results show an excellent adhesion properties of

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polydopamine as a certain amount of copper nanoparticles still adhere to its surface after 50 times of standard washing and the bursting strength dropped rarely after the loading of copper

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nanoparticles and the washing cycles (Table 2). 3.3. Hydrophobic property

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Initial cotton fabric and C-Dopa possess perfect hydrophilic properties due to the rich content

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of hydrophilic groups, while the copper modified cotton fabrics show a considerable increase

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in its hydrophobic property (Fig. 3f). The static contact angle (CA) for water droplets was measured by a drop shape analyzer and the results showed in Fig. 3a, 3b, 3c. As copper owns

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a good hydrophobic ability originally, the surface energy of C-Dopa-Cu was low enough to exhibit superhydrophobicity property with a static contact angle of 151.49o (Fig. 3a). Cu

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metal nanoparticles are generally hydrophilic, but it was found to have superhydrophobicity here in our report. This phenomenon might due to several reasons including the special nanostructure and the roughness. The water contact angle increased to 154.16o after 5 washing cycles (Fig. 3b) on account of a more uniform distribution of copper particles on the surface of C-Dopa-Cu fabrics. There are three reasons might be considered to increase the WCA value after 5 times of washing cycle. 1) Unreacted hydrophilic chemicals such as copper sulphate aggressive particles on the surface of the substrate were considered to be washed away totally. 2) The copper aggressive particles with large width (micro size) which performs more closely to the copper metal (generally hydrophilic) on the substrate surface were 12

ACCEPTED MANUSCRIPT considered to be washed away. 3) The copper nanoparticles are found easily to be oxidized and may generate hydrophobic copper oxide covering on its surface.

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After 30 times of standard washing, the water contact angle remained at a high level of

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150.88o (Fig. 3c). Different from the stable contact angles shown before, while after washing

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50 times, though the initial water CA is high, the water droplets are no longer stable with time and disappeared in 30 s.

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All the water droplets had high sliding angles and pinned on surfaces at any tilted angles even when it is turned upside down with a tilted angle of 90o or 180o (Fig. 3d, 3e), since the

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hydrophobic copper particles distributed on the surface sparsely and revealed the hydrophilic

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C-Dopa part, forming a staggered structure of hydrophilic and hydrophobic parts on the

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surface of cotton fabric[19, 20]. For the elucidation of the aforesaid superhydrophobic performance of the modified surface, the Cassie impregnating state (petal effect) was

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considered[21, 22], which was likely to happen when both microstructure pitch distance and nanostructure mass of the substrate surface were large. In Cassie impregnating state, liquid

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penetrates into grooves of the solid, and the drop finds itself on a substrate viewed as a patchwork of solid and liquid as we can see in fig.3g, while the surface of microstructure pitch fulfilled with nanostructures are dry. The special micro-nano structure of Cassie impregnating state provides both high WAC and large adhesion. After many times washing cycle, WAC was likely to decrease with the elution of microstructures as presumed in fig.3f. In summary, copper particles formed a micro-nano structure with high roughness and low surface energy on the modified cotton surface, which led to the superhydrophobicity performance. And the micro-nano structure disappeared as the micro size copper particles were washed off after 50 washing cycles as we discussed above (Fig. 1d). 13

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Fig. 3. Photos of water contact angles of (a) C-Dopa-Cu, (b) C-Dopa-Cu washed 5 cycles, (c) C-Dopa-Cu washed 30 cycles, (d, e) water drops on 90o and 180o C-Dopa-Cu surface, (f)

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digital photographs of water drops on C-Dopa-Cu and (g, h) presumed states before and after washing cycles.

Regarding to the initial color of polydopamine membranes, the modified cotton fabrics were dyed to applicable light colors to make the modification promising for real application. Fig. 4 shows the color change between C-Dopa-Cu and it dyed with reactive red dye. From the insets, we can see a slight decrease in its static contact angle (from 151.49 o to 149.08o) of the modified cotton fabrics, indicating a similar hydrophobic ability. The results proved that the polydopamine membrane does not hinder the reaction between dyes and the reactive group (-OH) of cotton fibers. What is more, the polydopamine may also 14

ACCEPTED MANUSCRIPT provide extra hydroxyl groups for dyeing and the surface of membrane can be covered with dyes, so that the treated fabric was feasible to be presented in different colors without

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changing the functional properties benefited from the modification.

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Fig. 4. Digital photographs of (a) C-Dopa-Cu, (b) C-Dopa-Cu after dyeing, the insets were the

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photos of water contact angles.

3.4. Antibacterial activity

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The antibacterial activity of modified cotton fabrics was explored on the basis of AATCC 100-2004, and the results were showed in Fig. 5. Then the number of E. coli colonies after 18 h incubation was counted and the reduction percent of bacteria was calculated as displayed in Table 3. From the results, colony growth was directly observable on initial cotton and C-Dopa added agar plates (Fig. 5b, 5c) with reduction percent only at 10.2% and 12.7%, while the C-Dopa-Cu fabrics achieved a perfect antibacterial property. As we can see in Fig. 5d, C-Dopa-Cu in this test completely inhibited the growth of bacterial, the reduction percent of which reached 99.9%, as well as the C-Dopa-Cu washed 5 cycles (Fig. 5e), which performs a little higher than other reports on antibacterial nanocopper (around 95%)[18, 23]. Moreover, 15

ACCEPTED MANUSCRIPT the modified samples washed 30 and 50 cycles were still able to kill 95.5% and 88.5% of the initial E. Coli present (Fig. 5f, 5g) which was barely achieved by other works without

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polydopamine. Fig. 5h showed only one colony-forming unit (CFU), the bacteria reduction

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percent of C-Dopa-Cu after dyeing reached 99.3% (Table 3). The outcome confirmed a

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durable antibacterial activity of C-Dopa-Cu and reflected a sufficient quantity of copper nanoparticles form by in-situ reduction. The results suggested an excellent and durable

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antibacterial activity of modified cotton fabric comparing to other reports.

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Fig. 5. Representative images of agar plates containing an equal amount of (a) blank control sample at “0” contact time, (b) initial cotton, (c) C-Dopa, (d) C-Dopa-Cu, (e) C-Dopa-Cu washed 5 cycles, (f) C-Dopa-Cu washed 30 cycles, (g) C-Dopa-Cu washed 50 cycles, (h) C-Dopa-Cu after dyeing.

Table 3. Average number of Escherichia coli colonies counted in Fig. 5 and the calculated reduction percent of bacteria after 18 h incubation. Sample

Average number of E.

Reduction percent

Coil colonies (CFU)

of bacteria (R%)

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Cotton

141

10.2%

C-Dopa

137

12.7%

C-Dopa-Cu

<1

C-Dopa-Cu washed 5 cycles

<1

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Blank control sample at “0” contact time

C-Dopa-Cu washed 30 cycles

95.5%

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88.5%

1

99.3%

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C-Dopa-Cu after dyeing

99.9%

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C-Dopa-Cu washed 50 cycles

99.9%

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4. Conclusions

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By controlling the experimental conditions, a uniform film of dopamine can be formed on the

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surface of cotton fibers. Successful preparation of copper nanoparticles was demonstrated by in-situ reduction of CuSO4 in the presence of poly-dopamine without any other reluctant. Copper nanoparticles were distributed and adhered to C-Dopa homogeneously due to the

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strong adhesive ability of poly dopamine, thus provides a perfect washability. C-Dopa-Cu is found to maintain a high contact angle (over 150o) and a high sliding angles in 30 washing cycles and after dyeing, which was seemed to be a sticky superhydrophobic property. C-Dopa-Cu also shows a durable antibacterial property for having an antibacterial reduction percent at 99.9% after modification, 99.3% after dyeing and over 85% after washed 50 cycles.

5. Acknowledgement This work was financially supported by the National Key Technology R & D Program (No. 2014BAC13B02). 17

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Graphical abstract

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ACCEPTED MANUSCRIPT Highlights 1. The uniform deposition of copper nanoparticles are formed by the in-situ reduction of

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dopamine.

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2. The fabric has superhydrophobicity after 30 washing cycles and after dyeing.

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3. The fabric has high antibacterial activity against E. Coli after 50 washing cycles and after

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dyeing.

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