The Comparison of the Effects of Β -Cyclodextrin Complex and Derivative Complex with Silver Nanoparticles on Cotton Fabric

10 In this study, sulfated β -cyclodextrin (S- β - CD) which is a β -cyclodextrin derivative was obtained by chemical 11 treatment of natural β - cyclodextrin (β -CD) with sulfuric acid. Afterwards, β -CD and S- β -CD were applied to 12 cotton fabrics. In different treatments, β -CD and S- β -CD were bonded to cotton fabrics with EDTA crosslinking 13 agent. Then, all the fabrics were treated with antibacterial agent silver nanoparticles (AgNPs) and inclusion 14 complexes were formed. The aims of this study were to increase the washing stability and the antibacterial activity 15 against microorganisms and to compa re the effects of β -CD complex and derivative complex with silver 16 nanoparticles on treated cotton samples. So, for this purpose, the properties of the treated samples like antibacterial 17 activity, washing stability, add-on, tensile strength, handle, thickness and color change were tested and compared 18 to each other. In addition, characterization analyzes such as SEM, EDX and FT-IR were performed on the samples 19 and XRD analysis was performed to characterize the AgNPs. As a result of the study, it was observed that AgNPs 20 alone were not sufficient to obtain antibacterial textiles with strong antibacterial effect and good washing stability. 21 The inclusion complexes formed with β -CD and S- β -CD had much more effective antibacterial activity and more 22 robust washing stability. In addition, when the physical properties except stiffness and yellowness were considered 23 besides antibacterial activity and washing stability, the treatment of derivative β -CD complex with AgNPs and 24 crosslinking this complex to cotton sample by means of EDTA was found to be the most favorable


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Textile products have long been known as susceptible media that support the growth and reproduction of 30 microorganisms such as bacteria and fungi. These microorganisms are found almost everywhere in the 31 environment and can multiply rapidly when basic requirements such as moisture, nutrients and temperature are

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They reported sulfated-β-cyclodextrin was important for biomedical applications in textile but they did not 114 investigate the physical properties of cotton in detail.

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In this study, silver nanoparticles (AgNPs) were used as an antibacterial agent and inclusion complexes between 116 β-cyclodextrin and its derivative (sulfated β-cyclodextrin) with silver nanoparticles were formed and applied to 117 cotton fabrics with and without cross-linking chemical (EDTA) by pad-dry-cure method. EDTA was selected due 118 to its chelating ability towards metal ions and binding ability towards cyclodextrins. In order to compare the effects 119 of the treatments, physical tests, antibacterial tests and characterization tests were applied to the cotton fabrics. Desized and bleached woven 100% cotton fabric with a weight of 245 g/m 2 was used in the study. Warp yarn 123 density was 45 threads/cm and weft yarn density was 20 threads/cm.

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The properties and supplier information of the chemicals used in the study are given in Table 1.

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Then the cotton samples were dipped into these solutions for 15 min. and padded by a 90% wet pick-up in the 147 laboratory type padding machine (Prowhite/Y002). After padding, they were dried at 80°C for 5 min. and cured at

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140°C for 3 min. by the laboratory type stenter machine (Prowhite/Y003). In the second step, pad-dry-cure 149 processes were repeated in the same conditions.

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In order to test the washing stability of the antibacterial treatment, all the samples were washed for once with a 5

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The antibacterial activity results of the treated fabrics against S. aureus are shown in Table 4 and Figure 1. The

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antibacterial activity results of the treated fabrics against E. coli bacteria are shown in Table 5 and Figure 2.

T R E A T M E N T 1 T R E A T M E N T 2 T R E A T M E N T 3 T R E A T M E N T 4 T R E A T M E N T 5
Control Sample Before Washing After Washing

T R E A T M E N T 1 T R E A T M E N T 2 T R E A T M E N T 3 T R E A T M E N T 4 T R E A T M E N T 5
Control Sample Before Washing After Washing In the first part of the study, the washing process was carried out at 60°C. But in the second part of the study, the 257 milder and widely used household type temperature (40°C) was preferred as washing condition for repeated 258 washings. The repeated washing cycles (1, 5 and 10) were applied to the sample treated by AgNPs, sulfated β-CD 259 and EDTA in other words treatment 5.

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The antibacterial activity test results of the sample treated by AgNPs, sulfated β-CD and EDTA against S. aureus 261 and against E. coli before washing and after 1, 5 and 10 washing cycles at 40°C are shown in Table 6 and 7 262 respectively.

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The add-on results are given in Table 8.

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Tensile strength results

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The tensile strength and elongation at break values in the weft and warp direction of fabrics treated with β-282 cyclodextrin, sulfated β-cyclodextrin, EDTA and silver nanoparticles and untreated fabrics are given in Table 9.

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The bending length and bending rigidity values of the samples are given in Table 10.

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After the finishing treatments, the bending length and bending rigidity of the fabrics increased. This fact showed 309 that the finishing processes caused stiffness in the fabric handle. In terms of the application of β-CD or sulfated β-310 CD, it was found that sulfated β-CD caused more stiffness and EDTA leaded the stiffness to increase. However,

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there was no significant difference between the untreated fabric and the fabric to which AgNPs alone were applied.

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This fact was attributed to the variation in the inclusion complex formation on the cotton surface as in the add-on 313 results.

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In order to verify the bending length and bending rigidity results by another test method, stiffness values of the 316 samples were also measured by pneumatic stiffness tester. Stiffness values of the samples are given in Table 11.

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The stiffness values were found to be in accordance with add-on and bending rigidity results, namely the more

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Thickness values of the samples are given in Table 12.

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The whiteness and yellowness index values are given in Table 13.

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these studies were considered, it can be said that the color change results of this study were in acceptable limits 342 since the final color of the sample whose color change was maximum was cream yellow.

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The spectra of β-cyclodextrin powder and sulfated β-cyclodextrin powder are given in Figure 3.

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According to the SEM images, the surface of the untreated cotton sample (Fig. 4a) was smooth and clear as 362 expected while the other surfaces included the residues of the silver nanoparticles. When the SEM image of the 363 sample treated by silver nanoparticles (AgNPs) alone was examined (Fig. 4b), it was found that silver nanoparticles 364 were less adhered to the surface of the samples than the samples treated by β-cyclodextrin and its derivative. When 365 the sample surfaces treated by β-cyclodextrin and silver nanoparticles (AgNPs) (Fig. 4c) were examined, it was 366 observed that silver nanoparticles did not show uniform distribution and formed aggregates in certain areas. When 367 the sample surfaces treated by sulfated β-cyclodextrin and silver nanoparticles (AgNPs) were examined (Fig. 4d),

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it was observed that silver nanoparticles showed a uniform distribution and the quantity of the inclusion complexes 369 formed on the surface increased. Moreover, the application of EDTA crosslinking agent also ensured a strong 370 adhesion of inclusion complexes to surfaces and supported the increase in the quantity of the inclusion complexes 371 ( Fig. 4e and 4f).

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By the EDX analysis, the atomic percentage of the silver nanoparticles (AgNPs) were determined. As mentioned 374 in the methods part, the samples were coated with a thin gold/palladium film layer to increase the conductivity 375 during SEM and EDX analysis. Therefore, in order to calculate the accurate atomic percentages of the elements, 376 the atomic percentages of gold and palladium elements related to the coating in the analysis were eliminated and 377 were remained as unidentified peaks in the images in Fig. 5. The atomic percentage of the silver nanoparticles in 378 the treated samples and in the untreated sample are given in Table 14 and related spectra of the samples are shown 379 in Fig. 5.  According to these results, it was seen that the amount of silver nanoparticles in the fabric sample treated by 387 sulfated β-cyclodextrin was much higher than the fabric sample treated by β-cyclodextrin. It was also observed 388 that the samples treated by EDTA crosslinking agent possessed higher Ag amount than the others, and thus, it was 389 observed that EDTA binded more silver nanoparticles (AgNPs) and inclusion complexes on the surface. It was 390 concluded that the sample with the highest quantity of silver nanoparticles was the sample treated by treatment 5, 391 in other words by S-β-CD + AgNPs + EDTA.

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XRD spectra of the silver nanoparticles are given in Figure 6.

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Antibacterial test results showed that the most effective treatment was S-β-CD + AgNPs + EDTA and this 408 treatment could be stable to 10 washing cycles as 79% against S. aureus bacteria and 77% against E. coli bacteria.

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Physical test results showed that the treatments caused an increase in weight, thickness, stiffness, tensile strength

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Funding The authors did not receive funding.

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Availability of data and material The data are available from the corresponding author.

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Code availability Not applicable.

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Conflict of interest The authors declare that they have no conflict of interest.

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Ethical approval This study does not involve any animal and human sample.