Antibacterial And UV Protection Properties Modied Cotton Fabric Using Curcumin/ TiO2 Nanocomposite For Medical Textile Applications

Medical textiles are one of the most rapidly growing parts of the technical textiles sector of the textile industry. This work was developed for biocompatible materials of curcumin / TiO 2 nanocomposite fabricated on the surface of cotton fabric for medical applications. Cotton fabric was pretreated with three crosslinking agents namely, citric acid, Quat-188, and GPTMS. Applying nanocomposite on modied cotton fabric using pad-dry cure method. The chemistry and morphology of modied fabrics are examined by Fourier-transformed infrared spectroscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. In addition, the chemical mechanism for nanocomposite modied fabric was reported. UV protection (UPF) and antibacterial properties against Gram - positive S. aureus and Gram - negative E. coli bacterial strains were investigated. The durability of fabrics to 20 washing cycles was also examined. Results demonstrated that nanocomposite modied cotton fabric exhibited superior antibacterial activity against Gram - negative bacteria that Gram - positive bacteria and excellent UV protection properties. Moreover, good durability was obtained, possibly due to the effect of the crosslinker used. Among the three pre-modication of cotton fabric, Quat-188 modied fabric reveals the highest antibacterial activity comparing with citric acid or GPTMS modied fabrics. This outcome suggested that curcumin / TiO 2 nanocomposite Quatt-188 modied cotton fabric could be used in biomedical textile as antibacterial properties.


Introduction
Nowadays, one of the most promising elds of new textile materials is the manufacture of antimicrobialacting medical textiles. Since too much work is being put into improving substances and procedures that can provide safe and adequate protection against various microorganisms. Usually, chemical materials have been used for antibacterial medical textiles, such as phenols, nitro compound, and formaldehyde derivatives (Czaja, Krystynowicz et al. 2006 Curcumin is a natural material that is used in medicinal textiles. It's a polyphenolic compound and a yellow pigment derived from the ground rhizomes of the Curcuma longa Linn plant, and it has a wide variety of bene cial properties. It has a wide range of pharmacological properties, including antiin ammatory, antioxidative, and anti-cancer properties (Bhawana, Buttar et al. 2011, Jaisamut, Wiwattanawongsa et al. 2018). Curcumin contains two phenolic hydroxyl groups and two carbonyl groups in the center, which can form keto-enol tautomers in solution. When it comes to curcumin modi cations, the phenolic group is the most important functional group. It is capable of a wide range of reactions, including nucleophilic substitution with organic acids, epoxides, and their derivatives (Bigand, Pinel et al. 2011). Several experimental studies have now concluded that these two groups exist primarily in enolic form at room temperature (Singh, Verma et al. 2010). Pure curcumin, on the other hand, has a low solubility, which limits its use in medical and clinical applications . In order to, solve this problem, it was used to prepare complex materials that are able to enhance the bioavailability of curcumin (Kuthati, Kankala et al. 2017, Pal andPaul 2019). Curcumin's therapeutic effectiveness is limited because of its low solubility, absorption, metabolism, and bioavailability (Anand, Kunnumakkara et al. 2007). In this regard, curcumin research has recently focused on the production of possible delivery systems to improve its aqueous solubility, stability, and bioavailability, controlled delivery of curcumin at speci c sites. For this, curcumin has been attempted to be incorporated into titanium dioxide nanoparticles. In addition, for enhanced antibacterial activity, we chose hydrophilic titanium dioxide nanoparticles to conjugate with hydrophobic curcumin. Titanium dioxide nanoparticles are used in a wide range of consumer products, including sunscreens, cosmetics, pharmaceutical additives, and food coloring agents. They are biodegradable (Anand, Kunnumakkara et al. 2007) and have good biocompatibility with no or little toxicity in vitro and in vivo. As a result, titanium dioxide nanoparticles may be one of the most promising nanoparticles for a broad variety of medical and pharmaceutical applications. Nano-titanium dioxide can be used in biomedical and bioengineering applications due to its special properties and high reactivity (Sherin, Sheeja et al. 2017). Curcumin was recently used to sensitize TiO 2 for improved photodegradation of dye (Buddee, Wongnawa et al. 2014) and photodegradation of phenols (Haghighatzadeh 2020). Also complex of titanium dioxide nanoparticles with curcumin was developed as wound dressing material using chitosan and polypropylene fabric (Marulasiddeshwara, Jyothi et al. 2020). The incorporation of positively charged sites, such as cationization, allows for the creation of an electrostatic attraction between the ber and negatively charged molecules. Cotton cationization yielded new cotton cellulose, which could lead to new uses in cotton pre-treatment and chemical nishing. Previous reports illustrate that cationization of cotton surfaces has been shown to improve silver nanoparticle adsorption In the current work, we aimed to developed biocompatible material based on cellulose for better and durable antibacterial applications. In order to achieve this, we use curcumin / TiO 2 nanocomposite for fabrication on surface of cotton fabric using pad-dry-cure method. Titanium dioxide nanoparticles was used to enhance the stability and bioavailability of curcumin. For enhancing the attraction force between nanocomposite and cotton fabric, modi cation of pretreated cotton fabric by cationic agent namely, 3-Chloro-2-hydroxypropyl trimethyl ammonium chloride (Quatt-188). For comparing of pre catonized cotton fabric, two other pretreatments were applied using [(3 glycidyloxy) propyltrimethoxysilane (GPTMS) and citric acid. The pretreatment process act both as a binding and stabilizing for curcumin / TiO 2 nanocomposite. In addition, chemical mechanism of modi ed fabric reported. Also, durability and mechanical properties of the modi ed cotton fabric were investigated.

Materials
Mill bleached pure 100% cotton fabric (138 g/m 2 ) were supplied by Misr Company for spinning and weaving Mehalla El-Kobra, Egypt.

Preparation of curcumin -TiO 2 nanocomposites
Solution of 0.5% TiO 2 nanoparticles were resuspended in 50 ml of isopropyl alcohol. Then 5% (w/v) curcumin powder in isopropyl alcohol was prepared with stirring. 0.5 ml of this solution was added drop wise to solution of TiO 2 with continuous stirring for 3-4 hr.

Cationization of cotton fabric
Chemical modi cation of the cotton fabric through cationization was carried out using the pad-dry-cure method. The experimental procedures adopted were as follows: 3-Chloro-2-hydroxypropyl trimethyl ammonium chloride (Quatt-188) was mixed with sodium hydroxide solution at a NaOH/Quatt-188 M ratio of 2:1. The cotton fabric was padded in this mixture in two dips and two nips, and then squeezed to a wet pick-up of about 100%. The fabric was dried at 40°C for10 min and cured at 120°C for 3 min. Finally cotton fabric was washed with cold water and 1% acetic acid, followed by several washing cycles and dried under the normal laboratory conditions. 2.6 Coating of cationized cotton fabric with TiO 2 / Curcumin nanocomposite Cationized cotton fabrics were padded in the 0.5 % (w/v) solution of TiO2 /curcumin nanocomposite prepared solution in two dip and nip and then squeezed to a wet pick-up of 100%. Padded fabrics were dried at 80 o C for 5 min and then cured at 180 o C for 3 min. Treated fabrics were rinsed with hot water then with cold water and nally dried at room temperature.

Coating of cotton fabric with GPTMS / Curcumin/ TiO 2 nanocomposite
Solution of 2 % ( w/v) GPTMS sol was added to 0.5 % (w/v) solution of TiO 2 /curcumin nanocomposite with continuous stirring under sonication for 2 hr. Cotton fabrics were padded in the previously prepared solution in two dip and nip and then squeezed to a wet pick-up of 100%. Padded fabrics were dried at 80 o C for 5 min and then cured at 180 o C for 3 min. Treated fabrics were rinsed with hot water then with cold water and nally dried at room temperature.

Coating of cotton fabric with Citric acid / Curcumin /TiO 2 nanocomposite
Aqueous solution of citric acid (30 g/l) with sodium hypophosphite (6% w/w) was added to 0.5 % (w/v) solution of TiO 2 /curcumin nanocomposite. Cotton fabrics were padded in the previously prepared solution in two dip and nip and then squeezed to a wet pick-up of 100%. Padded fabrics were dried at 80 o C for 5 min and then cured at 180 o C for 3 min. Treated fabrics were rinsed with hot water then with cold water and nally dried at room temperature.

Fourier-transformed infrared spectroscopy (FT-IR)
FTIR spectroscopy has been extensively used in cellulose research, since it presents a relatively easy method of obtaining direct information on chemical changes that occur during various chemical treatments. ATR-FTIR instrument (JASCO, Model IR 4700 Japan) and scanned from 4000 to 400 cm − 1 in ATR mode using KBr as supporting material 3.2 Scanning electron micrograph SEM/EDX analysis Samples for SEM/EDX were taken using FEI INSPECTS Company, Philips, Holland environmental scanning without coating. Elemental micro-probe and elemental distribution mapping techniques were used for analyzing the elemental constitution of solid samples. An elemental analysis of the particles was implemented by a SEM equipped with an energy dispersive spectroscope (EDX), to get rapid quantitative and qualitative analysis of the elemental composition.

Antibacterial test
The antibacterial activity of the treated samples against Staphylococcus aureus, (G + ve) and Escherichia coli (G − ve) bacteria were determined using agar plate. The antibacterial activity of fabric samples was evaluated using, (ATCC 1533) bacteria using disk diffusion method. A mixture of nutrient broth and nutrient agar in 1 L distilled water at pH 7.2 as well as the empty Petri plates were autoclaved. The agar medium was then cast into the Petri plates and cooled in laminar air ow. Approximately 105 colonyforming units of bacteria were inoculated on plates, and then 292 cm 2 of each fabric samples was planted onto the agar plates. All the plates were incubated at 37 o C for 24 h and examined if a zone of inhibition was produced around samples.

UV Protection factor
UV-vis spectrum was recorded on Perkin Elmer Lambda 3B UV-Vis spectrometer. Ultraviolet protection factor (UPF) was measured using UV Shimadzu 3101 Spectrophotometer. UV Protection and classi cation according to AS/NZS 4399:1996 were evaluated with a scan range of 200-600nm.

The add-on (%) loading
The add-on (%) loading was calculated as follows: Where W 1 and W 2 are the weights of the fabric specimens before and after treatment respectively.

Durability test
The treated fabric samples were subjected to 20 laundering cycles according the ASTM standard test method (D 737 − 109 96) to determine the antibacterial durability to washing.

Tensile strength
The tensile strength of the fabric samples was determined by the ASTM Test Method D-1682-94 (1994). Two specimens for each treated fabric were tested in the warp direction and the average value was recorded to represent the fabric breaking load (Lb).

Statistical analysis
Results were expressed as a mean value with its standard deviation (mean ± S.D.) of each sample that is repeated three times (n = 3). Statistical analysis was performed with Student's t-test and differences were considered as signi cant at p-values below 0.05.
Results And Discussion 4.1 Mechanism of deposition of curcumin / TiO 2 nanocomposite on surface of cotton fabric Figure 1 illustrated the schematic mechanism of formation and xation of curcumin / TiO 2 on the surface of cotton fabric. According to the experimental section, rstly, the formation of curcumin /TiO 2 nanocomposite. As presented in gure 1 (a) upon addition of curcumin solution to TiO 2 nanoparticles solution that suggests the dispersion of curcumin particles on the surface of titanium nanoparticles. This is because the -diketone functional group, which is located in the center of the curcumin molecule, has a high metal chelating potential. By forming charge transfer complexes, the -diketone group effectively chelated TiO 2 nanoparticles (Buddee, Wongnawa et al. 2014). Pretreatment of cotton fabric then adjusted. Figure 1

FTIR analysis
The existence of functional groups on treated cotton fabric investigated by fourier-transform infrared spectrum. Figure 2 (Farouk, Saeed et al. 2020). On other hand, the absorption peak at 3310 cm − 1 , which corresponded to the stretching vibration of phenolic O-H, was described by spectrum (e) for pure curcumin. Furthermore, sharp absorption peaks at the region range 1430 to 1630 cm − 1 . These peaks belong to the groups -OH, C = O, and C = C, respectively (enol). Other peaks were observed in region between 1000 cm − 1 and 1300 cm − 1 .
All peaks are ascribed to the con guration of the symmetric and asymmetric C-O-C groups (El-Hady and Saeed 2020). As can be seen in the spectrums (b), (c), and (d) are looked similar to untreated cotton fabric and curcumin patterns with little signi cant changes. This is attributable to the partial interaction of nanocomposite with modi ed cotton fabric. In addition, strong peaks at the region 400-600 cm − Figure 3(a) shows that unmodi ed cotton fabric has a ber with smooth surface. While Fig. 3 (b, c, and d) reveal the deposition of different modi cations of cotton fabric. All modi ed samples showed homogenous distribution of curcumin /TiO 2 nanocomposite with less agglomeration in some points. In addition, no bridges between cotton adjacent bers, which is desirable as air and vapor permeability is required for their potential application as wound dressings and medical materials. Figure 3

EDX Analysis:
The elemental analysis of cotton fabric after modi cation was determined using the EDX spectrum. Figure 4 (a) shows the atomic percentage of carbon as 57.30 %, oxygen as 40.61% along with titanium element as 1.41 % for curcumin /TiO 2 -citric modi ed cotton fabric. However, Fig. 4 (b) illustrates the modi ed cotton fabric by curcumin /TiO 2 -Quatt-100. It shows the atomic percentage of carbon at 55.97, oxygen at 36.76%, titanium at 2.42 % and a new peak for nitrogen as 4.84 %. Thus reveals the etheri cation reaction of cationization process on cotton fabric. On the other hand, cotton fabric modi ed by curcumin /TiO 2 -GPTMS is showed in Fig. 4 (c). It shows the atomic percentage of carbon as 65.91 %, oxygen as 28.55 %, titanium 0.66 % and new peak for silicon at 4.04 %. On the basis of the above results, the higher peaks of observed titanium element in Fig. 4(b) related to higher content of curcumin /TiO 2 nanocomposite deposited on the Quatt-100 modi ed cotton fabric.

Antibacterial activity
The antibacterial activity of curcumin / TiO 2 nanocomposite modi ed cotton fabric with various treatment was analyzed against representative microorganisms of open interest, both Gram-positive (S. aureus) and Gram-negative (E. coli) strains using agar diffusion method. The antibacterial effect for all treatments is ranging from 10 mm to 20 mm of clear zone of inhibition. Results mentioned in Table 1 indicated that Escherichia coli has higher response than Staphylococcus Aureus. This may be due to variations in bacterial cell wall organization structure. Gram-positive bacteria have a thicker layer cell than Gram-negative bacteria, which serves as a barrier to the spread of active ingredient into the cytoplasm and protects the cell wall (Kim, Kuk et al. 2007). On the other hand, TiO 2 nanoparticles coated modi ed cotton fabric showed higher antimicrobial activity. This attributed to the effect of metal ion may cause cytoplasmic leakage, protein denaturation, and enzyme malfunction. Reactive oxygen species (ROSs) are generated by photoactive metal oxides, which can cause oxidative stress, cell content leakage, and DNA damage (Behnam, Emami et al. 2018, Marulasiddeshwara, Jyothi et al. 2020). Since microbes are inhibited, these ROS can oxidize lipids and lipopolysaccharides. In addition, curcumin molecule in modi ed cotton fabric with curcumin / TiO 2 nanocomposite resulted in higher antibacterial activity. As reported before, curcumin being a lipophilic molecule, it can intercalate into the lipopolysaccharide containing cell membrane and increase the permeability of gram-negative bacteria. Further, it has been reported that the key mechanism involved in the killing action of curcumin is the disordering of 1,2dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) membranes found in both S. aureus and E. coli (Saha, Pramanik et al. 2021). Since, curcumin can easily form a complex with titania, so it may be able to break through bacteria's cell wall and enter the cell. Cell organelles will be disrupted, and bacteria will be killed by lysis. (Marulasiddeshwara, Jyothi et al. 2020). In addition, cotton fabric modi ed with Quatt − 188 had higher antibacterial properties compared with fabric modi ed by either citric acid or GPTMS. From the above results, the hindrance against pathogenic strains was accomplished in the following order: Curcumin /TiO 2 nanocomposite modi ed Quatt-188 cationized fabric > Curcumin/TiO 2 nanocomposite modi ed crosslinked fabric with citric acid /SHP> Curcumin/TiO 2 nanocomposite modi ed fabric with GPTMS.  [30][31][32][33][34][35][36][37][38][39][40], and excellent (UPF range > 40).
The calculated UPF values of untreated cotton fabric is 4.5. The UPF of coated cotton fabric is varied from 20 to 55 which is higher than the untreated fabric. Also, the results in Table 2  Moreover, the results in Table 2

Conclusion
In this work, biocompatible materials based on curcumin/ TiO 2 nanocomposite fabricated on the surface of cotton fabric for medical applications were successfully prepared. For achieving this goal, cotton fabric was per modi ed with citric acid, Quatt − 188, and GPTMS. The prepared nanocomposite modi ed fabrics were con rmed using FTIR, SEM, and EDX. It has been concluded that curcumin /TiO 2 nanocomposite modi ed Quatt-188 cationized fabric shows the highest antibacterial activity compared with either curcumin/TiO 2 nanocomposite modi ed crosslinked fabric with citric acid /SHP or curcumin/TiO 2 nanocomposite modi ed fabric with GPTMS. Moreover, Curcumin /TiO 2 nanocomposite modi ed Quatt-188 cationized fabric exhibited higher e ciency against Gram -negative bacteria that Gram-positive ones. Cationic modi cation can be used for the modi cation of cotton fabric for increasing curcumin / TiO 2 nanocomposite adsorption on their surfaces and producing stronger antibacterial activity. The results of UV protection also reveal that curcumin /TiO 2 nanocomposite modi ed Quatt-188 cationized fabric acquired the UPF value higher than 50, classi ed the excellent UV protection properties.
Declarations Figure 1 The schematic mechanism for deposition of curcumin/TiO2 nanocomposite on cotton fabric