Cellulose https://doi.org/10.1007/s10570-022-04726-z ORIGINAL RESEARCH Silica nanostructures against fungal growth: design and preparation of antifungal cotton fabrics Ming Liu · Albert Granados · David Reyes‑Mesa · E. Leonardo Arosemena‑Angulo · María Ángeles Calvo‑Torras · Roser Pleixats · Adelina Vallribera Received: 10 March 2022 / Accepted: 18 June 2022 © The Author(s) 2022 Abstract The preparation of antifungal-function- microscopic and spectroscopic techniques. The anti- alized silica nanoparticles by covalent attachment fungal activity of all the modified cotton textiles is of several silylated derivatives based on the topical tested against Trichophyton mentagrophytes CECT antifungal agent Micozanole is described. Grafting 2783, Aspergillus brasiliensis CECT 2091, Penicil‑ and co-condensation procedures are used to obtain lium chrysogenum CECT 2307 and Candida albi‑ mesoporous or dense nanoparticles. Cotton fabrics cans CECT 1001, resulting to be highly dependent have been coated with these antifungal-functional- on the microorganism. Remarkably, all of the modi- ized silica nanoparticles under ultrasonic conditions. fied fabrics are active against Candida albicans and The characterization of the functionalized nano- Trichophyton mentagrophytes, with up to 75 and 90% particles and coated cotton fabrics is performed by effectiveness, respectively. High expectations arise for topical cutaneous applications in wound dressings Dedicated to Professor Joan Bosch (Universitat de (bandages, gauzes, strips). Barcelona) on the occasion of his 75th anniversary. Albert Granados, Maria Angeles Calvo-Torras, Roser Pleixats and Adelina Vallribera are principal authors. Supplementary Information The online version contains supplementary material available at https://​doi.​ org/​10.​1007/​s10570-​022-​04726-z. M. Liu · A. Granados · D. Reyes‑Mesa · R. Pleixats · R. Pleixats A. Vallribera (*) e-mail: roser.pleixats@uab.cat Departament de Química and Centro de Innovación en Química Avanzada (ORFEO‑CINQA), E. L. Arosemena‑Angulo · M. Á. Calvo‑Torras Universitat Autònoma de Barcelona, Campus UAB, Departament de Sanitat i Anatomia Animals, 08193 Cerdanyola del Vallès, Barcelona, Spain Universitat Autònoma de Barcelona, Campus UAB, e-mail: adelina.vallribera@uab.cat 08193 Cerdanyola del Vallès, Barcelona, Spain e-mail: arosemenaleo80@gmail.com M. Liu e-mail: ming.liu@uab.cat M. Á. Calvo‑Torras e-mail: mariangels.calvo@uab.cat A. Granados e-mail: albert.granados@uab.cat D. Reyes‑Mesa e-mail: david.reyesm@autonoma.cat Vol.: (0123456789) 13 Cellulose Graphical abstract Keywords Antifungal · Click chemistry · Cotton this global problem has been overlooked and belit- fabrics · Functionalization of textiles · Silica tled for a long time. Additionally, in this complex nanoparticles scenario, global warming and accompanying climate changes have resulted in an increased incidence of many fungal diseases (Garcia-Solache and Casadevall Introduction 2010). Thus, in this context, the development of new drugs in order to treat fungal diseases is mandatory. In our daily life, it is inevitable to encounter a vari- On the other side, cotton fabrics are widely used ety of microorganisms, which may rapidly grow and materials because of their excellent properties includ- cause damage to people’s health. Fungal infections ing biodegradability, softness, permeability, and represent a huge global problem resulting in over hygroscope capacity. However, cotton textiles provide 1.7 million of deaths every year in humans and over a good living environment for fungi because of mas- one billion people suffer from severe fungal dis- sive hydrophilic cellulose and pores. Consequently, eases (Brown et al. 2012). Some hosts for the fungi much effort has been done in the preparation of func- proliferation are food crops, animal species and tex- tional materials for avoiding the global problem of tiles (Almeida et al. 2019). Focusing in the last one, fungi proliferation on cotton surfaces. textiles are excellent substrates for microbial prolif- Numerous antifungal molecular agents have been eration under appropriate moisture, nutrients, and selected for coating cotton fabrics (Emam et al. temperature conditions (Lim and Hudson 2004). 2021), including quaternary ammonium salts, N-hal- In the hospital environment, contaminated cotton- amines, recognized antifungal drugs (Ketoconazole) based materials can infect patients and professionals. and bioactive dyes. Rosenau’s group described the Moreover, contamination of these textiles in clinical covalent grafting of xanthene-derived photosensitiz- atmospheres can contribute to the spread of airborne ers onto cellulose sheets that produce single oxygen pathogens, which then fall by gravity and infect the upon white light illumination having photomicrobi- environment. cidal activity (Hettegger et al. 2015a). Sun et al. syn- Besides, in 2020 the World Health Organization thesized derivatives of polyquaternary ammonium developed the first meeting of the WHO antifungal salts based on N,N-dimethylaminoethyl methacrylate expert group for the identification of priority fungal which were deposited onto cotton fabrics after free pathogens to develop a priority pathogens list for radical polymerization. After a chlorine bleach the fungal infections of public health importance and to amide groups were transformed into N-halamines (Li define the R&D priorities (Getahun et al. 2020). So, et al. 2020a, b). β-Cyclodextrin with an encapsulated Vol:. (1234567890) 13 Cellulose antifungal drug was loaded on the surface of a wound cotton fabrics using the dip coating technique (Roy dressing and a controlled release of Ketoconazole to et al. 2020). El-Nahhal’s group used ultrasound irra- skin was achieved (Hedayatia et al. 2020). Moreo- diation for the deposition of ZnO NPs on cotton fib- ver, application of 1,3-bis[(furan-2-yl)methylene] ers (El-Nahhal et al. 2017). Gowri and collaborators thiourea (Jabar et al. 2020) and curcuma (Gargoubi described the obtention of antimicrobial T ­ iO2 nano- et al. 2020) dyes resulted in excellent finished textiles particles from titanium tetraisopropoxide and extracts against some fungi. The uniform dispersion of guana- derived from Aloe vera plant, after calcination at zole-metal complexes on cotton fabrics surface ­(Ag+ 500 °C (Gowri et al. 2016). In 2019, functional anti- and ­Zn2+) via self-assembly resulted in antifungal and microbial cotton was prepared applying ­TiO2 NPs and flame retardant materials (Nabipour et al. 2020). green walnut shell dye to modify the metal oxide NPs Among the antifungal agents, several and achieve natural dye coloration (Nazari 2019). nanostructures have been intensively studied, Djamaan and collaborators dispersed T ­iO2–SiO2/ including organic molecules-based nanoparticles chitosan NPs on cotton fabrics surface (Rilda et al. (NPs), metal NPs and metal oxide NPs. An effective 2016). The hybrid T ­ iO2–SiO2/chitosan (2:1) NPs pre- ultrasound assisted deposition of vanillin NPs, sented high ability to generate hydroxyl radicals and raspberry ketone NPs and camphor NPs on textiles the superoxide anion, which can destroy the fungi’s was reported by Gedanken’s group (Tzhayik et al. cell membranes. 2017). These nanomaterials were coated on cotton In some cases, mixtures of metal and metal fabrics and showed excellent antifungal activity on oxide NPs have been used for multifunctional thin- cotton bandages. Recently, carbon quantum dots, coating textile finishing. The use of hybrid A ­ l2O3/ nucleated from a pyrimidine-based compound or SiO2 modified with Ag/Cu NPs and ­TiO2 P25 was from carboxymethyl cellulose, were immobilized described in 2017 (Kowalczyk et al 2017). Gao’s within a textile matrix possessing microbial inhibition research group prepared silver/zinc oxide (Ag/ (Ahmed et al. 2021; Emam et al. 2021). ZnO) NPs with different molar ratios by chemical Among metals, Ag NPs are the most explored. precipitation method observing a synergism between Most of the recent publications use a green route ZnO and Ag NPs in the antimicrobial properties of for their preparation and stabilization. It has been coated cotton fabrics (Gao et al. 2020). described the biosynthesis of Ag NPs using the corn Considering the mentioned precedents, we envis- grain contaminant (Nigrospora oryzae) (Dawoud aged the development of a different approach to et al. 2020), an endophytic actinomycete strain of achieve modified cotton fabrics with antifungal Streptomyces laurentii previously isolated from properties. Taking advantage of the long experience the roots of the plant Achillea fragrantissima (Eid of the group in carrying out sol–gel processes for et al. 2020), Ulva lactuca extracts (Sahayaraj et al. the preparation of hybrid silicas (Trilla et al. 2009; 2019), Citrus sinensis peel juice (AnwarKhalid and Bernini et al. 2010; Boffi et al. 2011; Monge-Marcet Alghamdi 2020), Moringa oleifera extracts (El-Sayed et al. 2012; Borja et al. 2012); Fernández et al. 2014; et al. 2020) and Mikania micrantha leaves extracts Ferré et al. 2016) and in the coating of textiles (Soler (Fajar et al. 2020). All these Ag NPs were coated onto et al. 2011; Salabert et al. 2015; Montagut et al. 2017; cotton fabrics by different techniques and then stud- Montagut et al. 2019a, b; Li et al. 2020a), we envi- ied with good results against several common fungi sioned the covalent anchoring of well-known anti- strains. Another approach was based on coating, by fungal agents on silica nanoparticles (either dense pad-dry-cure process, Ag NPs previously formed on or mesoporous), which have deserved great attention siliceous matrixes dopped with carbon including a as a biocompatible form of silica (Tang et al. 2012; calcination step (Igal et al. 2019). Furthermore, bime- Tarn et al. 2013; Croissant et al. 2015; Ni et al. 2018). tallic Ag/Cu NPs exhibited a pronounced antimycotic Miconazole core was chosen as a model structure activity (Eremenko et al. 2016; Paszkiewicz et al because it has been traditionally used to topically 2016). treat superficial infections caused by fungi. Like other Among nanostructures of metal oxides, ZnO and azole antifungals, Miconazole exerts its effect by dis- ­TiO2 nanoparticles are the most studied. Gafur and rupting the cell membrane of the fungus. Micona- co-workers prepared ZnO NPs and coated them on zole inhibits ergosterol synthesis by interacting with Vol.: (0123456789) 13 Cellulose 14-alpha demethylase, a cytochrome P-450 enzyme Characterization techniques that is required for the conversion of lanosterol to ergosterol, an essential membrane component. Inhi- The 1H and 13C NMR spectra were recorded at bition of ergosterol synthesis results in increased 298.0 K on a Bruker DPX-360 or 400 MHz Bruker cell permeability, causing filtration of cell contents. Advance-III equipped with a BBFO probe with an Miconazole does not have the same effect on human automatic tuning. All the spectra were calibrated cholesterol synthesis. Other antifungal effects of imi- using the residual solvent signal (­CDCl3, δH, 7.26 dazole derivatives have been proposed that include and δC, 77.16 ppm and C ­ D3OD, δH, 3.31 and δC, inhibition of endogenous respiration, interaction with 49.0 ppm). Chemical shift data were expressed in membrane phospholipids, and inhibition of yeast ppm and coupling constant (J) values in Hz. Mul- transformation to mycelial forms. Other mechanisms tiplicity of peaks was abbreviated as s (singlet), d may involve inhibition of uptake and impairment of (doublet), t (triplet), q (quartet), and dd (doublet of triglyceride and phospholipid biosynthesis (Sheehan doublets). The 29Si and 13C CP-MAS NMR spectra et al. 1999). were obtained from a Bruker AV400WB, the rep- For this purpose, the drug must be derivatized by etition time was 5 s with contact times of 2 ms and adding a terminal group of the triethoxysilyl type that the number of scans acquired was between 800 and allows condensation with tetraethoxysilane (TEOS) 1600. This NMR instrument belongs to the Servicio in the presence of a catalyst. Alternatively, the graft- de Resonancia Magnética Nuclear de Sólidos del ing of the silylated derivatives to previously formed Instituto de Ciencia de Materiales de Madrid—CSIC. mesoporous silica nanoparticles of MCM-41 type FTIR spectroscopy was recorded with a Bruker Ten- would also be performed. The functionalized non- sor 27 spectrometer using a Golden Gate ATR mod- porous or mesoporous silica nanoparticles would be ule with a diamond window. High resolution mass dispersed onto cotton fabrics surfaces and studied for spectra were obtained by direct injection of the sam- potential topical anti-fungal applications in medical ple with electrospray techniques in Hewlett-Packard textiles (bandages, gauzes or strips). Furthermore, 5989A and microTOF-Q instruments, respectively. the presence of functionalized silica nanoparticles in Elemental analysis of C, N, and H were performed dressings would increase the roughness of the sur- using Flash 2000 Organic Elemental analyzer of face of the fabric and, consequently, its hydrophobic- Thermo Fisher Scientific with BBOT as an internal ity and durability (Wang et al. 2008; Xue et al. 2009; standard. Transmission electron microscopy (TEM) Zhang et al. 2013). The moisture rejection is advanta- analyses were performed on a JEM-2011 Electron geous for keeping dry the gauze, acting as a barrier to Microscope at 200 kV. Scanning electron micros- the microorganisms. copy (SEM), energy-dispersive X-ray spectroscopy (EDX), and element line scans mapping were taken on a SEM Zeiss Merlin with and INCA detector from Experimental section Oxford Instruments. Thus, microscopic investigations of the specimens were carried out using a ZEISS Materials MERLIN scanning electron microscope (SEM). The specimens were mounted on conductive carbon adhe- All chemicals were purchased from Fluorochem and sive tabs and images were taken after the specimens Merck, and they were used without further purifica- had been sputter-coated (K550X EMITECH) with a tion, unless specified. MCM-41 nanoparticles (Li very thin layer of gold. For the elemental composi- et al. 2020a), (3-iodopropyl)triethoxysilane (Guo tion of the fabric surface, an INCA energy disper- et al. 2013) and (3-azidopropyl)triethoxysilane (Li sive X-ray (EDX) detector from Oxford Instruments et al. 2019) were prepared as previously reported in was used. Dynamic light scattering (DLS) and zeta our group. potential measurements have been performed using a Zetasizer Nano ZS (Malvern Instruments) with 8 mg of silica NPs in 8 mL of Milli-Q water, and the pH of the solution was measured by CRISON pH meter Basic 20. The surface areas were determined by the Vol:. (1234567890) 13 Cellulose Brunauer − Emmett − Teller (BET) method from was washed with anhydrous pentane, affording the ­N2 adsorption − desorption isotherms obtained with corresponding imidazolium iodide in excellent yield. a Micromeritics ASAP2000 analyzer after degas- sing samples for 55 h at 30 °C under vacuum. Pow- Procedure for the preparation of 6 der X-ray diffraction (P-XRD) was performed with X’Pert Power (PANalytical, Almelo, Netherlands), Step 1: 3​‑ch​lor​o‑4​‑((​1‑(​2,4​‑di​chl​oro​phe​nyl​)‑2​‑(1​H‑i​ 45 kV/40 mA, Kα 1.5419 Å with a cooper anode. For mid​azo​l‑1​‑yl​)et​hox​y)methyl)benzaldehyde (5a) contact angle (CA) measurements, the hydrophobic tests performed were the measurement of the contact To a stirred solution of compound 5 (1 mmol, 0.41 g) angle of a water droplet (4 µL) deposited on top of in dry toluene at 0 °C was added 1.5 mL of a DIBAL each fabric. These experiments were carried out at solution in toluene (1 M). The reaction was stirred ICMAB installations with a Contact Angle Measur- at 0 °C for 60 min. Afterwards, hydrochloric acid ing System DSA 100 from KRÜSS, which is located 10 M (10 mL) was added to the mixture, and when in a physico-chemical laboratory (humidity and tem- the solution turned a white slurry, 20 mL of HCl perature control). 1 M was added. Then, a solution of 5% N ­ aHCO3 was added until the pH of the aqueous solution was General procedure for the preparation 10. The organic phase was separated, and the aque- of 4‑((1‑(2,4‑dichlorophenyl)‑2‑(1H‑imidazol‑1‑yl) ous phase was further extracted with dichlorometh- ethoxy)methyl) arenes (1 (Chevreuil et al. 2006), 2 ane. The organics were combined, dried over anhy- (Oh et al. 2011), 5 and 7) drous ­Na2SO4 and the solvent removed under high vacuum. The titled compound 5a was purified as an In a flame dried Schlenck the benzylic alcohol deriva- oil from the crude by flash column chromatography tive (1 equiv) was dissolved in 10 mL of anhydrous using hexane:ethyl acetate (1:9) as eluent (Rf = 0.3 THF under argon atmosphere. Then, sodium hydride (hexane:ethyl acetate (1:9)) (69% yield, 285 mg, (60% in mineral oil, 4 equiv) was added to the solu- 0.69 mmol). tion and the mixture was stirred at rt for 15 min. Then, the corresponding benzylic bromide (1.23 Step 2: (3‑chloro‑4‑((1‑(2,4‑dichlorophenyl)‑2‑(1H equiv) was added and the mixture was stirred at rt ‑imidazol‑1‑yl)ethoxy)methyl)phenyl)methanol (5b) until completion of the reaction (3 h). When the reaction was over, 10 mL of cold water was added, To a stirred solution of compound 5a (2.9 mmol, followed by the addition of 20 mL of dichlorometh- 1.2 g) in methanol (20 mL) at rt was added in one ane. The organic phase was separated, and the aque- portion 0.22 g (5.8 mmol) of NaBH4. After 3 h, ous layer was extracted with more dichloromethane. the methanolic solution was poured into 100 mL of The organics were combined, dried over anhydrous water. The solution was transferred into a separatory sodium sulphate and evaporated under reduced pres- funnel, and extractions with dichloromethane were sure. The products were purified by flash column performed. The organics were collected, dried over chromatography (Rf for product 1 = 0.3; Rf for prod- anhydrous sodium sulphate, and the solvent removed uct 2 = 0.28; Rf for product 5 = 0.25; Rf for product under high vacuum. The titled compound 5b (0.96 g, 7 = 0.45 (hexane: AcOEt 1:4)). 2.35 mmol, 81% yield) was obtained as oil after puri- fication from the crude by flash column chromatogra- General procedure for the preparation of imidazolium phy using ethyl acetate as eluent. iodides (3, 4 and 10) Step 3: 3‑chloro‑4‑((1‑(2,4‑dichlorophenyl)‑2‑(1H A solution of the corresponding imidazole derivative ‑imidazol‑1‑yl)ethoxy)methyl)benzyl (3‑(triethoxysi‑ (1 equiv.) and triethoxy(3-iodopropyl)silane (1 equiv.) lyl)propyl)carbamate (6) in dry acetonitrile (20 mL) was refluxed under argon overnight. After completion of the reaction, the sol- To a stirred solution of compound 5b (0.61 mmol, vent was removed under high vacuum. The final oil 250 mg) in dry THF (5 mL) was added triethoxy(3- isocyanatopropyl)silane (0.15 mL, 0.24 mmol) and Vol.: (0123456789) 13 Cellulose 0.01 mL of dibutyltin dilaureate. The reaction was Step 3: 4‑(3‑chloro‑4‑((1‑(2,4‑dichloroph led to proceed overnight under reflux. Next, the enyl)‑2‑(1H‑imidazol‑1‑yl)ethoxy)methyl) solvent was evaporated under high vacuum. The phenyl)‑1‑(3‑(triethoxysilyl)propyl)‑1H‑1,2,3‑triazole crude was purified by flash column chromatography (9) using ethyl acetate as eluent to obtain 6 as a color- less oil (Rf = 0.43 (ethyl acetate) (81% yield,324 mg, The alkyne 8a (400 mg, 1.0 mmol) and 3-(azidopro- 0.50 mmol). pyl)triethoxysilane (0.246 g, 1 mmol) were dissolved in dry acetonitrile (4 mL) in a microwave tube. Then Procedure for the preparation of 9 CuBr(PPh3)3 (9.2 mg, 0.01 mmol) was added and the system was closed. The tube was introduced in the Step 1: 4​‑(3​‑ch​lor​o‑4​‑((​1‑(​2,4​‑di​chl​oro​phe​ microwave apparatus and the reaction was led to pro- nyl​)‑2​‑(1​H‑i​mid​azo​l‑1​‑yl​)et​hox​y)m​eth​yl)​phe​ ceed at 120 °C and 200 W for 10 min. Afterwards, nyl)‑2‑methylbut‑3‑yn‑2‑ol (8) the solution was filtered through Celite® and then the solvent was evaporated. The residue was gen- Compound 7 (0.50 g, 1.08 mmol) was dissolved tly washed with dry pentane. The final compound 9 in a degassed mixture of 3 mL of water and 3 mL was obtained as a colorless oil in 92% yield (601 mg, of 1,2-dimethoxyethane under nitrogen atmos- 0.92 mmol). phere. To the solution were added ­K2CO3 (375 mg, 2.71 mmol), CuI (8.3 mg, 0.04 mmol), ­PPh3 (23 mg, General procedure for the preparation of functional- 0.08 mmol) and Pd/C (23 mg, 0.02 mmol). The mix- ized silica nanoparticles by co‑condensation method ture was stirred for 30 min at rt and then the alco- (dN1–dN5) holic alkyne was added through syringe (0.26 mL, 2.74 mmol). The reaction was stirred overnight at Tetraethoxysilane (2.08 g, 10.0 mmol) and the cor- 80 °C under inert atmosphere, then the mixture responding silylated antifungal (3, 4, 6, 9 or 10) was cooled to room temperature, filtered through (0.75 mmol) were dissolved in absolute EtOH Celite® and extracted with dichloromethane three (35 mL). Then, an ammonium hydroxide-ethanol times. The organics were washed with water, dried, solution was added (9 mL of 28% ­NH3 ­H2O in 35 mL and concentrated in vacuo. The residue was purified EtOH). The mixture was magnetically stirred inten- by flash column chromatography (AcOEt 100%) to sively (1400 rpm) at room temperature for 12 h. afford 8 as a white solid (Rf = 0.2 (ethyl acetate) (78% The functionalized nanoparticles were collected by yield,393 mg, 0.84 mmol). centrifugation (12,000 rpm for 10 min) and washed with ethanol until neutral pH was reached. Then, the Step 2: 1‑(2‑((2‑chloro‑4‑ethynylbenzyl) obtained white solid was washed successively with oxy)‑2‑(2,4‑dichlorophenyl)ethyl)‑1H‑imidazole (8a) Milli-Q water and 96% ethanol, and the nanomateri- als were dried under high vacuum. The alcohol 8 (720 mg, 1.44 mmol) was dissolved in dry toluene (30 mL) in a round-bottom flask. Then General procedure for the preparation of functional- NaH (60% in mineral oil, 0.6 mg, 0.014 mmol) was ized silica nanoparticles by grafting method (mN6– added and a distillation system was adapted. The sys- mN8) tem was heated at 130 °C for 2 h. After this time, the TLC showed full conversion and most of the toluene The corresponding silylated antifungal derivative has been distilled. The crude mixture was directly (0.30 mmol) and mesoporous silica nanoparticles poured into a flash silica gel column chromatography of MCM-41 type (360 mg) were refluxed in anhy- and eluted with pure AcOEt. Terminal alkyne 8a was drous toluene (60 mL) for 24 h in a 250 mL round obtained as a colorless solid in 93% yield (586 mg, bottom flask equipped with a Dean-Stark apparatus. 1.33 mmol). Then the suspension was centrifuged (13,500 rpm at 25 °C for 45 min). The solid was washed successively with ethanol (3 × 30 mL), acetone (2 × 30 mL) and dichloromethane (2 × 30 mL) (30 min at 50 °C under Vol:. (1234567890) 13 Cellulose sonication, 30 min for centrifugation), and further brasiliensis CECT 2091, Penicillium chrysogenum dried under high vacuum to give the grafted material CECT 2307 and Candida albicans CECT 1001). A as a white solid. suspension of known concentration was prepared by titration (by preparation of serial dilutions and seed- General procedure for the one‑step coating of cotton ing) of the order of 106 CFU / mL (Colony Forming fabrics with antifungal nonporous silica nanoparticles Units) of each fungal culture. In addition, two assays (Fabric dN1‑Fabric dN5) were performed where sterile Petri dishes were pre- pared and fragments of the fabrics were deposited Tetraethoxysilane (2.08 g, 10.0 mmol) and the cor- (each containing a different type of nanoparticle) and responding silylated antifungal (3, 4, 6, 9 or 10) each type of nanoparticle had four replicated impreg- (0.75 mmol) were dissolved in absolute EtOH nated each with one of the four types of fungus. One (35 mL). Then, an ammonium hydroxide-ethanol of the trials was at time 0 and another with a 24-h solution was added (9 mL of 28% ­NH3 ­H2O in 35 mL exposure (during this period they were kept at 25 °C EtOH). The mixture was magnetically stirred inten- and in aerobiosis). Immediately after impregnating sively (1400 rpm) at room temperature for 12 h and the fabrics, in the time trial 0, the deposited culture then ultrasonicated for 30 min. Afterwards, a piece was recovered using a sterile swab and reseeded in of white clean 100% cotton (3 × 3 cm) previously Petri dishes containing Agar Saboureaud (a suitable washed with soap and sodium carbonate and dried culture medium for the correct growth of the fungi). as previously reported in our group (Salabert et al. The results of this test correspond to the maximum 2015), was immersed in the prepared coating solu- number of CFU that can be recovered per plate just tion and the whole system was ultrasonicated for after the direct contact of the fungi with the studied 30 min. After this period of time, the cotton fabric fabrics. The inoculated plates were kept in an oven was removed from the solution, washed with water for 3–5 days at 25 °C in aerobiosis and then proceed several times and dried in a vacuum oven at 50 °C for to the reading of CFU developed at time 0 ­(CFU0). several hours. By contrast, the second group of fabrics was kept in contact with fungi for 24 h. After this time, the same General procedure for the coating of cotton fabrics procedure was done as with time group 0, obtaining with antifungal mesoporous silica nanoparticles in this case the CFU in 24 h ­(CFU24). Once the results (Fabric mN6‑Fabric mN8) were obtained, the effectiveness of the antifungal can be expressed in % effectiveness as [(CFU0 − ­CFU24)/ The corresponding silylated antifungal derivative CFU0] × 100. (0.30 mmol) and mesoporous silica nanoparticles of MCM-41 type (360 mg) were refluxed in anhy- drous toluene (60 mL) for 24 h in a 250 mL round Results and discussion bottom flask equipped with a Dean-Stark apparatus. The resulting mixture was ultrasonicated for 30 min Synthesis of silylated derivatives of antifungals and then a piece of clean cotton fabric (3 × 3 cm) was immersed in the prepared coating solution. The As we have mentioned, Miconazole core was chosen whole system was ultrasonicated for 30 min. After as a model structure. In order to covalently attach the this period of time, the cotton fabric was removed antifungal units onto silica nanoparticles, the pres- from the solution, rinsed with toluene and dried in a ence of a triethoxysilyl moiety on its structure was vacuum oven at 50 °C for several hours. selected. Different linkers to attach this silylated unit were evaluated (such as carbamate and triazole). Antifungal activity of the modified cotton fabrics Additionally, as Miconazole is pharmacologically used as a nitrate salt, the alkylation of the imidazole With the coated fabrics with nanoparticles in hand, ring with a silylated alkyl iodide was also considered their effectiveness against four microorganisms (fila- (Scheme 1). mentous fungi and yeast) was measured (Tricho- First, we developed a bimolecular nucleo- phyton mentagrophytes CECT 2783, Aspergillus philic substitution between Miconazole (1) and Vol.: (0123456789) 13 Cellulose Scheme 1  Synthesis of silylated drug derivatives 3, 4, 6, 9 and 10 Vol:. (1234567890) 13 Cellulose 3-iodopropyltriethoxysilane in dry acetonitrile, yield- temperature for 12 h and then the dense nanoparticles ing the corresponding imidazolium iodide 3 (95% were collected by centrifugation (13,500 rpm) and yield). As we also wanted to check the importance washed successively with ethanol, Milli-Q water, and of the position of the chlorine atoms in the benzy- ethanol until neutral pH. loxy moiety, we prepared the silylated imidazolium On the other hand, functionalized mesoporous iodide 4 from 2 by an analogous procedure (94% silica nanoparticles mN6–mN8 (Scheme 2) were pre- yield). Then, we replaced the chlorine atom in posi- pared by grafting the corresponding silylated drugs tion 4 of the aryl ring of the benzyloxy moiety pre- to previously synthesized mesoporous silica nano- sent in Miconazole by a silylated carbamate (6) or by particles of MCM-41 type (Théron et al. 2014) in a silylated triazole ring (9) (Scheme 1). refluxing toluene for 24 h. The NPs were collected by The preparation of 6 was undertaken from the centrifugation (13,500 rpm) and then washed succes- nitrile 5. First, the nitrile was reduced to the corre- sively with ethanol, acetone, and dichloromethane. sponding aldehyde (69%) by DIBAL at 0 °C in dry These nanomaterials were characterized by ele- toluene. Then, the carbonyl group was reduced to the mental analysis, transmission electron microscopy primary alcohol (81% yield) with sodium borohy- (TEM), dynamic light scattering (DLS), zeta-poten- dride. Finally, the alcohol reacted with the silylated tial, infrared spectroscopy, powder XRD and nitro- isocyanate efficiently in refluxing THF using dibu- gen-sorption measurements when appropriate. tyltin dilaureate as catalyst to afford the carbamate 6 In Table 1 are summarized some physical data (81% yield). Thus, compound 6 was prepared in three obtained after characterization. First, the nanometric steps in 45% overall yield from 5 (Scheme 1). On the size and morphology of these materials were analysed other hand, compound 9 was synthesized from the by TEM and DLS. Materials dN1, dN2 and dN3 pre- bromoarene 7 through a Sonogashira coupling with pared by co-condensation of silylated imidazolium 2-methylbut-3-yn-2-ol as a first step, yielding alkyne iodides 3, 4 and 10 in basic medium in the absence of 8 in a 78% yield. This alkyne was deprotected under template appeared as nonporous dense aggregates and catalytic NaH to afford the corresponding terminal they showed high polydispersity in the dynamic light alkyne (92% yield), which was coupled with (3-azido- scattering measurements (Table 1). propyl)triethoxysilane giving 9 (92% yield) through Contrarily, dN4 and dN5 prepared from neutral a click Cu-catalyzed azide-alkyne Huisgen reaction silylated precursors 6 and 9 under analogous condi- (Breugst and Reissig 2020; Hettegger et al. 2015b) tions exhibited spherical morphology, with diam- under microwave and anhydrous conditions (Bürglová eters around 136 ± 31 nm and 206 ± 45 nm (see the et al. 2011). Thus, the silylated triazole derivative TEM image of dN5 in Fig. 1, left, as an example) and 9 was prepared in a 66% global yield in three steps showed a good polydispersity index in DLS (Table 1 from 7 (Scheme 1). Finally, the silylated imidazolium and Supplementary Information). iodide 10 was prepared from 7 (95% yield) to check Besides, mN6–mN8 nanomaterials prepared by the effect of the change of the chlorine by a bromine grafting appeared as mesoporous spherical nanopar- atom in the antifungal activity (Scheme 1). ticles with average diameters of 86 ± 24, 140 ± 17 and 147 ± 31 nm (see Table 1 and Supplementary Infor- Preparation and Characterization of Antifungal‑Func- mation). A selected TEM image of mN6 is given tionalized Silica Nanoparticles in Fig. 1, right). The BET surface area of mN6 and mN8 were 313 and 192 m ­ 2 ­g−1, respectively. The p- With the modified silylated antifungal molecules (3, XRD analyses showed the organized porosity for the 4, 6, 9 and 10, Scheme 1) in hand, we turned to the MCM-41 materials, typical for a hexagonal 2D sym- covalent anchoring of these drugs to silica nanopar- metry (see Fig. 2 for the p-XRD of mN8). ticles. We followed two different approaches. First, In these cases, DLS measurements showed hydro- we prepared nonporous nanomaterials dN1–dN5 by dynamic diameters that are in agreement with the co-condensation of silylated precursors (3, 4, 6, 9 or TEM size of the corresponding dried nanoparticles if 10) with TEOS using a 28% aqueous ammonia solu- we consider the likely adsorption of water molecules tion in ethanol (Li et al. 2020a; Wang et al. 2008) onto the nanoparticle surface (Table 1). The drug (Scheme 2). The mixed solution was stirred at room Vol.: (0123456789) 13 Cellulose Scheme 2  Preparation of drug functionalized silica nanoparticles loading in the NPs was determined from the nitrogen elemental analysis (Table 1). Table 1  Characterization data of dN1–dN5 and mN6–mN8 The stability of all nanoparticles in milli-Q water Material Drug loading Particle size Z-potential (mV) suspension (1 mg/mL) was checked by zeta potential. (mmol ­g−1)a (nm) The nanomaterials (dN1, dN2, dN3, mN6 and mN7) TEM DLSb prepared from the imidazolium salts presented posi- tive values from + 35.6 to + 50.2 mV, which are in dN1 0.507 ndc ndc + 50.2 good agreement with a good stability in water sus- dN2 0.332 ndc ndc + 37.3 pension and the presence of cationic imidazolium dN3 0.360 ndc ndc + 37.4 moieties on the surface of the particles. On the other dN4 0.263 136 ± 31 427 − 64.7 hand, the nanoparticles (dN4, dN5 and mN8) synthe- dN5 0.244 206 ± 45 416 − 21.0 sized from neutral silylated derivatives showed nega- mN6 0.514 86 ± 24 120 + 37.0 tive zeta potential values (from − 21 to − 64.7 mV) mN7 0.471 140 ± 17 215 + 35.6 also indicative of a good stability. The negative sign mN8 0.377 147 ± 31 204 − 28.1 in these samples is in consonance with the non-pro- a Calculated from the N elemental analysis tonation of the basic imidazole ring and the residual b Hydrodynamic diameters deprotonated silanol groups. c Not determined, the sample presented high polydispersity Solid state 29Si and 13C NMR spectra ensured index the presence of the corresponding organic moiety in Vol:. (1234567890) 13 Cellulose Fig. 1  Left: TEM image of dN5. Right: TEM image of mN6 the nanomaterials. The 29Si CP MAS NMR showed Preparation and characterization of cotton fabrics two groups of chemical shifts: T units from -61 to coated with antifungal‑functionalized silica nanopar- -69 ppm formed from the organosilanes and Q units ticles ranging from − 90 to − 111 ppm resulting from TEOS. The presence of T signals suggested that the The preparation of cotton fabrics coated with drug- integrity of the Si–C bond was maintained during functionalized silica nanoparticles was performed the formation of the nanomaterials, which was also as represented in Scheme 3. On one hand, once the confirmed by a signal between 8 and 10 ppm in the grafting procedure for the preparation of mesoporous solid state 13C NMR spectra (see the Supplementary functionalized nanoparticles was finished, a piece of Information for the solid-state NMR spectra of the 3 × 3 cm of clean cotton fabric was immersed into nanoparticles). the previously sonicated solution (30 min) and fur- ther sonicated for 30 min. After this time, the cellu- lose material was removed, washed with toluene, and 80000 2θ=2.284 dried under high vacuum at 50 °C. On the other hand, a piece of 3 × 3 cm of clean cotton fabric was added to a previously sonicated 60000 (30 min) milky solution resulting from the co-hydrol- ysis of TEOS with organosilanes in aqueous ammo- Intensitity nia in ethanol, and further sonicated for 30 min. 40000 Afterwards, the cotton fabric was removed from the solution, washed with distilled water, and then dried 20000 under high vacuum at 50 °C. The cotton textiles coated with the nanostruc- 2θ=3.912 2θ=4.542 tures were analysed by scanning electron microscopy 0 (SEM). In Fig. 3 the SEM image of Fabric-dN5 is 1 2 3 4 5 6 2 Theta (°) presented (see Supplementary Information for the other modified cotton fabrics). In the SEM image the cotton fabrics appears covered by functionalized Fig. 2  p-XRD of mN8 Vol.: (0123456789) 13 Cellulose Scheme 3  Preparation of cotton fabrics coated with antifungal-functionalized silica nanoparticles silica nanoparticles. The surface composition was nature of the employed organosilane. The measured checked by energy dispersive X-ray spectroscopy contact angle for Fabric-dN3 and Fabric-dN5 were (EDX) and element mapping. The presence of Si, C, 131 and 148°, respectively, indicative of hydrophobic O, N and in some cases Cl and Br atoms were clearly surfaces. Contrarily, Fabric-mN7 and Fabric-mN8 observed (see Fig. 3 for the element mapping for were not hydrophobic as the water drop was absorbed Fabric-dN5 and the Supplementary Information for by the modified fabrics after a few seconds. the other modified textiles). The cotton fabrics (Fab‑ ric-dN1–Fabric-dN3) coated with dense nonporous Antifungal activity of the fabrics coated with nanoparticles prepared from silylated imidazolium anti‑fungal‑functionalized silica nanoparticles iodides presented cauliflower like structures, in agree- ment with the high polydispersity index observed in The antifungal activity of all the fabrics coated with the DLS measurements of the corresponding nano- antifungal-functionalized silica nanoparticles was particles (dN1-dN3). On the contrary, cotton fab- tested against four different microorganisms, three rics (Fabric-dN4 and Fabric-dN5) coated with filamentous fungi and a yeast (Trichophyton men‑ dense nanoparticles prepared from the non-charged tagrophytes CECT 2783, Aspergillus brasiliensis imidazole-containing organosilanes presented high CECT 2091, Penicillium chrysogenum CECT 2307 homogeneity regarding the particles size. This last and Candida albicans CECT 1001). Trichophyton feature was also observed in cotton fabrics (Fab‑ mentagrophytes is a fungus which causes ringworm ric-mN6–Fabric-mN8) coated with functionalized in companion animals, tinea infections in humans and mesoporous nanoparticles, regardless of the chemical one of the most common fungi that cause zoonotic Vol:. (1234567890) 13 Cellulose Fig. 3  Left: SEM image of Fabric-dN5. Right: Element Mapping of Fabric-dN5 skin disease. Aspergillus brasiliensis is a major envi- fragments of the impregnated cotton fabrics (Fabric- ronmental pollutant. Penicillium chrysogenum can dN2 and Fabric-dN3) and confronting them with the induce respiratory allergic symptoms such as aller- fungal strains. gic rhinitis, asthma and allergic broncho-pulmonary Small pieces of the cotton fabrics were deposited mycosis. Candida albicans is an opportunistic patho- on the surface’s plate and inoculated with each of the genic yeast that is a common member of the human microorganisms. They were incubated for 24–48 h gut flora but can cause infections in humans and ani- and the inhibition halos were observed (see Support- mals such as candidiasis and onychomycosis. ing information). Considering these initial positive Preliminary experiments were carried out follow- results, then we carried out a quantitative study of the ing the antibiogram technique (antifungigram) (Ser- activity of these impregnated fabrics, mimicking its rano et al 2004; Ramírez et al 2006; Espinel-Ingroff application on the surface of the skin of the affected et al 2007; Martos et al 2012; Colosi et al. 2012) organism. The methodology used was a modifica- to study the production of inhibition halos using tion of that indicated in international standards (UNE Vol.: (0123456789) 13 Cellulose Table 2  Antifungal activity (% effectiveness) of Fabrics-dN1 allows specific fungal treatments for each microor- to Fabric-dN5 and Fabrics-mN6 to Fabric-mN8 ganism. Within the same fungal or yeast strain, some Material Strain influence of the structural features of the organic moi- Trichophy‑ Aspergillus Penicillium Candida ety or the type of nanoparticles was also observed, ton menta‑ brasiliensis chrysoge‑ albicans although no clear general rule can be inferred from grophytes num the results. Within Trichophyton mentagrophytes the higher % effectiveness of Fabric-mN7 over Fabric- Fabric- 90 10 90 55 dN1 dN3 and of Fabric-mN8 over Fabric-dN5 (see Fabric- 25 25 0 25 Table 2) could be attributed to the differences in the dN2 hydrophilicity/hydrophobicity of the corresponding Fabric- 25 25 0 25 surfaces. As the microorganisms are grown in aque- dN3 ous medium, a hydrophobic antifungal cotton surface Fabric- 90 0 25 25 would make more difficult the interaction with the dN4 fungus. It is noteworthy that Fabric-dN1, Fabric- Fabric- 25 25 0 25 mN6 and Fabric-mN7 are good candidates to be dN5 used as topical antifungal agents in cotton medical Fabric- 90 10 90 55 mN6 textiles for the remarkable results. Fabric- 90 90 90 75 mN7 Fabric- 90 0 25 25 Conclusions mN8 In summary, several silylated derivatives have been prepared taking the topical antifungal agent Micon- EN ISO 846:2020 Plastics- Evaluation of the action azole as a model. Different linkers to attach the of microorganisms (ISO 846:2019)) to quantify the silylated unit have been employed (carbamate and capacity to reduce the viability of the fungal strains triazole). Additionally, as Miconazole is used as a tested. Thus, the modified fabrics were impregnated nitrate salt, the alkylation of the imidazole ring with with the corresponding strain and kept in the stove at a silylated alkyl iodide has also been performed. The 25 oC in aerobiosis for 24 h. The results are shown in covalent anchoring of these silylated derivatives to Table 2. The activity of the modified fabric has been mesoporous or dense silica nanoparticles has been expressed in % effectiveness as [(CFU0 – ­CFU24)/ achieved by grafting and co-condensation procedures, CFU0] × 100, where ­CFU24 is the number of fungal respectively. Furthermore, cotton textiles have been cells that are viable after the fabric is kept in con- coated with these antifungal-functionalized silica tact with fungi for 24 h and C ­ FU0 is the number of nanoparticles under ultrasonic conditions. The char- viable fungal cells at time 0 (CFU = Colony Forming acterization of the functionalized nanoparticles and Units). To our delight, all the fabrics were found to coated cotton fabrics has been carried out by micro- be moderately (25%) or highly active (90%) against scopic and spectroscopic techniques. The antifungal Trichophyton mentagrophytes. The effectiveness activity of all the modified fabrics has been tested against the yeast Candida albicans varies from 25 to against three filamentous fungi and a yeast (Tricho‑ 75%. Whereas Fabric-dN4 and Fabric-mN8 were phyton mentagrophytes CECT 2783, Aspergillus not active against Aspergillus brasiliensis, the other brasiliensis CECT 2091, Penicillium chrysogenum modified cotton fabrics exhibited low (10%), moder- CECT 2307 and Candida albicans CECT 1001) and ate (25%) or high (90%) activity. Excellent antifungal has been found to be highly dependent on the micro- properties (90% effectiveness) were found for Fabric- organism. Some influence of the structural features dN1, Fabric-mN6 and Fabric-mN7 against Penicil‑ of the organic moiety, the type of nanoparticles and lium chrysogenum, and moderate activity (25%) in the hydrophobicity of the cotton surface has been also the case of Fabric-dN4 and Fabric-mN8. Thus, the observed, although no general rule can be deduced. antifungal activity of the coated fabrics was found Remarkably, all of them have shown activity against to be highly dependent on the microorganism. That Candida albicans and Trichophyton mentagrophytes, Vol:. (1234567890) 13 Cellulose with up to 75 and 90% effectiveness, respectively, Boffi A, Cacchi S, Ceci P, Cirilli R, Fabrizi G, Prastaro A, being Fabric-dN1, Fabric-mN6 and Fabric-mN7 Niembro S, Shafir A, Vallribera A (2011) The Heck reac- tion of allylic alcohols catalyzed by palladium nanoparti- the best candidates to combat general fungal growth. cles in water: chemoenzymatic synthesis of (R)-(-)-Rho- High expectations arise for topical cutaneous applica- dodendrol. ChemCatChem 3:347–353 tions in wound dressings (bandages, gauzes, strips). Borja G, Monge-Marcet A, Pleixats R, Parella T, Cattoën X, Wong Chi Man M (2012) Recyclable hybrid silica- Acknowledgments We are thankful for financial sup- based catalysts derived from Pd–NHC complexes for port from Ministerio de Ciencia, Innovación y Universidades Suzuki, Heck and Sonogashira reactions. Eur J Org Chem (MCIU) of Spain (Project RTI2018-097853-B-I00) and 19:3625–3635 DURSI-Generalitat de Catalunya (SGR2017-0465). We are Breugst M, Reissig H-U (2020) The Huisgen reaction: mile- also thankful to China Scholarship Council (CSC) for predoc- stones of the 1,3-dipolar cycloaddition. Angew Chem Int toral scholarship to M. L. and Universitat Autònoma de Barce- Ed 59:12293–12307 lona for a postdoctoral contract to A. G. Brown GD, Denning DW, Gow NAR, Levitz SM, Netea MG, White C (2012) Hidden killers: human fungal infections. Funding Open Access Funding provided by Universitat Sci Transl Med 4:165rv13 Autonoma de Barcelona. Bürglová K, Moitra N, Hodacová J, Cattoën X, Wong Chi Man M (2011) Click approaches to functional water-sensitive Declarations organotriethoxysilanes. J Org Chem 76:7326–7333 Chevreuil F, Landreau A, Seraphin D, Larcher G, Bouchara Conflict of interest The authors declare that they have no GP, Richomme P (2006) Synthesis and antifungal activ- known competing financial interests or personal relationships ity of new thienyl and aryl conazoles. J Enzy Inhib Med that could have appeared to influence the work reported in this Chem 21:293–303 paper. Colosi IA, Faure O, Dessaigne B, Bourdon C, Lebeau B, Colosi HA, Pelloux H (2012) Susceptibility of 100 fila- mentous fungi: comparison of two diffusion methods, Open Access This article is licensed under a Creative Com- Neo-Sensitabs and E-test, for amphotericin B, caspo- mons Attribution 4.0 International License, which permits fungin, itraconazole, voriconazole and posaconazole. Med use, sharing, adaptation, distribution and reproduction in any Mycol 50:378–385 medium or format, as long as you give appropriate credit to the Croissant JG, Cattoën X, Wong Chi Man M, Durand JO, original author(s) and the source, provide a link to the Crea- Khashab NM (2015) Synthesis and applications of peri- tive Commons licence, and indicate if changes were made. The odic mesoporous organosilica nanoparticles. Nanoscale images or other third party material in this article are included 7:20318–20334 in the article’s Creative Commons licence, unless indicated Dawoud TM, Yassin MA, El-Samawaty ARM, Elgorban otherwise in a credit line to the material. If material is not AM (2020) Silver nanoparticles synthesized by nigros- included in the article’s Creative Commons licence and your pora oryzae showed antifungal activity. Saudi J Biol Sci intended use is not permitted by statutory regulation or exceeds 12:36–41 the permitted use, you will need to obtain permission directly Eid AM, Fouda A, Niedbala G, Hassan SE-D, Salem SS, Abdo from the copyright holder. To view a copy of this licence, visit AM, Hetta HF, Shaheen TI (2020) Endophytic strepto- http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/. myces laurentii mediated green synthesis of Ag-NPs with antibacterial and anticancer properties for developing functional textile fabric properties. 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