Abstract
This minireview presents recent developments in surface nano-structured textiles and their biomedical applications by up-to-date achievements, summarizing the coatings made of biopolymer films and nanoparticles on different textile substrates for enhanced medical applications, diminishing the incidence of the multiple range of hospital-acquired infections in the past 10 years. The combination of metal and metal oxide nanoparticles with biopolymers is an efficient technique to generate enhanced antibacterial, virucidal and antifungal properties to textiles. Only a few review articles offer a comprehensive insight into the surface tailoring of textiles by nanoparticles–biopolymers use as an alternative for surface modification of textiles, granting them biocidal performance. The overview points out the compelling reasons for scientists and experts to enhance the already existing results in the biomedical textiles domain, with an emphasis on antimicrobial responsivity, highlighting: (a) the benefit of the simultaneous nanoparticles–biopolymers deposition on textiles by various deposition techniques, meaning the wash fastness of the antibacterial attributes and the biocompatibility of the material in comparison with only nanoparticle coating; (b) the use of biopolymers to stabilize colloidal dispersions of nanoparticles, granting the nanoparticles functionalities for covalent immobilization on textiles with long-lasting antibacterial effect; (c) the most usual metal and metal oxide nanoparticles and biopolymers for antibacterial textile applications.
Recent developments in surface nano-structured textiles and their biomedical applications by nanoparticles–biopolymers have proved a promising alternative for surface modification of textiles as coatings made of biopolymer films and nanoparticles on different textile substrates for enhanced medical applications. The synergy between environmentally friendly biopolymers and nanoparticles leads to the improved functionality of nanocomposite materials, in terms of barrier, antimicrobial and antioxidant properties. An example of nanoparticles–biopolymers composite materials schematic development is presented graphically in Figure 1. There are various available methods for textiles functionalization by using nanocomposite coatings consisting of direct functionalization methods – the nanocomposite coating is formed directly onto the textile fibers – and indirect methods – the nanocomposite is fabricated and then applied onto the textile material. Each of those techniques requires a prior specific preparation of the textile substrates. There are a huge number of materials that can be used to form functional composites for textile surface modification. This minireview will focus on an overview of the simultaneous nanoparticles–biopolymers deposition on textiles by various deposition techniques, and benefits on the wash fastness; the antibacterial attributes and the biocompatibility of the material in comparison with using only nanoparticles coating. Second the use of biopolymers to stabilize colloidal dispersions of nanoparticles, granting the nanoparticles functionalities for covalent immobilization on textiles to impart long-lasting antibacterial effect will be approached. Finally, a synthetic overview of the most usual metal and metal oxide nanoparticles and biopolymers used for the antibacterial textile applications will be provided.

Nanoparticles–biopolymers composite materials schematic development.
Usual deposition techniques
One of the most usual techniques for added functionality to textiles is sonochemical coating. Textile finishing processes accompanied by ultrasound exposure have been reported in the literature since 1975 by deeper penetration of cross-linking resins such as urea–formaldehyde under ultrasonic irradiation on cotton fabric, and an excellent review regarding textile sonoprocessing was published by Harifi and Montazer in 2015 explaining in detail the technique and up to the respective date achievements on various metal, metal oxide and combination surface finishing of fabrics. 1 The schematic representation of this technique is shown in Figure 2.

Sonochemical coating of textiles.
Plenty of research has been done on the functionalization of textiles with inorganic nanoparticles (copper oxide (CuO), zinc oxide (ZnO), titanium dioxide (TiO2), magnesium oxide (MgO), silver (Ag), copper (Cu), Ag/TiO2, Zn/CuO, etc.)2–8 by the sonochemical method. The metal nano-oxides have a large surface area and are suitable for coating textile fibers. This made the metal oxide nanoparticles a good alternative to triclosan, quaternary ammonium salts, and other compounds with high toxicity that were dominating the antimicrobial market. The antibacterial efficiency of the sonochemically coated textiles was still present after 65 washing cycles. Moreover, two functions can be added to textiles simultaneously by sonochemical coating, color and biocide. 7 A recent good review of the subject was published in 2019 by Perelshtein et al. 8 In 2014, Petkova et al. used sonochemical coating of textiles with hybrid ZnO/chitosan nanoparticles to achieve antimicrobial activity of textiles. 9 Hybrid antimicrobial layers were produced on cotton supports by a one-step simultaneous sonochemical deposition of ZnO nanoparticles and chitosan. The process was supplementarily optimized in terms of precursors concentration and processing time in order to improve the antibacterial properties of the textile material and ensure their biocompatibility. The best antibacterial action against two pathologically relevant bacterial species was attained in a 30 min sonochemical coating process using 2 mM ZnO nanoparticle suspension. When chitosan was simultaneously deposited with the same amount of ZnO, the result is a hybrid nanoparticle coating with 48% and 17% higher antibacterial responsivity against Staphylococcus aureus and Escherichia coli, respectively as compared to only ZnO typical finishing. The existence of the biopolymer also improved the robustness of the antimicrobial effect by 21% for S. aureus and 40% for E. coli, assessed after multiple washing cycle applications in hospital laundering regimes. Finally, 87% biocompatibility enhancement proved by fibroblast viability was detected for the hybrid ZnO/chitosan coating compared to the steady decrease of cell viability over one week in contact with the fabrics coated only with ZnO. 9 Chitosan, as well as its precursor chitin, is also widely used as a biopolymer in textile functionalization. Chitin is the second most abundant natural polysaccharide found in the various marine, terrestrial, and microorganism sources. Chitosan is obtained by partial deacetylation of chitin. Both of them are widely used in different industries such as pharmaceutical, agriculture, water purification, biotechnology, biomedical applications, and the production of fibers and finishing processes of textile fibers. The large use is based on their interesting properties such as nontoxicity, biocompatibility, biodegradability, low allergenic action, that they are bioactive, low cost, etc. The most important applications of chitosan in textile finishing include antimicrobial, blood coagulant, antistatic, antiodor, and crease-resistant finishing. 10 Chitosan can be modified by using metal and metal oxide nanoparticles to achieve new functional materials, and it can be applied onto textile substrates by using various other deposition techniques not only sonochemical deposition. During their study, some authors successfully prepared binary chitosan–ZnO nanocomposite by using the precipitation method. 11 Cotton fabrics were treated with the respective bio-nano-composite using pad-dry-cure 12 and sol-gel 13 methods to increase their washing resilience at multiple cycles. (3-Glycidyloxypropyl) trimethoxysilane was used to improve the washing sturdiness of the coatings. Bionanocomposite coated fabrics were tested for their antibacterial and ultraviolet (UV) protection performance. A ternary chitosan–ZnO–TiO2 nanocomposite was also synthesized to detect the changes in UV properties. The results revealed that chitosan–ZnO binary complex provided very good antibacterial and UV protective properties. The results also proved that the sol-gel application by (3-glycidyloxypropyl) trimethoxysilane improved the effects of multi-washing cycles of the treated cotton fabrics in comparison to simple chitosan-treated fabrics. The use of the ternary coating treatment changed the UV protection factor to the ‘excellent protection’ category.
The use of ultrasonication for the preparation of eco-friendly cellulose fabrics containing silver or gold nanoparticles was reported by Kwiczak-Yiğitbaşı et al. 14 According to the authors, the mechano-chemistry of cellulose is based on the breakage of glycosidic bonds and the formation of mechano-radicals. These mechano-radicals can reduce Au3+ and Ag+ ions in solution, and the reduced metals can be stabilized by the cellulose chains on nanoparticles. The preparation method is shown to produce antibacterial silver nanoparticle-fabric and catalytically active gold nanoparticle-fabric composites, having up to a 14% yield of metal ion reduction. As the method consists of only the sonication of the fabric in aqueous solutions, and no hazardous reducing and stabilizing agents are used, it provides quick and environmentally friendly availability of fabric nanocomposites, for applications in medical textiles. 14
Xu et al. reported on durable antibacterial and UV protective properties of cotton fabric coated with carboxymethyl chitosan and Ag/TiO2 composite nanoparticles. 15 Ag/TiO2 colloid solution was prepared by using carboxymethyl chitosan as a stabilizer, then the carboxymethyl chitosan and Ag/TiO2 composite nanoparticles were coated on the fabric via finishing technology of pad-dry-cure. The modified fabric proved to have excellent antibacterial and UV protective properties, with the values of bacterial reduction and UV protection factor of 99.5% and 79.0, respectively. Furthermore, even after 50 washing cycles, these properties of the finished fabrics were not changed. 15 Another suitable biopolymer for use alone and in combination with nanoparticles for the achievement of antibacterial activity onto textile surfaces is cyclodextrin. Cyclodextrins are cyclic oligosaccharides with a hydrophilic outer surface and a lipophilic central cavity. Cyclodextrins show great feasibility in sustainable textile finishing. There are three derivatives of commercial cyclodextrin: α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin – that are composed of six, seven, and eight α-1,4-glycosidic bonds. β-Cyclodextrin is the most consumed, used and attractive cyclodextrin due to its availability, lower price, facile synthesis, no skin sensitization and irritation, and no mutagenic effect. The ability of cyclodextrins to form complexes with host molecules finds significant application in distinct commercial sectors. Various applications of cyclodextrins in textiles to aid properties such as antimicrobial, fragrance, and dyeing have been intensely studied. A clear overview of this can be found in the chapter by Singh and Sahu. 16
Other natural polymers such as starch derivatives, cellulosic materials, maltodextrins, agar, alginate, Arabic gum, chitosan, and gelatins have been reported as excellent materials for microencapsulation. 17 Plant extracts such as limonene, geranium leaf extracts, Calendula officinalis, Mexican daisy, neem oil, tulsi leaf extract, ozonated red pepper seed oil, vitex neguno leaf extract, polyphenolic olive extracts, etc., are the ingredients that have been applied to textile materials in an encapsulated form to improve the antimicrobial activity and their durability to laundering.18–22 By microencapsulation, the active ingredient can be released in a controlled manner instead of directly discharge from the textile fibers. A major advantage of microencapsulation is that it prevents loss of essential oils present in extracts which are highly volatile in substances in the air. These kinds of biopolymers used in microencapsulation can also be combined with metal and metal oxide nanoparticles for fabrication of coatings onto textile fiber surfaces in order to obtain enhanced germicidal properties of textile materials. Some of the recent nanoparticles–biopolymers coating combinations reported in the scientific literature and their specific properties are presented in Table 1.23–69
Some of the recent nanopolymers–biopolymers coating combinations reported in the scientific literature and their specific properties
Ag: silver; CHTS: chitosan; CMC: carboxymethyl cellulose; NPs: nanoparticles; PLA: polylactic acid; PVA: poly(vinyl alcohol); SeNPs: selenium nanoparticles; TiO2: titanium dioxide; UV: ultraviolet; ZnO: zinc oxide.
Discussion
These combinations of nanoparticles and biopolymers have proved potential suitability for use on textile fabrics for medical applications such as medical apparel, blankets, bed linings, etc. as well as wound dressing in some cases. ‘Recent advancements in biopolymer and metal nanoparticle-based materials in diabetic wound healing management’ 70 is an example of recent work on wound dressing applications of combined nanoparticle–biopolymer functionalized textile materials. In that paper, Vijayakumar et al. reported in 2019, a review regarding natural polymers in combination with bioactive nanoparticles with antimicrobial, antibacterial, and anti-inflammatory activities for wound care with a role in accelerating the healing process of diabetic wound infections. The sequence of antibacterial nanoparticles such as silver nanoparticles, copper nanoparticles, etc. with biocompatible and bioactive polymeric matrices accurately restrain bacterial advancement. At the same time, a wound’s healing process is accelerated.
A recent paper by Guan et al. 71 reported on the nanocomposite film (sodium alginate (SA)–chitosan (CS)@CuO/ZnO) composed of sodium alginate and chitosan functionalized by CuO and ZnO nanoparticle fabrication and antibacterial mechanisms against E. coli and S. aureus. At contents of 1.5% (w/w) and 0.5% (w/w), respectively, of CuO and ZnO nanoparticles, the SA–CS@CuO/ZnO composite films exhibited excellent optical, mechanical, and shielding activities. Incorporation of ZnO nanoparticles added to the photocatalytic ability of SA–CS@CuO/ZnO, producing a high level of reactive oxygen species under light irradiation. Further, antibacterial results showed that SA–CS@CuO/ZnO coatings inhibited the growth of E. coli and S. aureus over 60% in the dark and over 90% under light irradiation. This was also accompanied by incompleteness of bacterial cell structure, unstable cellular redox balance and DNA disruption.
The functions of differentially expressed genes screened by transcriptome analysis were mainly involved in membrane transport, cell wall and membrane synthesis, cellular antioxidant defense system, cell membrane and DNA repair system. The changes in bacterial transcriptional regulation reflected the disturbance in the physiological activities and loss of cell integrity, leading to damage of bacterial cells or death. 71
The paper entitled ‘Wound dressing properties of functionalized environmentally biopolymer loaded with selenium nanoparticles’ was recently published by Ahmed et al. 72 using a polymeric blend based on chitosan/poly(vinyl alcohol) (PVA) containing different concentrations of selenium nanoparticles and fabricated via the casting technique. The results illustrated that the nanocomposite killed and inhibited the growth of E. coli and S. aureus bacteria. 72 Smart polymeric films may act as surfaces that not only kill bacteria but also limit their adhesion and interaction with surfaces. An elaborate account of the recent advances and updated accomplishments of nanoparticle-impregnated biopolymeric films to combat microbial biofilms, thus inspiring innovations for cutting-edge research and development in this area was just published by Ghosh et al. 73 That review speculated that various passive and active mechanisms are behind the inhibition and disruption of biofilms using nanoparticle–polymer composite films. 73
The paper ‘Preparation of antibacterial film-based biopolymer embedded with vanadium oxide nanoparticles using one-pot laser ablation’ was recently reported by Menazea et al. 74 An environmentally friendly and cost effective film of vanadium oxide (V2O5) nanoparticles embedded PVA/chitosan was fabricated. The authors used the one step pulsed laser ablation in liquid technique for the preparation of V2O5 nanoparticles followed by mixing the prepared nanoparticles with polymer solution preceding the film formation. The use of V2O5 nanoparticles enhanced the antibacterial properties of the produced PVA/chitosan film. The antibacterial efficacy of the PVA/chitosan/V2O5 nanoparticles was increased by increasing the V2O5 nanoparticle concentration.74–78
As one will notice, in the past few years the progress in the quest for achieving excellence with respect to wash fastness, antibacterial attributes and the biocompatibility of textile materials in comparison with using only nanoparticle coating has been quite significant and is ongoing. By using nanoparticles–biopolymers deposition on textiles by various deposition techniques, the antibacterial attributes and the biocompatibility of the textile materials can easily be achieved simultaneously. The synergy between biopolymers and nanoparticles leads to the improved functionality of nanocomposite materials, in terms of barrier and antimicrobial properties. Using environmentally friendly biopolymers combined to improve wash fastness adds value to the novel nano-functionalized textiles and reduces their environmental impact. The research on the subject is still open and promises to impact strongly the future of the textile industry.
With respect to the present advantages and disadvantages of using the various biopolymers in combination with nanoparticles in textile fabrics, some of the most usual characteristics are summarized in Table 2.79–95
Advantages and disadvantages of using some usual biopolymers in textile fabrics
CO2: carbon dioxide; O2: oxygen.
A summary of the types of nanoparticles used for the germicidal properties of textile fibers and fabric enabling is presented in Table 3.96–116
Referenced summarized data regarding the use of metal nanoparticles for antibacterial or antifungal performance
Ag: silver; SiO2: silica dioxide; TiO2: titanium dioxide; ZnO: zinc oxide.
All these nanoparticles proved to be effective for antibacterial applications and most of them are already used in some commercial applications, but there are some concerns regarding their long-term toxicity issues as well as their environmental impact if they get loose from the substrate. Their use in combination with biopolymers for textile functionalization seems to minimize those issues, and further studies may soon provide nano-textiles with proper attributes and minimum risks in use.
Conclusions and perspectives
Recent developments of surface nano-structured textile coatings made of biopolymer films and nanoparticles on different textile substrates for enhanced medical applications to diminish the incidence of the multiple range of hospital-acquired infections have been summarized. Their up-to-date biomedical applications and attributes/performance were synthetically revised. The combination of metal and metal oxide nanoparticles with biopolymers has proved to be an efficient technique to generate enhanced antibacterial, virucidal and antifungal properties in textiles, as shown by the most recent publications included in this minireview. The surface tailoring of textiles by nanoparticles–biopolymers used as an alternative for surface modification of textiles, in order to give them biocidal performance is an important research and development topic that is growing day by day. The benefits of the synergistic effects resulting from the simultaneous nanoparticles–biopolymers deposition on textiles by various deposition techniques are the wash fastness of the antibacterial additives to the surface and enhanced biocompatibility of the material in comparison with nanoparticle coating alone. The use of biopolymers to stabilize colloidal dispersions of nanoparticles is giving the particles functionalities for covalent immobilization on textiles to convey a higher durability of antibacterial effect. A synthetic overview of the most usual metal and metal oxide nanoparticles and biopolymers for the antibacterial textile applications was presented. The present state of the art research on the subject opens large perspectives for the further development of green and sustainable routes for the creation of enhanced functionality textiles as well as environmentally friendly solutions for fashion and industrial applications.
Footnotes
Author contributions
Conceptualization: NV, CMR, MPS; methodology: NV, MPS; software: NV, SB, MPS; validation: NV, SB, CMR, SFB, MPS; formal analysis: NV, MPS; investigation: NV, SB, CMR, MPS; resources: NV, CMR, SNV, MPS; data curation: NV, SB, MPS; writing – original draft preparation: NV, MPS; writing – review and editing: NV, MPS, SB; visualization: NV, SB, CMR, SNV, SFB, MPS; supervision: NV, CMR, SNV, SFB, MPS; project administration: NV; funding acquisition: NV. All authors have read and agreed to the published version of the manuscript.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.
Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: The project was financed by Lucian Blaga University of Sibiu and Hasso Plattner Foundation research grants LBUS-IRG-2021-07.
