The Durable Chitosan Functionalization of Cellulosic Fabrics.

In this work, the durability of chitosan functionalization of cellulosic textile substrates, cotton and cotton/polyester blended fabrics, was studied. Chitosan is a naturally occurring biopolymer that can be produced inexpensively. It should be dissolved in an acidic solution to activate its antimicrobial and other properties, i.e., good biocompatibility, bioabsorbability, wound healing, hemostatic, anti-infective, antibacterial, non-toxic, and adsorptive properties. The application of chitosan to textile products has been researched to achieve antimicrobial properties, but the durability, after several maintenance cycles, has not. Chitosan functionalization was carried out using maleic acid (MA) and 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinking and chitosan-activating agents and sodium hypophosphite monohydrate as a catalyst. To determine durability, the fabrics were subjected to 10 maintenance cycles according to ISO 6330:2012 using Reference detergent 3 and drying according to Procedure F. The properties were monitored after the 3rd and 10th cycles. The crosslinking ability of chitosan with cellulosic fabrics was monitored by Fourier infrared spectrometry using the ATR technique (FTIR-ATR). Changes in mechanical properties, whiteness and yellowing, and antimicrobial properties were determined using standard methods. Compared to maleic acid, BTCA proved to be a better crosslinking agent for chitosan.

Influence of Cotton Cationization on Pigment Layer Characteristics in Digital Printing.

The paper examines the influence of cotton cationization on the print quality in terms of penetration, colour yield and colour depth, which have been analysed in comparison to cotton untreated and pretreated with conventional acrylate binder. The process of cationization during mercerization was performed with a cationizing agent Rewin DWR (CHT Bezema). Standard (non-cationized) and cationized fabric, with and without additional layering of binder have been printed by digital inkjet pigment printing method. Moisture management testing (MMT) and dynamic contact angle measurement (drop shape analyzer-DSA30S) were performed on standard and cationized fabric, with and without binder, both with and without pigment layer. After printing, the objective values of colour depth (K/S) and colour parameters L*, C* and h° were analysed. The samples were also analysed by the method of microscopic imaging using a DinoLite microscope. Printed samples were tested to washing fastness, and the results are presented in terms of total colour difference (dECMC), according to CMC(l:c) equation, after the 1st, 3rd, 5th, 7th and 10th washing cycles. Results showed that the cotton cationization will improve the uniformity and coverage of the printed area as well as increase the K/S value. For the samples with binder, the positive effect of cationization on the stability and bond strength between the polymer layer as a pigment carrier with the cotton fabric was confirmed.

Sustainable Alkaline Hydrolysis of Polyester Fabric at Low Temperature.

High crystallinity leads to low hydrophilicity of fabric made of (poly(ethylene terephthalate)) fibers (PET) causing problems in finishing, washing, and dyeing processes. To improve these properties, the surface of PET fibers is usually modified by hydrolysis. Alkaline hydrolysis is a conventional process usually performed at a temperature higher than 100 °C for more than 1 h. However, the use of strong alkali and high processing temperatures (>100 °C) can lead to fabric damage and a negative impact on the environment. Therefore, in this paper, the possibility of hydrolysis of the PET fibers in the fabric in a sustainable, energy-efficient process was researched. The influence of low temperature (60-100 °C) and an accelerator (a cationic surfactant HDTMAC) to PET alkaline hydrolysis was studied through weight loss, the loss in breaking force, and fiber morphology. The kinetics of PET dissolution in 1.5 mol cm-3 NaOH at low temperature with and without the addition of HDTMAC was determined and the activation energy was calculated according to the theoretical model. It has been confirmed that PET hydrolysis can be carried out in 1.5 mol cm-3 NaOH with the addition of HDTMAC as an accelerator at 80 °C for 10 min. This process is more economically and energetically acceptable than the conventional process, and is therefore more sustainable.

Natural Dyeing of Modified Cotton Fabric with Cochineal Dye.

Natural dyes are not harmful to the environment owing to their biodegradability. For dye application to textiles, salts are necessary as mordant or electrolytes and make an environmental impact. In this paper, the influence of cationization during mercerization to the dyeing of cotton fabric with natural dye from Dactylopius coccus was researched. For this purpose, bleached cotton fabric as well as fabric cationized with Rewin OS was pre-mordanted using iron(II) sulfate heptahydrate (FeSO4·7H2O) and dyed with natural cochineal dye with and without electrolyte addition. For the characterization of surface changes after cationization, an electrokinetic analysis on SurPASS was performed and compared to pre-mordanting. For determination of dye exhaustion, the analysis of dye solution was performed on a UV/VIS spectrophotometer Cary 50 Solascreen. Spectrophotometric analysis was performed using a Datacolor 850 spectrophotometer, measuring remission "until tolerance" and the whiteness degree, color parameters, color depth (K/S), and colorfastness of dyed fabric were calculated. Levelness was determined by visual assessment. Cationized cotton fabrics showed better absorption and colorfastness. Pre-mordanting and cationization showed synergism. The electrolytes improved the process of dye absorption. However, when natural dyeing was performed on cotton fabric cationized during mercerization, similar chromacity, uniform color, and colorfastness were achieved with and without electrolyte, resulting in pure purple hue of cochineal. For achieving a violet hue, pre-mordanting with Fe-salt was needed. Therefore, salt can be reduced or even unnecessary, which makes this process of natural dyeing more environmentally friendly.

Trichromatic Vat Dyeing of Cationized Cotton.

This article deals with cationization of cotton during mercerization and its effects on trichromatic vat dyeing. If cationization is carried out during the after-treatment, regardless of cotton pretreatment, the reaction takes place on the surface and blocks cellulose groups, subsequently resulting in uneven coloration. However, when cationization is carried out with an epihalohydrin during the mercerization process, new cellulose is formed in which the cationic compound is uniformly distributed and trapped between cellulose chains, resulting in uniform coloration after the dyeing process. The reaction time for the process during mercerization is 24 h, thus a more favorable process was researched. Based on electrokinetic analysis, it was found that 5 h was sufficient for the reaction with 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC). The cationization of cotton contributed to the processes of vat dyeing. The change in charge upon cationization resulted in very high adsorption of vat-dye anions, indicating that ionic bonding occurred in addition to van der Waals forces. The color depth improved by more than 10 times. It should be emphasized that the colors with higher chroma and targeted color hue, especially in trichromatic dyeing, were obtained on cationized cotton, in contrast to standard cotton fabrics. The color differences obtained under the different light sources indicate the occurrence of metamerism. Considering the color fastness to laundering, vat-dyed cationized fabrics of all colors may be used in hospitals or other environments where high hygiene and oxidative bleaching are required.

Poly(ε-caprolactone) Titanium Dioxide and Cefuroxime Antimicrobial Scaffolds for Cultivation of Human Limbal Stem Cells.

Limbal Stem Cell Deficiency (LSCD) is a very serious and painful disease that often results in impaired vision. Cultivation of limbal stem cells for clinical application is usually performed on carriers such as amniotic membrane or surgical fibrin gel. Transplantation of these grafts is associated with the risk of local postoperative infection that can destroy the graft and devoid therapeutic benefit. For this reason, electrospun scaffolds are good alternatives, as proven to mimic the natural cells surroundings, while their fabrication technique is versatile with regard to polymer functionalization and scaffolds architecture. This study considers the development of poly(ε-caprolactone) (PCL) immune-compatible and biodegradable electrospun scaffolds, comprising cefuroxime (CF) or titanium dioxide (TiO2) active components, that provide both bactericidal activity against eye infections and support of limbal stem cells growth in vitro. The PCL/CF scaffolds were prepared by blend electrospinning, while functionalization with the TiO2 particles was performed by ultrasonic post-processing treatment. The fabricated scaffolds were evaluated in regard to their physical structure, wetting ability, static and dynamic mechanical behaviour, antimicrobial efficiency and drug release, through scanning electron microscopy, water contact angle measurement, tensile testing and dynamic mechanical analysis, antimicrobial tests and UV-Vis spectroscopy, respectively. Human limbal stem cells, isolated from surgical remains of human cadaveric cornea, were cultured on the PCL/CF and PCL/TiO2 scaffolds and further identified through immunocytochemistry in terms of cell type thus were stained against p63 marker for limbal stem cells, a nuclear transcription factor and cytokeratin 3 (CK3), a corneal epithelial differentiation marker. The electrospun PCL/CF and PCL/TiO2 successfully supported the adhesion, proliferation and differentiation of the cultivated limbal cells and provided the antimicrobial effect against Pseudomonas aeruginosa, Staphylococcus aureus and Candida albicans.

Conjugates of Chitosan and Calcium Alginate with Oligoproline and Oligohydroxyproline Derivatives for Potential Use in Regenerative Medicine.

New materials that are as similar as possible in terms of structure and biology to the extracellular matrix (external environment) of cells are of great interest for regenerative medicine. Oligoproline and oligohydroxyproline derivatives (peptides 2-5) are potential mimetics of collagen fragments. Peptides 2-5 have been shown to be similar to the model collagen fragment (H-Gly-Hyp-Pro-Ala-Hyp-Pro-OH, 1) in terms of both their spatial structure and biological activity. In this study, peptides 2-5 were covalently bound to nonwovens based on chitosan and calcium alginate. Incorporation of the peptides was confirmed by Fourier transform -infrared (FT-IR) and zeta potential measurements. Biological studies (cell metabolic activity by using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test and Live/Dead assay) proved that the obtained peptide-polysaccharide conjugates were not toxic to the endothelial cell line EA.hy 926. In many cases, the conjugates had a highly affirmative influence on cell proliferation. The results of this study show that conjugates of chitosan and calcium alginate with oligoproline and oligohydroxyproline derivatives have potential for use in regenerative medicine.

The Chitosan Implementation into Cotton and Polyester/Cotton Blend Fabrics.

Chitosan is an environmentally friendly agent that is used to achieve the antimicrobial properties of textiles. Nowadays, the binding of chitosan to the textiles has been thoroughly researched due to the increasing demands on the stability of achieved properties during the textile care processes. Most crosslinking agents for chitosan are not safe for humans or environment, such as glutaric aldehyde (GA) and formaldehyde derivatives. Eco-friendly polycarboxyilic acids (PCAs) are usually used in after-treatment. In this work, chitosan powder was dissolved in citric acid with sodium hydrophosphite (SHP) as a catalyst. Standard cotton (CO) and polyester/cotton (PES/CO) fabrics were pretreated in 20% NaOH, similar to mercerization, in order to open the structure of the cotton fibers and hydrolyze polyester fibers, continued by finishing in the gelatin chitosan bath. Afterwards, the hot rinsing process, followed by drying and curing, closed the achieved structure. The main objective was to achieve durable antimicrobial properties to multiple maintenance cycles CO and PES/CO fabric in order to apply it in a hospital environment. The characterization of fabrics was performed after treatment, first and fifth washing cycles according ISO 6330:2012 by field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR-ATR), electrokinetic analysis (EKA), by the determination of tensile properties and mechanical damage (wear), and the antimicrobial activity. The application of 20% NaOH led to the swelling and mercerization of cotton cellulose, and hydrolysis of polyester, resulting in better mechanical properties. It has been confirmed that the chitosan particles were well implemented into the cotton fiber and onto to the polyester component of PES/CO blend. The presence of chitosan was confirmed after five washing cycles, but in lower quantity. However, achieved antimicrobial activity is persistent.

Enzymatic Modification of Polyamide for Improving the Conductivity of Water-Based Multilayer Nanocoatings.

Enzymatic modification, using a protease from Bacillus licheniformis (Subtilisin A), was carried out on polyamide 6.6 (PA6.6) fabric to make it more amenable to water-based nanocoatings used to impart electrical conductivity. The modified PA6.6 fibers exhibit a smoother surface, increased hydrophilicity due to more carboxyl and amino groups, and larger ζ-potential relative to unmodified polyamide. With its improved hydrophilicity and surface functionality, the modified textile is better able to accept a water-based nanocoating, composed of multiwalled carbon nanotubes (MWCNT) stabilized by sodium deoxycholate (DOC) and poly(diallyldimethylammonium chloride) (PDDA), deposited via layer-by-layer assembly. Relative to unmodified fabric, the enzymatically modified fibers exhibit lower sheet resistance as a function of PDDA/MWCNT-DOC bilayers deposited. This relatively green technique could be used to impart a variety of useful functionalities to otherwise difficult-to-treat synthetic fibers like polyamide.

Modified cotton socks--possibility to protect from diabetic foot infection.

Diabetes has become a major public health problem and grows rapidly in the most developed countries of the world. Beside genetic and environmental factors, lifestyle habits play an important role in the development and progression of diabetes mellitus. According to the World Health Organization (WHO) about 15% of diabetic patients develop a foot ulcer in need of medical care. Infection is a serious complication and it is the major responsible cause of lower limb amputation. In this paper the possibility to protect from diabetic foot infection with modified cotton socks. Therefore, the socks made of modified cotton yarn by natural minerals and active carbon were investigated in vitro (fabric hand-friction and adsorption) and in vivo (3 IDDM, 4NIDDM, 3 GDM to sweat and fabric hand) to accomplish highest possible level of comfort for diabetic patients. Antimicrobial protection to Gram positive, Gram negative and micro fungi was determined as well. For durability all the characteristics were investigated after 15 washing cycles.

Discrepancy of whiteness and UV protection in wet state.

The incidence of skin cancer is increasing by epidemic proportions. Basal cell cancer remains the most common skin neoplasm, and simple excision is generally curative. On the other hand, aggressive local growth and metastasis are common features of malignant melanoma, which accounts for 75 percent of all deaths associated with skin cancer. In Croatia only, more than 20,000 new cases of skin cancer has been diagnosed in 2008 of which melanoma 286 new cases and 118 yearly deaths in men, and 275 new cases and 79 deaths in women population. The back sides in men and women, as well as the lower limbs in women, are the most common site for melanomas. The primary cause of skin cancer is believed to be a long exposure to solar ultraviolet (UV) radiation crossed with the amount of skin pigmentation in the population. There are indications that other parts of solar spectrum (e.g., blue light) might also have effects on skin and eyes. Most people think all clothing will protect them, but that's not the case. UV clothing can show UVprotection, but in the most cases it does not provide full sun screening properties. UV protection ability highly depends on large number of factors such are type of fiber, fabric surface and construction, type and concentration of dyestuff, fluorescent whitening agent (FWA), UV-B protective agents, as well as nanoparticles, if applied. For that reason, jeans and tightly woven fabrics offer a very good level of protection. However, on a hot summer day, those aren't the kinds of clothing people usually reach for. More often, when they are on the beach, they wear T-shirt, as well during the swimming in the sea, thinking that it will protect them. Therefore, in this paper the discrepancy of UVprotection in wet state was researched. For the purpose, FWA and UVabsorber were applied in wide concentration range to white cotton knit fabrics commonly used for T-shirts. Afterwards, the discrepancy in whiteness and UVprotection was research in distilled water as well as Adriatic Sea water.

UV clothing and skin cancer.

Skin cancer incidence in Croatia is steadily increasing in spite of public and governmental permanently measurements. It is clear that will soon become a major public health problem. The primary cause of skin cancer is believed to be a long exposure to solar ultraviolet (UV) radiation. The future designers of UV protective materials should be able to block totally the ultraviolet radiation. The aim of this paper is to present results of measurements concerning UV protecting ability of garments and sun-screening textiles using transmission spectrophotometer Cary 50 Solarscreen (Varian) according to AS/NZS 4399:1996; to show that standard clothing materials are not always adequate to prevent effect of UV radiation to the human skin; and to suggest the possibilities for its improvement for this purpose.