Anthraquinones from the Fungus Dermocybe sanguinea as Textile Dyes

This study is based on the multidiciplinary approach of using natural colorants as textile dyes. The author was interested in both the historical and traditional aspects of natural dyeing as well as the modern industrial applications of the pure natural compounds. In the study, the anthraquinone compounds were isolated as aglycones from the ectomycorrhizal fungus Dermocybe sanguinea. The endogenous beta-glucosidase of the fungus was used to catalyse the hydrolysis of the O-glycosyl linkage in emodin- and dermocybin-1-beta-D-glucopyranosides. The method, in which 10.45 kg of fresh fungi was starting material, yielded two fractions: 56.0 g of Fraction 1 (94% of the total amount of pigment,) consisting almost exclusively of the main pigments emodin and dermocybin, and 3.3 g of Fraction 2 (6%) consisting mainly of the anthraquinone carboxylic acids. The anthraquinone compounds in Fractions 1 and 2 were separated by one- and two-dimensional thin-layer-chromatography (TLC) using silica plates. 1D TLC showed that neither an acidic nor a basic solvent system alone separated completely all the anthraquinones isolated from D. sanguinea, in spite of the variation of the rations of the solvent components in the systems. Thus, a new 2D TLC technique was developed, applying n-pentanol-pyridine-methanol (6:4:3, v/v/v) and toluene-ethyl acetate-ethanol-formic acid (10:8:1:2, v/v/v/v) as eluents. Fifteen different anthraquinone derivatives were completely separated from one another. Emodin, physcion, endocrocin, dermolutein, dermorubin, 5-chlorodermorubin, emodin-1-beta-D-glucopyranoside, dermocybin-1-beta-D-glucopyranoside and dermocybin, and five new compounds, not earlier identified in D. sanguinea, 7-chloroemodin, 5,7-dichloroemodin, 5,7-dichloroendocrocin, 4-hydroxyaustrocorticone and austrocorticone, were separated and identified on the basis of their Rf-values, UV/Vis spectra and mass spectra. One substance remained unidentified, because of its very low concentration. The anthraquinones in Fractions 1 and 2 were preparatively separeted by liquid-liquid partition, with isopropylmethyl ketone and aqueous phosphate buffer as the solvent system. Advantage was taken of the principle of stepwise pH-gradient elution. The multiple liquid-liquid partition (MLLP) offered an excellent method for the preparative separation of compounds, which contain acidic groups such as the phenolic OH and COOH groups. Due to their strong aggregation properties, these compounds are, without derivatization, very difficult to separate on a preparative scale by chromatographic methods. By the MLLP method remarkable separations were achieved for the components in each mixture. Emodin and dermocybin were both obtained from Fraction 1 in a purity of at least 99%. Pure emodin and dermocybin were applied as mordant dyes to wool and polyamide and as disperse dyes to polyester and polyamide, using the high temperature (HT) technique. A mixture of dermorubin and 5-chlorodermorubin was applied as an acid dye to wool. In these experiments, synthetic dyes were used as references. Experiments were also performed using water extract of the air-dried fungi as dye liquor for wool and silk. The main colouring compounds in the crude water extract were emodin and dermocybin, which indicated that the O-glycosyl linkages in emodin- and dermocybin-1-beta-D-glucopyranosides were broken by the beta-glucosidase enzyme. Apparently, the hydrolysis occurred during the drying of the fungi and during the soaking of the dried fruit bodies overnight when preparing the dyebath. The colour of each dyed material was investigated in terms of the CIELAB L*, a* and b* values, and the colour fastness to light, washing and rubbing was tested according to the ISO standards. In the mordant dyeing experiments, emodin dyed wool and polyamide yellow and red, depending on the pH of the dyebath. Dermocybin gave purple and violet colours. The colour fastness of the mordant-dyed fabrics varied from good to moderate. The fastness properties of the natural anthraquinone carboxylic acids on wool were good, indicating the strength of the ionic bonds between the COO- groups of the dyes and the NH3+ groups of the fibres. In the disperse dyeing experiments, emodin dyed polyester bright yellow and dermocybin bright reddish-orange, and the fabrics showed excellent colour fastness. In contrast, emodin and dermocybin successfully dyed polyamide brownish-orange and wine-red, respectively, but with only moderate fastness. In industrial dyeing processes, natural anthraquinone aglycone mixtures dyed wool and silk well even at low concentrations of mordants, i.e. with 10% of the weight of the fibre (owf) of KAl(SO4)2 and 1 or 0.5% owf of other mordants. This study showed that purified natural anthraquinone compounds can produce bright hues with good colour-fastness properties in different textile materials. Natural anthraquinones have a significant potential for new dyeing techniques and will provide useful alternatives to synthetic dyes.

Studies on Mechanical Properties of Full-Biodegradable Starch-PVA-Polyester Films

A kind of full-biodegradable film material is discussed in this article. The film material is composed of starch, PVA, degradable polyesters(PHB, PHB-V, PCL) with built plasticizer, a cross-linking reinforcing agent and a wet strengthening agent. It contains a high percentage of starch, costs cheap and is excellent in weather fastness, temperature resistance and waterproof and it could be completely biodegraded. The present paper deals mainly with a new technical route using a new type of electromagnetic dynamic blow molding extruder and some effects on mechanical properties of the system.

Tributyltin (TBT) resistance in Aeromonas molluscorum Av27

O tributilestanho (TBT) é considerado um dos xenobióticos mais tóxicos, produzidos e deliberadamente introduzidos no meio ambiente pelo Homem. Tem sido usado numa variedade de processos industriais e subsequentemente descarregado no meio ambiente. O tempo de meia-vida do TBT em águas marinhas é de várias semanas, mas em condições de anóxia nos sedimentos, pode ser de vários anos, devido à sua degradação mais lenta. Embora o TBT tenha sido descrito como sendo tóxico para eucariotas e procariotas, muitas bactérias podem ser resistentes a este composto. O presente trabalho teve como objetivo principal elucidar o mecanismo de resistência ao TBT em bactérias. Para além disso, pretendeu-se desenvolver um biorepórter para detectar TBT no ambiente. Para atingir estes objetivos foram delineadas várias tarefas cujos principais resultados obtidos se apresentam a seguir. Várias bactérias resistentes ao TBT foram isoladas de sedimento e água do Porto de Pesca Longínqua (PPL) na Ria de Aveiro, Portugal. Entre estas, Aeromonas molluscorum Av27 foi selecionada devido à sua elevada resistência a este composto (concentrações até 3 mM), à sua capacidade de degradar o TBT em compostos menos tóxicos (dibutilestanho, DBT e monobutilestanho, MBT) e também por usar o TBT como fonte de carbono. A. molluscorum Av27 foi caracterizada genotipica e fenotipicamente. Os fatores de virulência estudados mostraram que esta estirpe i) possui atividade lipolítica; ii) não é citotóxica para células de mamíferos, nomeadamente para células Vero; iii) não possui integrões de classe I e II e iv) possui cinco plasmídeos com aproximadamente 4 kb, 7 kb, 10 kb, 100 kb e mais de 100 kb. Estes resultados mostraram que a estirpe Av27 não é tóxica, aumentando assim o interesse nesta bactéria para futuras aplicações, nomeadamente na bioremediação. Os testes de toxicidade ao TBT mostraram que este composto tem um impacto negativo no crescimento desta estirpe, bem como, na densidade, no tamanho e na atividade metabólica das células e é responsável pela formação de agregados celulares. Assim, o TBT mostrou ser bastante tóxico para as bactérias interferindo com a atividade celular geral. O gene Av27-sugE, que codifica a proteína SugE pertencente à família das “small multidrug resistance proteins” (SMR), foi identificado como estando envolvido na resistência ao TBT nesta estirpe. Este gene mostrou ser sobreexpresso quando as células crescem na presença de TBT. O promotor do gene Av27-sugE foi utilizado para construir um bioreporter para detetar TBT, contendo o gene da luciferase do pirilampo como gene repórter. O biorepórter obtido reúne as características mais importantes de um bom biorepórter: sensibilidade (intervalo de limite de detecção de 1-1000 nM), rapidez (3 h são suficientes para a deteção de sinal) e, possivelmente, não é invasivo (pois foi construído numa bactéria ambiental). Usando sedimento recolhido no Porto de Pesca Longínqua da Ria de Aveiro, foi preparada uma experiência de microcosmos com o intuito de avaliar a capacidade de Av27 para bioremediar o TBT, isoladamente ou em associação com a comunidade bacteriana indígena. A análise das amostras de microcosmos por PCR-DGGE e de bibliotecas de 16S rDNA revelaram que a comunidade bacteriana é relativamente estável ao longo do tempo, mesmo quando Av27 é inoculada no sedimento. Para além disso, o sedimento estuarino demonstrou ser dominado por bactérias pertencentes ao filo Proteobacteria (sendo mais abundante as Delta e Gammaproteobacteria) e Bacteroidetes. Ainda, cerca de 13% dos clones bacterianos não revelaram nenhuma semelhança com qualquer dos filos já definidos e quase 100% afiliou com bactérias não cultiváveis do sedimento. No momento da conclusão desta tese, os resultados da análise química de compostos organoestânicos não estavam disponíveis, e por essa razão não foi possível tirar quaisquer conclusões sobre a capacidade desta bactéria remediar o TBT em sedimentos. Esses resultados irão ajudar a esclarecer o papel de A. molluscorum Av27 na remediação de TBT. Recentemente, a capacidade da estirpe Av27 remediar solo contaminado com TBT foi confirmada em bioensaios realizados com plantas, Brassica rapa e Triticum aestivum (Silva 2011a), e também com invertebrados Porcellionides pruinosus (Silva 2011B). Assim, poder-se-á esperar que a bioremediação do sedimento na experiência de microcosmos também tenha ocorrido. No entanto, só a análise química dos compostos organostânicos deverá ser conclusiva. Devido à dificuldade em realizar a análise analítica de organoestânicos, um método de bioensaio fácil, rápido e barato foi adaptado para avaliar a toxicidade do TBT em laboratório, antes de se proceder à análise química das amostras. O método provou a sua utilidade, embora tenha mostrado pouca sensibilidade quando se usam concentrações de TBT baixas. Em geral, os resultados obtidos contribuíram para um melhor entendimento do mecanismo de resistência ao TBT em bactérias e mostraram o potencial biotecnológico de A. molluscorum Av27, nomeadamente, no que refere à sua possível aplicação na descontaminação de TBT no ambiente e também no desenvolvimento de biorepórteres.

Efecto de la glicemia materna en la monitoría electrónica fetal

Introducción: Después del ingreso de la monitoría fetal electrónica como estudio de bienestar fetal, se ha considerado por décadas que un aporte de carbohidratos a la gestante antes de la realización de la monitoría fetal influye en el reporte pero existen estudios que consideran que los niveles de glicemia materna no afecta la variabilidad de la monitoría fetal. Metodología: Se realizó un estudio de corte transversal, para evaluar el efecto de la glicemia materna en la monitoría fetal electrónica comparando los valores de glicemia materna con su resultado, según la categorización del ACOG. Las principales variables fueron las horas de ayuno, valores de glicemia, variabilidad de la monitoría fetal y presencia de aceleraciones. Resultados: Se incluyeron un total de 60 pacientes, que ingresaron al servicio de obstetricia y ginecología del Hospital Universitario Mayor Méderi en el periodo de estudio. No se encontraron diferencias estadísticamente significativas entre los resultados de monitoría fetal y los valores de glicemia materna. Ninguna paciente presentó monitoría categoría III (según categorización de la ACOG). Discusión Se requieren estudios analíticos más amplios para evaluar el papel de la glicemia en el resultado de la monitoría, pero el presente estudio sugiere que no existe relación entre la glicemia materna y el resultado de la monitoría fetal electrónica en la categorización del Colegio Americano De Ginecología Y Obstetricia (ACOG).

Comparative analysis of two selective bleaching methods on alpaca fibers

Dark brown Alpaca fiber was reduced in shade via selective bleaching with peroxide. Two selective oxidative bleaching methods were tested on alpaca top to assess their effectiveness for color removal and fiber quality properties. Color change, bundle strength, weight loss, fiber diameter, surface modification, dye-ability and dye wash fastness were assessed for both methods and compared with the original brown top. Bleach method 1 (BL-I) showed little surface modification, 5.8 % weight loss and 2.4 % strength loss. D1925 yellowness index was reduced to 74.3 from 83.1 and provided a good base for the dyeing of medium to deep shades. Bleach method 2 (BL-II) displayed considerable surface modification, 7.8 % weight loss and 18 % strength loss. BL-II also resulted in a mean diameter reduction of 1.9 micron during bleaching. Yellow-ness was reduced to 64.5 from 83.1 and provided a very good base for the dyeing of medium to deep shades. BL-I showed better exhaustion of the pre-metallised dye Lanaset Violet B than BL-II. Wash fastness for BL-II was 1 grey scale unit poorer than BL-I. BL-II showed far better color clarity at pale depths however the wash fastness of the finished product was not good enough to maintain the depth or clarity of the color. BL-I showed poorer clarity of color but exhibited better wash fastness results.

Photochromic wool fabrics from a hybrid silica coating

In this work, a photochromic wool fabric has been prepared by applying a photochromic-dye hybrid silica sol-gel onto the surface of fabric. The photochromic fabric was found to have a very quick optical response. Two types of silica were used as the matrix material, and the type of silica had a small effect only on the photochromic performance, the fabric washing fastness, and water contact angle, but affected the fabric handle property considerably. The silica from a precursor containing a long alkyl chain showed very little influence on the fabric handle and better photochromic performance than that containing a phenyl group.

Conductive poly(α,ω-bis(3-pyrrolyl)alkanes)-coated wool fabrics

Cross-linked poly(α,ω-bis(3-pyrrolyl)alkanes) were directly applied to woven wool substrates by either chemical, vapour or mist polymerization methods. Choice of dopant could greatly improve the surface resistance. The optimum coating on textiles with the lowest surface resistance, highest colour-fastness and stability was achieved using a mist polymerization method with 1,8-bis(pyrrolyl)octane, iron(III) chloride (FeCl₃) as the oxidant and p-toluene sulfonic acid sodium salt (pTSA) as the dopant.

Improving the color yield of ink-jet printing on cationized cotton

This study examines the performance of digital ink-jet printing on cationized cotton treated with polyepichlorohydrin-dimethylamine (PECH-amine). The results show that the color yield of ink-jet printing with reactive inks on cationic modified cotton is much greater than that on untreated cotton. The effect on the increase of color yield by cationic modification is greater than that by preparation with alkali, urea, and thickener. The reason for this is that introducing positively charged sites increases dye uptake and dye fixation on cationized cotton. The results also show that cationic modification with PECH-amine decreases the rub fastness but increases the wash fastness of the treated cotton.

Nano zinc oxide for UV protection of textiles

This paper describes the effect on the fading of dyed polyester fabrics in artificial sunlight, when the Ultra Violet (UV) component of the radiation was blocked by coating the fabric with zinc oxide nanoparticles, dispersed in an acrylic polymer. Zinc oxide is photoactive and generates superoxide and hydroxyl radicals (Reactive Oxygen Species; ROS) when irradiated with UV in the presence of oxygen and water. The results for the four dyes studied show that different dye chromophores interact differently with ROS. Selection of dyes with anti oxidant properties or addition of other anti oxidants may reduce the adverse effects of ROS

One-bath union dyeing of wool/polytrimethylene terephthalate blends

The one-bath dyeing of blends of polytrimethylene terephthalate (PTT) staple and wool has been investigated. The exhaustion of selected Terasil disperse dyes on PTT fibre and Lanasol reactive dyes on wool was measured as a function of temperature, together with the cross-staining of the Terasil dyes on the wool component and the Lanasol dyes on PTT component. Most Terasil disperse dyes achieved satisfactory dye uptake on PTT at 110 °C, whereas on conventional polyester (polyethylene terephthalate) temperatures of up to 130 °C are required. An optimised union-dyeing technique for wool/PTT blends was developed which minimised the staining of Terasil disperse dyes on wool and produced dyed goods with high levels of wet colour fastness. Carriers were not required to enhance the dyeability of PTT at low temperatures. The wool component appeared to be protected against damage at 110 °C by the reactive dyes. The results indicate the potential for blending PTT fibre and wool to produce fabrics that are easier to dye at lower temperatures than conventional wool/polyester blends.

Fast response photochromic textiles from hybrid silica surface coating

In this study, a hybrid silica sol-gel embedded with a photochromic dye has been applied to wool fabric to form a photochromic coating. The treated wool fabrics showed very quick photochromic response. Five different silanes have been used as the silica precursor, and the resultant coating showed slight differences in photochromic performance, fabric washing fastness, and surface hydrophilicity. However, the silica type had a considerable influence on fabric handle property. The silica matrix from the silane containing a long alkyl chain had a very little influence on the fabric handle and better photochromic performance than those from other different silane precursors.

Nanoparticle coatings for UV protective textiles

As the intensity of UV radiation increases every year, effective methods to block UV rays to protect human skin, plastics, timber and other polymer materials are urgently sought. Textiles serve as important materials for UV protection in many applications. The utilisation of nanoparticles to textile materials has been the object of several studies aimed at producing finished fabrics with different performances. This article reviews the recent advancement in the field of UV blocking textiles and fibers that are functionalised with nanostructured surface coatings. Different types of UV blocking agents are discussed and various examples of UV blocking textiles utilising ZnO and TiO₂ are presented. Future challenges such as wash-fastness and photocatalysis are also discussed.

Effect of atmospheric plasma treatment on pad-dyeing of natural dyes on wool

Plasma treatment is an emerging surface modification technique that alters dye uptake of wool without using chemicals or water for pre-treatment. Padding is an established continuous dyeing technique known for its efficient use of water, time and energy. This study combined these two techniques for colouration of wool fabric using two natural dyes derived from the Acacia plant family. The investigation focused on the effects of plasma treatment and obtaining unique patterning effects. Helium (100%) and a mixture of helium and nitrogen (95%/5%) were used as the plasma gases under atmospheric conditions. Plasma treated wool fabric was padded with the above natural dyes. Copper sulphate and ferrous sulphate were applied on the dyed fabric as mordant yielding neutral shades of beige and grey respectively. Up to a 30% enhancement of dye adsorption on plasma treated wool substrate was observed as compared to untreated sample for both gases used. This higher adsorption indicates the hydrophilic character of the natural dyes used. Key performance parameters such as fastness to washing, rubbing and light were tested and found to be satisfactory. A single process tone-on-tone pattern was achieved by controlling the plasma exposure of treated area. This study concluded that a merger of natural dyes with modern plasma treatment and padding techniques for wool colouration was feasible.

Coloration of cotton fibers with anisotropic silver nanoparticles

Anisotropic silver nanoparticles were assembled on cotton fibers to realize the coloration of cotton. The assembly of silver nanoparticles on fibers was achieved by linking of poly(diallyldimethylammonium chloride) (PDDA) at room temperature. The silver nanoparticle treated cotton showed different colors because of localized surface plasmon resonance (LSPR) property of silver nanoparticles. The coloration was completed through electrostatic interaction between the PDDA treated cotton surface and the anisotropic silver nanoparticles in the reaction system. Scanning electron microscopy (SEM) characterization demonstrated that the morphologies of silver nanoparticles remained unchanged during the coloration process, so the treated cotton inherited the LSPR optical features of silver nanoparticles. Moreover, the cotton colorated with silver nanoparticles showed reasonably good color fastness to washing, which will facilitate the practical application of this coloration process.

Functionalization of bamboo pulp fabrics with noble metal nanoparticles

Noble metal (gold and silver) nanoparticles (NPs) were synthesized in-situ on bamboo pulp fabrics. The gold NPs were reduced by bamboo pulp fabrics and bonded to fibers under heating, and an alkaline condition was needed to synthesize silver NPs in the presence of bamboo pulp fabrics. The synthesized gold and silver NPs endowed bamboo pulp fabrics with different colors because of their localized surface plasmon resonance (LSPR) property. The colors of the fabrics treated with metal NPs were extended through complex synthesis of gold and silver NPs in different proportions. The bamboo pulp fabrics treated with noble metal NPs showed good fastness to light and rubbing. In addition, the gold and silver NPs imparted bamboo pulp fabrics excellent UV protection property and remarkable antibacterial activity.