Application of Capillary Electromigration Methods in the Analysis of Textile Dyes—Review

Fiber traces are one of (micro)traces that can be found at a crime scene. They are easily transferable and, like other forms of evidence, can provide a link between a suspect and a victim. The main purpose of this review is to present methods developed to examine textile dyes extracted for forensic purposes using different capillary electromigration methods (CEMs). Scientific papers, mainly from the 20th century, provide reliable methods for the separation of water-soluble dyes. However, dyes insoluble in aqueous solutions have been and still are a challenge. Another problem is the sensitivity of the developed methods, which is, in most cases, insufficient for forensic examination of dyes extracted from a single fiber preserved at the crime scene. Although the methodologies already developed and presented in this review have the potential to be applied in a comparative analysis of textile dye traces, there seems to be a lot of work to be conducted. Some ideas on how to resolve these problems are presented and discussed in the article.     

Development of the Microemulsion Electrokinetic Capillary Chromatography Method for the Analysis of Disperse Dyes Extracted from Polyester Fibers

The study aimed to develop a method for the separation of dispersed dyes extracted from polyester fibers. Nine commercially available disperse dyes, which were used to dye three polyester fabrics, were tested. Extraction of dyes from 1 cm long threads was carried out in chlorobenzene at 100 °C for 6 h. The separation was performed using microemulsion electrokinetic capillary chromatography (MEEKC) with photodiode array detection. Microemulsion based on a borate buffer with an organic phase of n-octane and butanol and a mixture of surfactants, sodium dodecyl sulphate and sodium cholate, were used. The addition of isopropanol and cyclodextrins to microemulsion resulted in a notable improvement in resolution and selectivity. The content of additives was optimized by using the Doehlert experimental design. Values of the coefficient of variance obtained in the validation process, illustrating the repeatability and intermediate precision of the migration times fit in the range of 0.11–1.24% and 0.58–3.21%, respectively. The developed method was also successfully applied to the differentiation of 28 real samples—polyester threads collected from clothing. The obtained results confirmed that proposed method may be used in the discriminant analysis of polyesters dying by disperse dyes and is promisingly employable in forensic practice.     

Chemical cationization of cotton fabric for improved dye uptake

Cotton fabric is usually dyed with reactive dyes. During the dyeing process, a large amount of salt is required to achieve higher exhaustion of the dye from the dyebath onto the fiber. Dyeing of cotton with reactive dyes has a substantial environmental impact due to the discharge of a large volume of highly colored and saline effluents. Chemical cationization allows cotton fibers to be dyed without salt by chemically modifying cellulosic macromolecules to introduce positively charged sites. In this study, cotton fabric was cationized using (3-chloro-2-hydroxylpropyl) trimethyl-ammonium chloride (CHPTAC). Dye uptake was assessed using two reactive dyes, CI Reactive Blue 235 and CI Reactive Blue 19. Dye exhaustion kinetics were determined using a Datacolor-HueMetrix Monitor system. Analysis of variance demonstrated significant effects of CHPTAC concentration and exhaustion time on the percent exhaustion. Color strength at the end of the dyeing cycle was significantly higher for cationized fabrics compared to the control fabric. This work shows that treatment of cotton with CHPTAC enhanced dye uptake properties due to the introduction of cationic sites and resulted in superior dyeing without the addition of salt.     

丝素蛋白纤维的接枝聚合Ⅲ．丝素蛋白纤维的接枝聚合染色

本文提出了通过接枝聚合物将丝素蛋白纤维的染色的设想：在染料分子上引入丙烯酰基，然后将其接枝到丝素蛋白纤维表面。将2－羟基－4－丙烯酰氧二苯酮（HAOBP），1－羟基－2－丙烯酰氧蒽醌（HAOAQ）和1，5，8－三羟基－2－丙烯酰氧蒽醌（THAOAQ）等三种染料，分别用无引发剂存在下的接枝聚合法接枝到丝素蛋白纤维表面，使丝素蛋白纤维分别染成了浅黄、浅红和浅紫三种颜色。这样染色了的丝素蛋白纤维在浓酸或浓碱溶液中回流，未发生任何裉色现象，并且其热稳定性和紫外稳定性也得到了显著的改善。力学性能未下降。采用甲基丙烯酸甲酯（MMA）与染料单体共同进行接枝聚合染色，可以提高丝素蛋白纤维的光泽度，并可将接枝整理和染色两道工序合而为一。HAOBP、HAOAQ和THAOAQ在丝素蛋白纤维上的接枝率（mol单体／g丝），具有如下顺序，HAOBP＞HAOAQ＜THAOAQ。该顺序与它们的亲水性顺序恰好相反，这一结果支持了Imoto等人的无引发剂存在下的接枝聚合发生在丝素蛋白纤维的疏水区域的观点。     

Synthesis and Characterization of Novel Monoazo Naphthalimide Disperse Dyes Containing Carboxylic Acid Group with High Heat Fastness Properties

A group of novel monoazo disperse dyes containing carboxylic acid‐1,8‐naphthalimide group has been synthesized. All intermediates and dyes were purified by recrystalization and the column chromatography method. The purified products were characterized by ¹H NMR, ¹³C NMR, FTIR, DSC, UV‐VIS and Elemental Analysis. Spectrophotometric investigations of the synthesized dyes in different solvents were carried out in order to obtain their absorption maxima, molar extinction coefficients and solvatochromic effects. The absorption maxima of the synthesized dyes in acetone varied (513‐549 nm) and the molar extinction coefficient was (17405‐38939 l/mol cm). By changing the media from chloroform to DMF, the solvatochromism effect for all dyes increased. Dispersion of the synthesized dyes was prepared in water containing dispersing agent and applied to polyester fabrics. The dyed fabrics showed that all of the synthesized dyes were suitable for coloring polyester fibers, producing deep red to bluish red with very good fastness properties.     

Polyurethanes as polymerizable dyes for hydrophobic polyester fabric

The present invention is to provide a novel benzothiazole-type polymerizable dye containing a urethane bond. A series of monomeric dyes have been prepared by diazotization of various 2-aminobenzothiiazole and coupled with Resorcinol. The polymeric dyes have been prepared by polycondensation of monomeric dyes with hexamethylene diisocyanate (HMDI), and they are characterized by molecular weight, non-aqueous conductometric titration, thermogravimetry analysis, IR, visible spectroscopy, and elemental analysis. The monomeric dyes have also been characterized by elemental analysis and IR spectra. The purity of all the dyes have been checked by thin layer chromatography, and their dyeing performance on nylon and polyester was assessed. The dyeing on polyester fiber had yellow, orange and pink shades with moderate to good light and wash fastness. Polymerizations of monomeric dyes with HMDI on dyed polyester have also been carried out. Color and dyeability of the polymeric dyes have been discussed by comparing them with their corresponding monomeric dyes. The percentage dye bath exhaustion and fixation on fiber have been found to be from good to very good. The dyeing of monomeric dyes showed very good color fastness properties, and their corresponding polymeric dyes showed excellent fastness to light, washing, perspiration, solvent resistance, and sublimation.     

Dyeing of multiple types of fabrics with a single reactive azo disperse dye

Three novel reactive azo disperse dyes were prepared using 7-acetamide-4-hydroxy-2-naphthalene sodium sulphate as the precursor. The structure of the dyes has the combined characteristics of reactive, disperse, and cationic dyes. Under alkaline conditions (pH 9), the dyes can be applied to cotton, silk, wool, and nylon. Under neutral conditions, they can be used to dye polyester. Under acidic conditions (pH 4.5), they can colour acrylic fabric after conversion of the tertiary amine group to the quaternary ammonium cation. The colour-fastness of the dyed fabrics were also evaluated.     

Influence of Neem oil pretreatment on the dyeing and antimicrobial properties of wool and silk fibers with some natural dyes

Wool and silk fibers pretreated with neem oil and dyed with chlorophyll, saffron red and yellow natural dyes using economic methods such as microwave heating and ultrasonic energy. The effect of neem oil concentrations on color strength (K/S) was measured. The results indicated that, wool and silk fibers pretreated with neem oil recorded higher color strength values than the untreated fibers. Fastness properties and the color yield of the dyes under investigation on wool and silk fibers were evaluated. The results indicated that, color fastness to rubbing, washing and perspiration of all dyes are excellent to good and are approximately the same in microwave and ultrasonic method. The antimicrobial activity against bacteria and fungi were tested, and the results indicated that the samples pretreated exhibited higher inhibition percent than the untreated fibers. The morphologies structure of the untreated and treated wool fibers were examined by scanning electron microscopy (SEM). The untreated samples have a rough surface. The pretreated samples of wool fibers were swelling compared to the untreated fibers .The diameter of the fibers increased and have smooth and even surfaces. The changes in the surface morphology due to the effect of active ingredients of treatment with neem oil. This behavior as swelling and increase in diameter of the fibers leads to high penetration of the dyes in the fibers.     

Synthesis of some novel pyrazolo[1,5-a]pyrimidine derivatives and their application as disperse dyes

A series of novel monoazo-disperse dyes containing pyrazolo[1,5-a]pyrimidine structures were synthesized starting with the coupling reaction between ethyl cyanoacetate and 4-hydroxybenzenediazonium chloride, followed by treatment of the resulting hydrazone product with hydrazine hydrate. The pyrazolohydrazone 6 is then treated with either 2,4-pentandione and enaminonitrile or aryl-substituted enaminoketones to give the target pyrazolo[1,5-a]pyrimidine dyes 7 and 15a-d. Structural assignments to the dyes were made using NMR spectroscopic methods. A new high temperature method, using microwave heating, was employed to apply these dyes to polyester fibers. Most of the dyed fabrics tested displayed moderate light fastness and excellent washing fastness properties.     

Characterization of synthetic dyes for environmental and forensic assessments: A chromatography and mass spectrometry approach

Dyes have become common substances since they are employed in mostly all objects surrounding our daily activities such as clothing and upholstery. Based on the usage and disposal of these objects, the transfer of the dyes to other media such as soil and water increases their prevalence in our environment. However, this prevalence could help to solve crimes and pollution problems if detection techniques are proper. For that reason, the detection and characterization of dyes in complex matrices is important to determine the possible events leading to their deposition (natural degradation, attempts of removal, possible match with evidence, among others). Currently, there are several chromatographic and mass spectrometric approaches used for the identification of these organic molecules and their derivatives with high specificity and accuracy. This review presents current chromatographic and mass spectrometric methods that are used for the detection and characterization of disperse, acid, basic, and reactive dyes, and their derivatives.     

Automated extraction of direct,reactive, and vat dyes from cellulosic fibers for forensic analysis by capillary electrophoresis

Systematic designed experiments were employed to find the optimum conditions for extraction of direct, reactive, and vat dyes from cotton fibers prior to forensic characterization. Automated microextractions were coupled with measurements of extraction efficiencies on a microplate reader UV–visible spectrophotometer to enable rapid screening of extraction efficiency as a function of solvent composition. Solvent extraction conditions were also developed to be compatible with subsequent forensic characterization of extracted dyes by capillary electrophoresis with UV–visible diode array detection. The capillary electrophoresis electrolyte successfully used in this work consists of 5 mM ammonium acetate in 40:60 acetonitrile–water at pH 9.3, with the addition of sodium dithionite reducing agent to facilitate analysis of vat dyes. The ultimate goal of these research efforts is enhanced discrimination of trace fiber evidence by analysis of extracted dyes. Figure Fitted absorbance response surface for extraction of a direct dye, C. I. yellow 58, using a ternary solvent system.     

杂环-双氰乙基系列分散染料的合成、表征及染色性能

以4个杂环芳香胺为重氮组分, 3个N,N-二氰乙基芳香胺为偶合组分, 经重氮化、 偶合反应合成了12个杂环-双氰乙基系列偶氮物; 采用紫外-可见吸收光谱、 红外光谱及核磁共振氢谱等对其结构进行了表征; 还考察了它们在涤纶织物、 乙酰化杉改性木粉和氰乙基化改性木粉上的染色性能. 结果表明, 12个偶氮物为目标产物, 在N,N-二甲基甲酰胺(DMF)中的最大可见吸收波长为417～621 nm, 摩尔吸光系数均大于10⁴. 这些化合物染色涤纶织物的色光分属黄色、 红色、 紫红色和蓝色系列, 并具有高水洗牢度和高日晒牢度; 染色乙酰化木粉和氰乙基木粉的色光和水洗牢度与染色涤纶织物相近. 这12个分散染料具有色谱范围广、 色泽鲜艳、 高发色强度和高牢度等特点, 可用于多种纤维的染色.     

Analyses of trace amounts of dyes with a new enhanced sensitivity FTIR spectroscopic technique: MU-ATR (metal underlayer ATR spectroscopy)

The identification of organic dyes is a challenging task in all the fields such as the forensic and conservation sciences, especially in cases where the amount of sample is extremely small. In this paper we propose a new enhanced FTIR method (MU-ATR metal underlayer ATR spectroscopy), which we believe is the first of its kind, for the analysis of a few ng of dyes. With this method, dyed fiber micro-extracts can be analyzed using a commercial FTIR microscope with a fixed incident angle, obtaining the same separation between the different classes of dyes investigated as we obtained analyzing pure dyes in transmission mode.     

Trace element distributions in man-made fibers

A preliminary study to evaluate the use of neutron activation analysis for the characterization of six groups of man-made fibers for forensic purposes has been made. A total of 81 samples of acetate, acrylic, modacrylic, nylon, polyester and rayon were analyzed. Small samples, approximately the size typically found during a crime scene search, were analyzed using a Ge(Li) detector system following a 20 min irradiation at a flux of 5·10¹³ n·cm⁻²·sec⁻¹. The following elements were determined quantitatively in one or more of the samples: Ti, Sr, Au, Zn, Sb, Br. Mn, Mg, Cu, In, Co, Cu, V, K, Al, Cl, Na, Ca, and S. Significant qualitative and quantitative differences were found both between and within the six groups. However, within certain groups some fibers from different manufacturers showed marked similarities in qualitative and quantitative composition.     

Determination of gasoline and diesel residues on wool,silk, polyester and cotton materials by SPME–GC–MS

The identification of ignitable liquids is very important and challenging aspect in arson crime investigations. The detection of gasoline and diesel fuel components using solid phase micro-extraction prior to gas chromatography–mass spectrometry for the forensic analysis of fire debris has been carried out. Previous works show that the absorption characteristics of the substrate are one of the most important factors in determining the evaporation rate of the accelerants. In order to determine the presence of the fuel residues, four of the most common substrate materials were tested in this work; wool, cotton, silk and polyester. The obtained results indicate that both gasoline and diesel fuel accelerants persisted longer on wool and silk than on the other selected substrates. Such information illustrates the influence of fuel persistence times after extinguishing and the best materials to be scanned for ignitable liquids at the fire scene.     

DNA‐Forensik

Forensics deals with the scientific methods to gather information at a crime scene for solving criminal actions. DNA forensics uses genetic material for these purposes. DNA fingerprinting is established as an important method for police detective work since the end of the 1980s. Currently, DNA forensics faces completely new possibilities through the application of more efficient high‐throughput sequencing methods, summarized as Next Generation Sequencing (NGS). Using NGS it could be possible to predict numerous externally visible characteristics including the complete facial shape of an unknown perpetrator. This article aims at presenting practices of forensic DNA analyses used to date and extending the picture for future possibilities and challenges.     

涤/绵纤维用丁烯二酸单酰胺染料的研究

涤/棉混纺纤维的同浴一步法染色由于可简化工艺、提高生产率已有不少研究.侯毓芬等研究过含β-羟乙基砜硫酸酯的水溶性活性分散染料.这类染料能溶於水,在热熔染色条件下能与棉纤维成共价结合,以乙烯砜结构存在於聚酯纤维内部,达到同浴上染涤/棉纤维的目的.     

Laboratory and outdoor assessment of UV protection offered by flax and hemp fabrics dyed with natural dyes

The safest protection from UV radiation (UVR) exposure is offered by clothing and its protectiveness depends on fabric composition (natural, artificial or synthetic fibers), fabric parameters (porosity, weight and thickness) and dyeing (natural or synthetic dyes, dye concentration, UV absorbing properties, etc.). In this study the UV protection properties of two fabrics made of natural fibers (flax and hemp) dyed with some of the most common natural dyes were investigated. UVR transmittance of fabrics was measured by two methods: one based on the utilization of a spectrophotometer equipped with an integrating sphere (in vitro test), and the other based on outdoor measurements taken by a spectroradiometer. Transmittance measurements were used to calculate the ultraviolet protection factor (UPF). Experimental results revealed that natural dyes could confer good UV protection, depending mainly on their different UVR-absorbing properties, provided that the fabric construction already guaranteed good cover. An increase in cover factor caused by the dyeing process was also detected. Weld-dyed fabrics gave the highest protection level. The comparison between the two methods applied to measure fabric transmittance pointed out that the UPFs calculated by in vitro measurements were generally lower than those based on outdoor data, indicating an underestimation of the actual protection level of tested fabrics assessed by the in vitro test.     

涤／棉纤维用丁烯二酸单酰胺染料的研究Ⅱ

为了简化涤/棉混纺织物印染上色的工艺流程,节约设备和能源,设计合成能同时上染涤/棉混纺纤维的单一染料,已成为目前国际染料界争相研究的热门课题。本文在前文的基础上设计合成了9种颜色以红和棕红为主的丁烯二酸单酰胺染料,以硝基苯胺为重氮组     

Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures

A novel water-soluble macromolecular light stabilizer was synthesized by grafting 2-chloro-4,6-bis- [(2,2,6,6-tetramethylpiperidin-4-yl)amino]-l,3,5-triazine onto polyvinylamine.The intermediate 2- chloro-4,6-bis-[(2,2,6,6-tetramethylpiperidin-4-yl)arnino]-1,3,5-triazine and the obtained macromolecular light stabilizer were characterized by ~1H NMR,HRMS,IR and UV spectroscopy.Cotton fabrics dyed with C.l.Reactive Yellow 145,C.I.Reactive Red 195 and C.I.Reactive Blue 19 were finished with the macromolecular light stabilizer,and the lightfastness of the dyes was tested.The results showed that the lightfastness of the reactive dyes was improved by 0.5-1.0 grade after being finished and the macromolecular light stabilizer exhibited good wash fastness and thermal stability.