Fluorescent Whitening Agents Research Articles

Synthesis, Optical Physical Properties and Whitening Effect on Filter Paper of Novel Stilbene-ethyl Acrylate Derivatives as Fluorescent Brighteners

Two novel stilbene-ethyl acrylate derivatives were synthesized by a three-step condensation reaction. The optical physical properties of synthesized compounds I and II were confirmed by the analysis of ultraviolet absorption and fluorescence emission spectra. Compounds I and II showed efficient brightening and whitening effect on filter paper at four different concentrations as novel fluorescent brighteners compared to the untreated paper. They had better dyeing properties at a concentration of 0.2% for compound I and 0.25% for compound II, respectively.

Suitability of fluorescent whitening compounds (FWCs) as indicators of human faecal contamination from septic tanks in rural catchments

Rural river catchments are impacted by diffuse pollution sources from agricultural practices and on-site domestic wastewater treatment systems (DWWTS), mainly septic tanks. Methods that can distinguish between contamination sources will significantly increase water management efficiency as they will allow for the development and application of targeted remediation measures. Fluorescent whitening compounds (FWC), are used as optical brighteners in laundry detergents and enter the environment through the discharge of domestic wastewater effluents. Due to their human specific source and potential simple fluorometric measurement this represents a very attractive method to be used by state monitoring agencies.In this study the suitability of FWCs as chemical indicators for human faecal contamination has been investigated in rural Irish catchments. It was found that no quantitative measurements are possible for FWCs in natural waters when using simple fluorometric methods. Hence a simple presence/absence approach needs to be applied. The detectability of FWCs was quantified and found to decrease with higher organic matter content of the river water which has its own fluorescence. This enabled the establishment of equations to predict detection limits and assess the method's suitability for individual catchments based on organic matter concentrations. Furthermore a modified photodecay method is suggested that increases sensitivity of the technique by up to 59%. Applications at rural study sites found some removal of FWCs in percolation areas of DWWTSs but they were still detectable 40 cm below the infiltration depth. FWCs were also detected as distinguishable peaks in impacted streams where septic tank effluents have a high contribution to the river flow.

Assessment of toxicity of raw textile wastewater and after its reuse

Five consecutive dyeings were made using the treated effluent in every step. All photochemical treatments obtained decolourization efficiency (DE) above 90%, allowing the effluent to be reused in dyeings with fluorescent brighteners, from the first until the last treated effluent. In this proposed process, the rate of total organic carbon (TOC) presented after five consecutive dyeings achieved with treated effluent was 34 mg L-1 compared with 435 mg L-1 of the final effluent that was obtained after five conventional processes. The salinity of the final effluent obtained by this proposed process was 2.34 g L-1 of NaCl compared with 25.00 g L-1 presented in the effluent obtained by the conventional process. The values of the colour fastness to water showed no significant differences between the colours that were made by two processes. The average water consumption for a one-kilogram cotton dyeing after fifteen dyeings achieved by this proposed process was approximately 24 litres compared with the 70 litres that were consumed by the conventional process. However, the final treated effluent presented values of toxicity < 6.25% (EC50, with 95% confidence interval) against 10.25% of the raw effluent. It means that in the sample concentration of the treated effluent presented 100% of Daphina similis mortality, indicating that this sample was more toxic than the raw effluent.

Preparation and Characterization of Poly-1,2,3-triazole with Chiral 2(5H)-Furanone Moiety as Potential Optical Brightening Agents.

A series of novel heterocyclic polymers with fluorescent brightening properties are synthesized via Click polymerization. Fast synthesis of poly-1,2,3-triazoles (Mn ≥ 9.31 kDa) is described herein, with a high yield of up to 95%. The Click polymerization approach has a number of advantages, including facile operation and outstanding isolation yield. The resultant polymers have a high thermal stability, excellent UV resistance, as well as acid and light fastness. On embedding with optical brightening agents, the polymers display strong fluorescent brightening properties in the tetrahydrofuran solution. Moreover, these products have a strong solution emission intensity and extraordinary photostability under UV light.

Movement of traditional fecal indicator bacteria and source-tracking targets through septic drainfields

The past three decades' data on outbreaks in the United States indicate that homes dependent on untreated groundwater (e.g. wells) for household drinking water that are also reliant on onsite treatment of household wastewater (e.g. septic systems) may be at greater risk for waterborne disease. While groundwater quality monitoring to protect public health has traditionally focused on the detection of fecal indicator bacteria, the application of emerging source tracking strategies may offer a more efficient means to identify pollution sources and effective means of remediation. This study compares the movement of common fecal indicator bacteria (E. coli and enterococci) with a chemical (optical brighteners, OB) and a molecular (Bacteroides HF183) source tracking (ST) target in small scale septic drainfield models in order to evaluate their potential utility in groundwater monitoring. Nine PVC column drainfield models received synchronized doses of primary-treated wastewater twice daily, with influent and effluent monitored bi-weekly over a 7-month period for all targets. Results indicate that E. coli and enterococci concentrations were strongly associated (Spearman's rank, p<0.05), and correlations between enterococci and optical brighteners were moderately strong. Bacteroides HF183 was significantly, but not strongly, associated with optical brighteners and both indicator bacteria (Point-biserial correlation, p<0.05), most likely due to its sporadic detection. Application of human ST marker monitoring in groundwaters at risk of contamination by human sewage is recommended, although consistent interpretation of results will rely on more detailed evaluation of HF183 incidence in source contamination waters.

Acylhydrazone bond dynamic covalent polymer gel monolithic column online coupling to high-performance liquid chromatography for analysis of sulfonamides and fluorescent whitening agents in food

A new dynamic covalent polymer (DCP) gel was well designed and constructed based on imine chemistry. Polycondensation of 4,4′-biphenyldicarboxaldehyde and 1,3,5-benzenetricarbohydrazide via Schiff-base reaction resulted in an acylhydrazone bond gel (AB-gel) DCP. AB-gel DCP had three-dimensional network of interconnected nanoparticles with hierarchically porous structure. AB-gel DCP was successfully fabricated as a monolithic column by an in-situ chemical bonding method for online enrichment and separation purpose with excellent permeability. AB-gel DCP based monolithic column showed remarkable adsorption affinity towards target analytes including sulfonamides (SAs) and fluorescent whitening agents (FWAs) due to its strong π-π affinity, hydrophobic effect and hydrogen bonding interaction. Then, AB-gel DCP based monolithic column was applied for online separation and analysis of trace SAs and FWAs in food samples coupled with high-performance liquid chromatography (HPLC). Sulfathiazole (ST) and sulfadimidine (SM2) in one positive weever sample were actually found and determined with concentrations of 273.8 and 286.3μg/kg, respectively. 2,5-Bis(5-tert-butyl-2-benzoxazolyl) thiophene (FWA184) was actually quantified in one tea infusion sample with the concentration of 268.5ng/L. The spiked experiments suggested the good recoveries in range of 74.5–110% for SAs in weever and shrimp samples with relative standard deviations (RSDs) less than 9.7% and in range of 74.0-113% for FWAs in milk and tea infusion samples with RSDs less than 9.0%. AB-gel DCP monolithic column was proved to be a promising sample preparation medium for online separation and analysis of trace analytes in food samples with complex matrices.

Introduction of Red-Green-Blue Fluorescent Dyes into a Metal-Organic Framework for Tunable White Light Emission.

The unique features of the metal-organic frameworks (MOFs), including ultrahigh porosities and surface areas, tunable pores, endow the MOFs with special utilizations as host matrices. In this work, various neutral and ionic guest dye molecules, such as fluorescent brighteners, coumarin derivatives, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM), and 4-(p-dimethylaminostyryl)-1-methylpyridinium (DSM), are encapsulated in a neutral MOF, yielding novel blue-, green-, and red-phosphors, respectively. Furthermore, this study introduces the red-, green-, and blue-emitting dyes into a MOF together for the first time, producing white-light materials with nearly ideal Commission International ed'Eclairage (CIE) coordinates, high color-rendering index values (up to 92%) and quantum yields (up to 26%), and moderate correlated color temperature values. The white light is tunable by changing the content or type of the three dye guests, or the excitation wavelength. Significantly, the introduction of blue-emitting guests in the methodology makes the available MOF host more extensive, and the final white-light output more tunable and high-quality. Such strategy can be widely adopted to design and prepare white-light-emitting materials.

Water‐soluble, antiyellowing polymeric fluorescence brighteners

ABSTRACTIn this study, a type of polymeric fluorescence brightener (PFB) with a triazine–stilbene structure was synthesized through a three‐step condensation reaction, and the performance of this PFB on antiyellowing was also investigated by the whiteness of paper coated with the as‐prepared PFB. Fourier transform infrared spectra revealed that the chlorine atom (·Cl) was substituted by a poly(vinyl alcohol) (PVA) group ([CH2CHOH]n). According to the UV aging experiment, the PFB not only enhanced the whiteness of the paper but also improved the anti‐UV aging properties [compared to those of VBL 4′‐double‐(6‐diethanolamine‐4‐sulfanilic acid‐1,3,5‐triazine‐2‐amino)‐stilbene‐2,2′‐disulfonic acid sodium, a type of commonly used fluorescent whitening agent as a light stabilizer and fluorescent brightening agent]. Moreover, the results of UV–visible spectra indicated that the substitution of PVA suppressed the isomerization of trans conformers to cis conformers under UV light irradiation; this was attributed to the big space steric hindrance of PVA in the as‐prepared samples being restricted the isomerization reaction. Meanwhile, the solubility of the as‐prepared sample was also improved because more hydroxyl groups were introduced into the PFB with the substitution of PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45536.

Synthesis and performances of extended conjugated stilbene fluorescent dye

PurposeThe purpose of this paper is to explore the optic performance of extended stilbene derivative.Design/methodology/approachFive steps were adopted to synthesise novel 4, 4′-bis (2-cyanostyryl) stilbene, which contained three vinyl units in the skeleton (S3E). The structure of S3E was characterised by 1H NMR and EI-MS. Its absorption and emission spectra were also given.FindingsCompared to C.I. Fluorescent Brightener 199, which contains two vinyl units in the skeleton, S3E showed obvious bathochromic shifts in both UV-VIS and FL spectra. The maximum absorption wavelength and fluorescent wavelength were at 390 nm and 464 nm, respectively, with Stoke’s shift of 74 nm. The absolute fluorescence quantum yield was 0.42. Thermogravimetric analysis (TGA) revealed that the weight loss of S3E was less than 5 per cent at 300 °C. Moreover, the light resistance test showed that S3E in PVC plate can keep the good fluorescent intensity for more than seven days exposed to xenon light. Therefore, it is believed that S3E could satisfy the requirements of colouring PVC as a fluorescent dye.Practical implicationsS3E can be used as a candidate of fluorescent dye in the development of thermoplastics.Originality/valueThe present paper designed and synthesised a new derivative of stilbene, which showed its preference to be a colourant of thermoplastics.

Impact of spectral power distribution of daylight simulators on whiteness specification for surface colors

AbstractThe impact of spectral power distribution of daylight simulators (ie, D65 simulators) on surface whiteness specification was investigated by focusing on how CIE whiteness and tint values of 8 whiteness samples with fluorescent whitening agents (FWAs) vary under different D65 simulators. Large variations in both whiteness (∼16 points) and tint (∼1.6 points) are observed under the D65 simulators above BB grade, as characterized using the CIE metamerism index. However, it is found the variations of the whiteness and tint values are smaller under the D65 simulators whose radiant power in the UVA band (ie, 300‐340 nm) was within ±30% in comparison to CIE standard D65 illuminant, as defined in BS 950, which may be a better alternative for evaluating the quality of a D65 simulator for surface white specification using CIE whiteness and tint formulas. The findings also suggest the necessity to fine‐tune or revise the CIE whiteness and tint formulas to characterize the surface whiteness under nonperfect D65 simulators or arbitrary light sources.

Spain: Archroma – optical brighteners

Spain: Archroma – optical brighteners

Direct determination of migration amount of fluorescent whitening agents in facial mask

Facial mask is a kind of skin care cosmetics, in which fluorescent whitening agents(FWAs) were added to make face skin look whiter and brighter. In this work, pig skin was used instead of human skin to test the methods. Three methods, including pig skin migration fluorescent spectrophotometry(FS), fiber paper migration FS, and fiber paper migration visual colourimetry(VC), were developed for determining the migration amount of FWAs from facial mask to pig skin. In the methods, a self-assembly light source and fluorescence collecting unit was used. The unit can be easily moved and the measurement was very convenient. Some experimental conditions were optimized. The fiber paper migration VC can give semi-quantitative results and was the simplest one in the three methods because collection, separation and detection of the fluorescence were not needed. Both the pig skin migration FS and fiber paper migration FS can give quantitative results and compared with fiber paper migration FS, the pig skin migration FS could give more practical results by simulating the real way of using facial mask. The limits of detection for disodium 4,4′-bis[(4-anilino-6-hydroxyethylamion-1,3,5-triazin-2-yl)amion]stilbene-2,2′-disulphonate(VBL) obtained by pig skin migration FS and fiber paper migration FS were 0.03 and 0.05 mg/m2, respectively. 96 kinds of samples were analyzed and the migration amounts of FWAs in 21 kinds of samples were detectable. Correlations between migration amounts obtained by the three methods were very good. Experimental results indicate that the present methods can be applied to the determination of migration amount of FWAs in facial masks.

Long-chain ionic liquid based mixed hemimicelles and magnetic dispersed solid-phase extraction for the extraction of fluorescent whitening agents in paper materials.

A novel mixed hemimicelles and magnetic dispersive solid-phase extraction method based on long-chain ionic liquids for the extraction of five fluorescent whitening agents was established. The factors influenced on extraction efficiency were investigated. Under the optimal conditions, namely, the pH of sample solution at 8.0, the concentration of long chain ionic liquid at 0.5mmol/L, the amount of Fe3 O4 nanoparticle at 12mg, extraction time at 10min, pH 6.0 of methanol as eluent, and the desorption time at 1min, satisfactory results were obtained. Wide linear ranges (0.02-10ng/mL) and good linearity were attained (0.9997-0.9999). The intraday and interday RSDs were 2.1-8.3%. Limits of detection were 0.004-0.01ng/mL, which were decreased by almost an order of magnitude compared to direct detection without extraction. The present method was applied to extract the fluorescent whitening agents in two kinds of paper samples, obtaining satisfactory results. All showed results illustrated that the detection sensitivity was improved and the proposed method was a good choice for the enriching and monitoring of trace fluorescent whitening agents.

Concept Evaluation of Predicting UPF Values for Artificial Cellulose Fabrics by Varying the Optical Brightener Chemical Structure Applied

The publication presents investigation results and statistical analysis showing that by varying the chemical structure of optical brighteners from the derivative group of stilbene used for fabrics of artificial cellulose fibre modification, resulting in a different manufacturing process, it is possible to predict the level of the UPF value of the index of such modified fabric. In addition, statistically it was confirmed by results from early research that both the fibre finish (in this case, roughening the pigment TiO2 ) used for fabric manufacture as well as the FBA concentration used for fabric modification influence their UPF index value. Fabric UV -barrier studies also showed that despite a partial decrease in UPF values for such finished fabrics, the dependence of such an index on subtle differences in the chemical structure of the FBAs is maintained. Primarily the possibility and range of improving textile barriers against UV radiation through the use of the UV-absorption abilities of optical brighteners with subtle differences in their chemical structure was recognised, creating a premise to elaborate a mathematical control concept to steer a textile UV-barrier.

Unified Synthesis of 1,2-Oxy-aminoarenes via a Bio-inspired Phenol-Amine Coupling

Summary 1,2-Aminophenols and their related nitrogen-containing heterocycles are ubiquitous in medicine, agriculture, and materials science. Here, we describe a bio-inspired and unified approach for their synthesis through a direct, catalytic aerobic coupling of phenols and amines. Key to the formation of the aromatic C–N bond is a facile condensation between the amine and an ortho -quinone, which triggers redox isomerization to an ortho -iminophenol before a series of downstream events. We discuss the factors that govern regioselectivity during aerobic ortho -oxygenation of the phenol and condensation of the amine, and we demonstrate synthetic utility by preparing a structurally diverse family of immunosuppressive heterocycles and the indole alkaloid cephalandole A. Our conditions involve a wide range of simple, un-activated substrates, occur at room temperature with an earth-abundant copper-catalyst and a commercially available diamine ligand, and produce water as the only stoichiometric by-product.

MBR 공정 적용을 위한 전처리 오존산화에 의한 형광증백제 제거 연구

In this study, ozone oxidation experiment was carried out for the removal of fluorescent whitening agent which is widely used in textile dyeing and paper industry. The stilbene fluorescent whitening agent has been industrialized since the earliest, and the amount of current production is the highest. Due to the characteristics of the fluorescent whitening agent that can not be removed by conventional wastewater treatment methods, the fluorescent whitening agent in wastewater treatment has difficulty in using as recycled water in the process. Pre-treatment ozone oxidation experiment was conducted prior to the introduction of Membrane Bio Reactor(MBR) treatment process by converting biodegradable materials into biodegradable materials. The removal efficiencies of fluorescent whitening agents, a diaminostilbenedisulfonic acid derivative by ozone oxidation were evaluated by <TEX>$UV_{254}$</TEX> Scan, <TEX>$COD_{Mn}$</TEX>, T-N and color using a synthetic wastewater sample (<TEX>$COD_{Mn}=433.0mg/{\ell}$</TEX>) and paper and paper mill wastewater (<TEX>$COD_{Mn}=157.2mg/{\ell}$</TEX>).

Effect of Carrier Chemicals on the Optical Properties of Paper Surface-Sized with Fluorescent Whitening Agents

Fluorescent whitening agents (FWAs) are important chemicals for improving the CIE whiteness and ISO brightness of papers. However, papermakers must reduce the amount of FWAs added to their products because FWAs present many disadvantages associated with the papermaking process, as well as paper quality; the public also has concerns about these chemicals in papers. Because the first step to reducing FWAs in the papermaking process is to improve their whitening effect, a new strategy for the effective use of FWA carrier chemicals must be developed. In this study, the whitening effects of tetra-sulpho FWA (T-FWA) and hexa-sulpho FWA (H-FWA) are compared in surface sizing, as well as with carrier chemicals. H-FWA showed a greater whitening effect than T-FWA in surface sizing, and carrier chemicals improved the optical properties of the paper when surface-sized with FWAs. It is concluded that carboxymethyl-celluloses (CMCs) were a more effective carrier chemical for T-FWA; polyvinyl alcohol (PVOH) is effective with H-FWA in the surface-sizing process to increase paper sheet whiteness.

Functionality of Metdi5511gene in Methylobacterium dichloromethanicum DM4

A knockout mutant of Methylobacterium dichloromethanicum DM4 with an inactivated gene of a putative transcription regulator METDI5511 (ΔMETDI5511) has been obtained. The expression of this gene increases many times when the strain is grown on dichloromethane compared to methanol. The mutant had a low growth rate on dichloromethane as compared with the original strain and was found to be more sensitive to influences of various types of stress (oxidative, osmotic stress, heat, and drying). The cells were stained with Fluorescent Brightener 28 (Calcofluor white), and the intensity of their fluorescence showed that the ΔMETDI5511 mutant had significantly increased numbers of surface polysaccharides with β-1,3 and β-1,4-glycoside bonds. The results indicate that the METDI5511 gene is involved in the regulation of surface polysaccharides that play an important role in adaptation of cells to growth on dichloromethane.

Recent Advances in the Use of Chemical Markers for Tracing Wastewater Contamination in Aquatic Environment: A Review

There has been increasing research focus on the detection and occurrence of wastewater contamination in aquatic environment. Wastewater treatment plants receive effluents containing various chemical pollutants. These chemicals may not be fully removed during treatment and could potentially enter the receiving water bodies. Detection of these chemical pollutants and source identification could be a challenging research task due to the diversified chemical and functional groups, concentration levels and fate and transportation mechanisms of these pollutants in the environment. Chemical markers such as pharmaceuticals and personal care products, artificial sweeteners, fluorescent whitening agents, sterols and stanols, and nitrate and nitrogen isotopics have been widely used by most research as markers. These markers served as indicators of wastewater contamination to the receiving bodies due to their frequent usage, resistance to biodegradability and, more importantly, anthropogenic origin. These markers are commonly used in combination to identify the contaminant source of different origins. This article discusses the main chemical markers that are used to identify wastewater contamination in receiving bodies, the current trends, and approach to select suitable chemical markers.

Midgut-based resistance to oral infection by a nucleopolyhedrovirus in the laboratory-selected strain of the smaller tea tortrix, Adoxophyes honmai (Lepidoptera: Tortricidae).

A strain of Adoxophyes honmai resistant to Adoxophyes honmai nucleopolyhedrovirus (AdhoNPV) was established from a field-collected colony by repeated selection. Fifth-instar larvae of this resistant strain (R-strain) had over 66 666-fold greater resistance in terms of 50 % lethal concentration values to oral infection of AdhoNPV than non-selected strain larvae (susceptible for AdhoNPV; S2-strain). In this study, the mechanism of resistance to AdhoNPV was determined in R-strain larvae. An assessment of viral genome replication in AdhoNPV-infected S2- and R-strain larvae by quantitative PCR showed no viral genome replication occurring in R-strain larvae. Transcription of AdhoNPV ie-1, vp39 and polyhedrin genes was also not detected in R-strain midgut cells. Besides, a fluorescent brightener had no effect on AdhoNPV infection in either S2- or R-strain. However, binding and fusion of occlusion-derived virus with R-strain were significantly lower than those of S2-strain. These findings suggest that R-strain Adoxophyeshonmai larvae possess a midgut-based resistance to oral infection by AdhoNPV in which midgut epithelial cells are infected less efficiently.