Fluorescent Whitening Agents Research Articles

Employing Singlet-Singlet Energy Transfer for Boosting the Reactivity of Type I Photoinitiators in Radical Photopolymerization.

A remarkable and unexpected increase in the photopolymerization efficiency of an acrylic resin by a bisacylphosphine oxide photoinitiator was observed when an optical brightener was present in the medium. High values for the maximal rates of photopolymerization were obtained by RT-FTIR at 365 nm under a very low irradiance of 1 mW/cm2. Fluorescence studies revealed that the quenching process occurs through singlet-singlet energy transfer between the first singlet excited state of the optical brightener and the ground state photoinitiator. This mechanism acts as an additional pathway for the excitation of the photoinitiator, thereby increasing the total amount of initiating radicals. Using the Förster resonance energy transfer model, we calculated the relative efficiency of the photosensitization process with respect to the direct excitation efficiency of the photoinitiator. The results demonstrate that the photosensitization process can be predicted, paving the way for further improvements in photoinitiating systems.

Employing Singlet‐Singlet Energy Transfer for Boosting the Reactivity of Type I Photoinitiators in Radical Photopolymerization

AbstractA remarkable and unexpected increase in the photopolymerization efficiency of an acrylic resin by a bisacylphosphine oxide photoinitiator was observed when an optical brightener was present in the medium. High values for the maximal rates of photopolymerization were obtained by RT‐FTIR at 365 nm under a very low irradiance of 1 mW/cm2. Fluorescence studies revealed that the quenching process occurs through singlet‐singlet energy transfer between the first singlet excited state of the optical brightener and the ground state photoinitiator. This mechanism acts as an additional pathway for the excitation of the photoinitiator, thereby increasing the total amount of initiating radicals. Using the Förster resonance energy transfer model, we calculated the relative efficiency of the photosensitization process with respect to the direct excitation efficiency of the photoinitiator. The results demonstrate that the photosensitization process can be predicted, paving the way for further improvements in photoinitiating systems.

Microbial source tracking and identification of fecal contamination patterns in saltwater estuaries between base- and storm-flow events using dual genome-based approaches

Fecal contamination from natural and anthropogenic sources poses significant threats to saltwater estuaries, particularly after storms or heavy rainfall. Monitoring fecal contamination is essential for protecting these vulnerable ecosystems having important ecological and economic values. In this study, we investigated the abundance, sources, and potential causes of fecal contamination at three marine and seven freshwater stations across Vaughn Bay (WA, USA), a shellfish growing district, during base- and storm-flow events. Additionally, we evaluated the performance of fecal indicator bacteria (FIB) quantification, optical brightener assessment, and qPCR analysis for fecal contamination quantification. We compared the effectiveness of qPCR-based microbial source tracking (MST), which targeted a broad range of hosts including, such as humans, birds, cows, horses, ruminants, dogs, and pigs, with sequencing-based MST in identifying fecal contamination sources. Both MST analysis approaches identified birds and humans as the primary sources of fecal contamination. For marine water stations, freshwater creeks VBU001, VBU002, and VB047, along with drain VB007, were identified as the main sources of human-derived fecal contamination in Vaughn Bay, based on Kendall's tau analysis (τ: 0.58–0.97). This information indicates that the septic systems in the catchment areas of these creeks and drains require further investigation to achieve effective fecal contamination control. Optical brightener, FIB enumeration and qPCR quantification results were generally higher during storm-flow events, although they showed poor correlation with each other (Pearson r < 0.40), likely due to physiological and phylogenetic differences among the target organisms of these methods. However, the sequencing-based method faces challenges in precise quantitative identification of differences in fecal contamination between base- and storm-flow events. Due to its high-throughput and cost-effectiveness, we recommend using sequencing-based analysis for large-scale identification of the primary sources of fecal contamination in water environments, followed by targeted qPCR quantification of MST markers for more precise assessments.

Analytical Spectral Semi-quantitative Dating Method of Printed Text Toner Using Raman Spectroscopy and the Fluorescence signal of Paper Sheet Cellulose

Abstract: The chemical processes that occur during the surface degradation of document paper under the influence of external factors were studied by Raman spectroscopy. The possibility of comparing the same processes occurring on clean free paper and under printed text toner letters is of interest. It is assumed that the transformation of cellulose can occur at different rates in the areas of paper exposed to direct atmospheric and light exposure and in the areas containing an intermediate layer of the toner. The most stable temporal changes occur in the region of C–C–C and C– C–O vibrations of glycosidic rings in the short-wavelength region of the Raman spectrum. Background: The main areas of research in the field of document dating, mainly focused on chromatographic methods. These methods are based on studying the dynamics of evaporation of volatile ink components. There is also a variety of chromatography techniques, including gas chromatography, ion chromatography, high performance liquid chromatography, thin layer chromatography and gas chromatography-mass spectrometry. This indicates the wide range of approaches and techniques used to determine the age of written materials. However, all these methods are used mainly during the first two years after writing the document details, which does not allow examining documents that are more than two years old. Methods: Raman spectroscopy was used as the main research method. The object of the study was sheets of white A4 paper with printed text printed on them, produced on a laser printer. The subject of the study was areas of paper free of text, as well as areas of paper under toner. The integrated fluorescence of a paper optical brightener based on stilbene was studied in the wavelength range of 400–500 nm. Also, all objects were studied using optical microscopy. Results: The comparison of peak intensity values averaged over 10 brands over the years made it possible to reveal the following regularities: – the ratio of peaks in the paper spectra from which the toner was removed is greater than in the blank paper spectra, and the difference becomes less noticeable as the age of the paper decreases. The ratio of the intensity of the 330 cm-1 peak to the intensity of the 1603 cm-1 peak: the older the document becomes, the lower the average ratios of these peaks in both the blank paper spectra and in the spectra of paper from which the toner has been removed. –the intensity of the peak in the region of 280 cm-1 and 1 086 cm-1 of the Raman shift increases with decreasing the age of the toner-free paper.– a gradual increase in the intensity of the 380 cm-1 peak is observed when comparing the paper samples from which the toner was removed for 2016, 2018, 2020, and 2022. Regularity was also found in the change in the ratio of the average statistical values of the peak at 280 cm-1 in the spectra of the paper under the toner to a similar peak in the spectra of the paper free from text: the value of this ratio decreases with decreasing the paper age. At the same time, the paper fluorescence signal is an informative parameter that makes it possible to establish some facts from the document’s history. With artificial document aging, a significant broadening of the dispersion region and the appearance of its “splitting” into two or three strata are observed in the distribution of the fluorescence signal level of a paper sheet relative to the average value. The average fluorescence signal of a naturally aged sheet decreases with the age of the document. Conclusion: As a result of research, it has been established that Raman spectroscopy can be successfully used as a method for dating documents. When comparing the degree of degradation of the surface of open areas of paper and areas protected by toner of printed text, different effects of external factors on these areas were established, leading to different rates of degradation processes. The use of Raman peak intensity ratios for paper components in exposed areas compared to peaks under printed text further expands the methodology. The emphasis on spectral methods, in particular fluorescence signal distribution and Raman spectroscopy, to detect surface changes is well justified. It demonstrates a holistic approach to document analysis, taking into account both the chemical changes observed using Raman spectroscopy and the fluorescence signal distribution that may indicate signs of artificial aging through light exposure. This combination of methods appears to be reliable for assessing the age of documents and can make significant contributions to the field of forensic document examination.

Green whitening of polyester fabric using fluorescent brightener OB-1 in a mixture of water and decamethylcyclopentasiloxane media

Fluorescent brightening agent OB-1 (OB-1) is often used in plastic goods because of its non-toxic nature, chemical stability, remarkable heat resistance, and light stability. Raw OB-1 is challenging to use in textiles using the exhaustion method. This study used a novel method using raw OB-1 powder to whiten polyester fabric in water and decamethylcyclopentasiloxane (D5). The Taguchi approach investigated the interaction between whitening process parameters such as temperature, OB-1 mass, water: D5 ratio, and treatment time with four levels. The study shows that the temperature and water: D5 ratio during the whitening process significantly affect the whiteness of polyester fabric (P < 0.05), with contribution percentages of 74.2 % and 25.2 %. Subsequently, various analytical techniques were employed, including FTIR, SEM, TGA, and XRD, to characterise the whitened fabric. The findings imply that using water: D5 medium was effective in whitening polyester fabric without causing major alterations to the structure of the PET fabric. The study also examined the fastness of washing and crocking to determine their whitening stability. Overall, polyester fabric whitened with water and D5 medium exhibited satisfactory whitening performance and might be a potential scope for use on a larger scale in developing the sustainable textile industry.

β-Cyclodextrin/calix[4]arene hybrid porous organic polymer membrane for synergistic extraction of fluorescent whitening agents migrating from food contact materials

Acurate and sensitive determination of hazards from food contact materials is important to monitor food safety. It is necessary to excavate efficient adsorbent for simultaneous recognition and adsorption of food hazards of trace level for sample preparation. In this work, β-cyclodextrin and calix[4]arene were employed as hybrid functional monomers to prepare macrocyclic porous organic polymer (β-CD-CX4 POP). It was proved that the supramolecular cavities of β-CD-CX4 POP could form inclusion complexes with fluorescent whitening agents (FWAs) through host-guest recognition, which greatly improved the adsorption performance. The hydrophobic cavities of β-cyclodextrin and calix[4]arene of β-CD-CX4 POP exhibited synergistic effect for simultaneous recognition of FWAs. The high-throughput enrichment of FWAs was realized by β-CD-CX4 POP membranes coupled with a multiple-channel syringe pump. Based on membrane-based solid-phase extraction combined with UHPLC-MS/MS, a sensitive analytical method was established to determine six FWAs. The LODs was in range of 3-50 ng/L with the linear range of 0.02-100 μg/L. The developed method was used to quantify FWAs in bread wrapper and bread, and the spiked recoveries ranged from 78.1%-119% with RSD of 2.3%-9.7%. This work indicated that β-CD-CX4 POP was promising for the simultaneous recognition and adsorption of FWAs migrating from food contact materials.

Update on methods used for mycological testing: wide diversity and opportunities for improvement persist

Past analysis of laboratory methods used for mycology specimens revealed significant variation in practices, many of which fell short of recommended procedures. In 2016 these findings led to a set of recommendations for laboratories to consider modification of their methods where appropriate, to analyse current laboratory methods used by participants in the Royal College of Pathologists of Australasia Quality Assurance Programs (RCPAQAP) Mycology module, and to compare these to the 2016 recommendations. Seven test items, with 105-107 participants each, were analysed. Several laboratories (7-12%) did not handle specimens as recommended in an appropriate biological safety cabinet. Direct microscopy was not performed on tissue specimens 23-25% of the time. The most used staining method was potassium hydroxide with an optical brightener for fluorescent microscopy (49%) followed by Gram stain (33%). While 17-25% of laboratories used three or more media, use of four or more was uncommon (<3%). Between 9-13% of participants used only a single non-inhibitory medium for cultures. Urine specimens were incubated longer than recommended with 57% of laboratories incubating for >7days and 24% >21 days. Duration of incubation was shorter than recommended for several specimen types with 36% of skin specimens and 37-48% of tissue specimens being kept ≤21 days. For cultures kept >7 days, 13% were inspected daily but for those incubating >14 days only 3%. The methods of several laboratories remain outside recommended practice. An updated set of recommendations are made.

Plastic particles and fluorescent brightener co-modify Chlorella pyrenoidosa photosynthesis and a machine learning approach predict algae growth

Global release of plastics exerts various impacts on the ecological cycle, particularly on primary photosynthesis, while the impacts of plastic additives are unknown. As a carrier of fluorescent brightener, plastic particles co-modify Chlorella pyrenoidosa (C. pyrenoidosa) growth and its photosynthetic parameters. In general, adding to the oxidative damage induced by polystyrene, fluorescent brightener-doped polystyrene produces stronger visible light and the amount of negative charge is more likely to cause photodamage in C. pyrenoidosa leading to higher energy dissipation through conditioning than in the control group with a date of ETR (II) inhibition rate of 33 %, Fv/Fm inhibition rate of 8.3 % and Pm inhibition rate of 48.8 %. To elucidate the ecological effect of fluorescent brightener doping in plastic particles, a machine learning method is performed to establish a Gradient Boosting Machine model for predicting the impact of environmental factors on algal growth. Upon validation, the model achieved an average fitting degree of 88 %. Relative concentration of plastic particles and algae claimed the most significant factor by interpretability analysis of the machine learning. Additionally, both Gradient Boosting Machine prediction and experimental results indicate a matching result that plastic additives have an inhibitive effect on algal growth.

Fluorescent labeling of micro/nanoplastics for biological applications with a focus on “true-to-life" tracking

The increased environmental presence of micro-/nanoplastics (MNPLs) and the potential health risks associated with their exposure classify them as environmental pollutants with special environmental and health concerns. Consequently, there is an urgent need to investigate the potential risks associated with secondary MNPLs. In this context, using “true-to-life” MNPLs, resulting from the laboratory degradation of plastic goods, may be a sound approach. These non-commercial secondary MNPLs must be labeled to track their presence/journeys inside cells or organisms. Because the cell internalization of MNPLs is commonly analyzed using fluorescence techniques, the use of fluorescent dyes may be a sound method to label them. Five different compounds comprising two chemical dyes (Nile Red and Rhodamine-B), one optical brightener (Opticol), and two industrial dyes (Amarillo Luminoso and iDye PolyPink) were tested to determine their potential for such applications. Using commercial standards of polystyrene nanoplastics (PSNPLs) with an average size of 170 nm, different characteristics of the selected dyes such as the absence of impact on cell viability, specificity for plastic staining, no leaching, and lack of interference with other fluorochromes were analyzed. Based on the overall data obtained in the wide battery of assays performed, iDye PolyPink exhibited the most advantages, with respect to the other compounds, and was selected to effectively label “true-to-life” MNPLs. These advantages were confirmed using a proposed protocol, and labeling titanium-doped PETNPLs (obtained from the degradation of milk PET plastic bottles), as an example of “true-to-life” secondary NPLs. These results confirmed the usefulness of iDye PolyPink for labeling MNPLs and detecting cell internalization.

Highly sensitive detection of fluorescent whitening agents in flour using sheathless capillary electrophoresis-electrospray ionization-tandem mass spectrometry

Fluorescent whitening agents (FWAs) are dyes that emit visible blue or blue-purple fluorescence upon ultraviolet-light absorption. Taking advantage of light complementarity, FWAs can compensate for the yellow color of many substances to achieve a whitening effect; thus, they are used extensively in various applications. FWAs are generally stable, but their presence in the environment can lead to pollution and accumulation in the body through the food chain. Recent studies have revealed that some types of FWAs, such as coumarin-based FWAs, may exhibit photo-induced mutagenic effects that can trigger allergic reactions in humans and even pose carcinogenic risks. Hence, the development of an accurate and highly sensitive method for detecting FWAs in food-related samples is a crucial endeavor. Owing to the high polarity and structural similarity of FWAs, the accurate determination of these substances in complex food samples requires an analytical method that offers both efficient separation and sensitive detection. Capillary electrophoresis (CE) exhibits essential features such as high separation efficiency, short analysis times, very small sample injection requirements, minimal use of organic solvents, and simple operation. Thus, it is often used as an effective alternative to liquid chromatographic techniques. Over the past few decades, electrospray ionization mass spectrometry (ESI-MS) has been utilized as a highly sensitive and accurate detection method in numerous chemical analytical fields because it enables the analysis of molecular structures. By combining the high separation efficiency of CE with the high sensitivity of ESI-MS, a powerful tool for identifying and quantifying trace amounts of FWAs in food samples may be obtained. In this study, we present a method based on sheathless CE coupled with electrospray ionization tandem mass spectrometry (ESI-MS/MS) for the simultaneous detection of six trace FWAs in flour. In the proposed method, the CE separation device is directly coupled to the mass spectrometer through a sheathless interface without the need for a sheath liquid for electric contact, thereby avoiding the dilution of the analytes and improving detection sensitivity. Various conditions that could affect extraction recovery, separation efficiency, and detection sensitivity were evaluated and optimized. The FWAs were effectively extracted from the sample matrix with reduced matrix effects by ultrasonic-assisted extraction at a temperature of 30 ℃ for 20 min using CHCl3-MeOH (3∶2, v/v) as the extraction solvent. The extract was centrifuged, dried under N2, and reconstituted in CHCl3-MeOH (1∶4, v/v) for subsequent analysis. During the detection process, the CE device was coupled to the ESI-MS/MS instrument via a highly sensitive porous spray needle, which served as the sheathless electrospray interface. The target FWAs were scanned in positive-ion mode (ESI+) to ensure the stability and intensity of the obtained signals. Additionally, multiple-reaction monitoring (MRM) mode and MS/MS analysis were used to simultaneously quantify the six targets with high selectivity. The developed sheathless CE-ESI-MS/MS method detected the FWAs with high sensitivity over wide linear ranges with low method limits of detection (0.04-0.67 ng/g). The recoveries of the six target FWAs at three spiked levels were between 77.5% and 97.2%, with good interday (RSD≤11.5%) and intraday (RSD≤10.2%) precision. Analyses of the six target FWAs in eight commercial flour samples were performed using this method, and four positive samples were identified. These results demonstrate that the proposed CE-ESI-MS/MS method is a promising strategy for the determination of trace FWAs in complex food sample matrices with efficient separation and high sensitivity.

Identification of Hydrocarbon Sulfonates as Previously Overlooked Transthyretin Ligands in the Environment.

Incidences of thyroid disease, which has long been hypothesized to be partially caused by exposure to thyroid hormone disrupting chemicals (TDCs), have rapidly increased in recent years. However, known TDCs can only explain a small portion (∼1%) of in vitro human transthyretin (hTTR) binding activities in environmental samples, indicating the existence of unknown hTTR ligands. In this study, we aimed to identify the major environmental hTTR ligands by employing protein Affinity Purification with Nontargeted Analysis (APNA). hTTR binding activities were detected in all 11 indoor dust and 9 out of 10 sewage sludge samples by the FITC-T4 displacement assay. By using APNA, 31 putative hTTR ligands were detected including perfluorooctanesulfonate (PFOS). Two of the most abundant ligands were identified as hydrocarbon surfactants (e.g., dodecyl benzenesulfonate). Moreover, another abundant ligand was surprisingly identified as a disulfonate fluorescent brightener, 4,4'-bis(2-sulfostyryl)biphenyl sodium (CBS). CBS was validated as a nM-affinity hTTR ligand with an IC50 of 345 nM. In total, hydrocarbon surfactants and fluorescent brighteners explain 1.92-17.0 and 5.74-54.3% of hTTR binding activities in dust and sludge samples, respectively, whereas PFOS only contributed <0.0001%. Our study revealed for the first time that hydrocarbon sulfonates are previously overlooked hTTR ligands in the environment.

Occurrence, migration and health risks of fluorescent whitening agents and phthalates in bottled water

The occurrence and health risks of fluorescent whitening agents (FWAs) in bottled water were reported for the first time. FWA184 and FWA393 were the most frequently detected FWAs, with mean concentrations of 3.99–17.00 ng L−1. Phthalates (PAEs) such as dibutyl phthalate (DBP), di-iso-butyl phthalate (DiBP), and diethylhexyl phthalate (DEHP) were prevalent in bottled water, with mean levels of 40.89–716.66 ng L−1, and their concentrations in bottled water were much higher than those of FWAs. FWAs and PAEs in bottles and caps were extracted using organic solvent, and the correlation analysis showed that FWA393 and DEHP most likely originated from bottles, while bottle caps were the main sources of DBP and DiBP. The calculated risk quotients (RQs) of target substances and all age groups were considerably lower than the threshold of 0.1, indicating that consuming bottled water containing these plastic additives was unlikely to pose health risks for people of all ages. However, RQ values for underage people were several times higher than those for adults and hence cannot be neglected; therefore, special attention should be paid to understand the potential risks posed by the exposure to these plastic additives during early life stages, especially the infant stage.

The influence of reed nanocellulose on the quality indicators of paper-basis for wallpapers

Improving the production technology of products with improved quality indicators and with less impact on the environment remains an urgent scientific and practical problem of paper industry enterprises. This refers to the technology for the production of paper-bases for wallpaper using environmentally safe chemical additives, in particular nanocellulose (NC), which was obtained by acid hydrolysis from reed cellulose. The production of cellulose was carried out in two stages - extraction from reed stalks with a solution of alkali and an organosolvent method of cooking in a solution of peracetic acid. The obtained organosolvent cellulose contained the remains of lignin and mineral substances, which allows it to be used for the preparation of NC. As a result of the hydrolysis of organosolvent cellulose, a time-stable NC suspension was extracted, the properties of which were investigated by scanning electron microscopy (morphological changes in the structure of reed cellulose-containing materials), atomic force microscopy (determination of topographic characteristics of NC), analysis of electronic absorption spectra (transparency of NC films). It was established that reed NC films had nanoparticles with a cross-sectional size of 5-25 nm, density up to 1.52 g/cm3, transparency up to 81.6 %, tensile strength up to 65 MPa. For the production of castings of paper-bases for wallpaper samples, sulfated pine bleached cellulose and polyester synthetic fiber were used, to the fibrous mass of which were added the following chemical additives: alkyl ketene dimer, reed NC, binder, and optical brightener. It has been shown that the use of nanocellulose at a rate of 0.35 % to 1.0 % of the paper mass leads to a significant improvement in the physical and mechanical quality indicators of the paper base for wallpaper. It was established that the replacement of 50 % of the synthetic chemical auxiliary substance alkyl ketene dimer with nanocellulose or additional application of nanocellulose at a rate of 0.5 g/m2 on the surface of the casting with 0.7 % alkyl ketene dimer allows to obtain paper that meets the requirements of the standard. The obtained results indicate the prospects of using reed nanocellulose for the production of other mass types of paper and cardboard.

An integrated method for rapid extraction of fluorescent whitening agents from selected cosmetics by in situ formation of deep eutectic solvent

A novel extraction methodology was developed based on deep eutectic solvent (DES) in situ formation. The solvent was synthesized from a binary mixture of L-cysteine, functioning as a hydrogen bond acceptor, and 2-methylphenol, serving as a hydrogen bond donor. The DES’s inherent molecular structures and extensive hydrogen bonding networks were characterized using the Fourier-transform infrared spectroscopy (FT-IR), while its hydrophobic nature was assessed by determining molecular polarity. Its extraction efficiency was demonstrated through the extraction of fluorescent whitening agents (FWAs) in cosmetic products, acting as a model analytical application. This was accomplished using vortex-assisted emulsification solid–liquid extraction (SLE) method, followed by high-performance liquid chromatography-fluorescence detection. Response surface methodology was employed to optimize extraction conditions in a multivariate experimental design. This approach streamlined the multi-operation extraction process via ingeniously integrating extraction and clean-up into a single step, resulting in significant reductions in extraction time required and high sample throughputs of approximately 40 samples per hour. The methodology was validated and exhibited excellent linearity in concentration ranges of 0.01–24 mg/L for five FWAs and 0.01–40 mg/L for other three FWAs, with correlation coefficients (r) ranging from 0.9985 to 1.000. The limits of detection and quantification were in the range of 0.03–0.26 mg kg−1 and 0.10–0.87 mg kg−1, respectively. The reliability and practicality of the proposed method were affirmed by quantifying eight FWAs in ninety-four commercially available facial masks and whitening creams, yielding recoveries values between 90.0 % and 106.0 % with relative standard deviations (RSDs) of 1.0–4.3 %. Inorganic ions and organic compounds present in the samples had minimal impact on FWAs detection following sample pre-treatment. This procedure showcased exceptional extraction capabilities towards a diverse array of FWAs with the aid of multiple interactions, suggesting significant potential for increasing sample throughput while reducing organic solvent and material consumptions compared with conventional SLE methods. The low-toxicity DES is an excellent alternative to traditional extractants typically applied to SLE techniques.

Decamethylcyclopentasiloxane-based sustainable and recyclable polyester fabric whitening using OB-1 fluorescent brightener

Fluorescent whitening agent OB-1 (OB-1) has non-toxicity, chemical stability, exceptional heat resistance, and light stability, and it is widely used in plastic products. However, raw OB-1 is difficult to apply in textiles by exhaustion process. The present investigation employed raw OB-1 without adding an auxiliary to bestow a whitening effect on polyester fabric in a sustainable medium of decamethylcyclopentasiloxane (D5). The Taguchi methodology was employed to optimize the whitening parameters. An L16 orthogonal array was utilized to investigate the optimal conditions for whitening temperature, whitening time, and OB-1 mass, with four whiteness levels. The signal-to-noise ratio was optimized using a larger-is-better approach to enhance the parameter responses. The study analyzed the main effect and interaction plot of multiple factors. The findings indicate that the temperature of the whitening process significantly impacts the whiteness of the polyester fabric (P < 0.05), with a 98.4 % contribution percentage. Under the optimal conditions, a whiteness value of 109.9 was observed for the polyester fabric. Subsequently, various analytical techniques, including FT-IR, SEM, TGA, and XRD, were employed to characterize the treated fabric. The results indicate that using D5 medium was viable for whitening polyester fabric. The study also examined the duration of washing and rubbing to determine their whitening performance. The study evaluated the whitening efficacy of polyester fabric treated with recycled D5 medium and demonstrated its potential for application at the pilot scale in the textile sector.

Tunable Circularly Polarized Luminescence by Confining Dye Molecules within Chiral Layered Metal–Organic Framework

AbstractCircularly polarized luminescence (CPL) active materials have attracted widespread attention because of their potential applications. Nonetheless, it is still a great challenge to fabricate CPL materials with both high fluorescence quantum efficiency (Φ) and high luminescent asymmetry factor (glum). According to the unique structure characteristics of chiral layered metal–organic frameworks (CLMOFs), herein a novel strategy to construct high‐performance CPL materials, by utilizing the confinement effect of CLMOFs is developed. Conjugate dye molecules, such as fluorescent brighteners, fluorescein, and rhodamine B, which are readily subjected to aggregation‐caused quenching (ACQ) effect, are successfully intercalated into CLMOF matrix, affording blue, yellow–green, and red CPL, respectively. Both high Φ and glum values of up to 91% and 0.069 are obtained, owing to the distinct confinement effect of CLMOFs. After confining dye molecules within CLMOF, the ACQ effect is effectively inhibited, which is beneficial for fluorescence enhancement; simultaneously, the chirality transfer from CLMOF matrix to dyes by controlling their arrangement in the chiral confinement microenvironment, leading to the high glum values. Based on the full‐color and strong CPL, a multi‐dimensional code system is proposed. This work paves a new avenue to design and assemble CPL materials with high Φ and glum, which can be widely adopted.

Characterizing Water Composition with an Autonomous Robotic Team Employing Comprehensive In Situ Sensing, Hyperspectral Imaging, Machine Learning, and Conformal Prediction

Inland waters pose a unique challenge for water quality monitoring by remote sensing techniques due to their complicated spectral features and small-scale variability. At the same time, collecting the reference data needed to calibrate remote sensing data products is both time consuming and expensive. In this study, we present the further development of a robotic team composed of an uncrewed surface vessel (USV) providing in situ reference measurements and an unmanned aerial vehicle (UAV) equipped with a hyperspectral imager. Together, this team is able to address the limitations of existing approaches by enabling the simultaneous collection of hyperspectral imagery with precisely collocated in situ data. We showcase the capabilities of this team using data collected in a northern Texas pond across three days in 2020. Machine learning models for 13 variables are trained using the dataset of paired in situ measurements and coincident reflectance spectra. These models successfully estimate physical variables including temperature, conductivity, pH, and turbidity as well as the concentrations of blue–green algae, colored dissolved organic matter (CDOM), chlorophyll-a, crude oil, optical brighteners, and the ions Ca2+, Cl−, and Na+. We extend the training procedure to utilize conformal prediction to estimate 90% confidence intervals for the output of each trained model. Maps generated by applying the models to the collected images reveal small-scale spatial variability within the pond. This study highlights the value of combining real-time, in situ measurements together with hyperspectral imaging for the rapid characterization of water composition.

Effect of Polymer Host on Aggregation-Induced Enhanced Emission of Fluorescent Optical Brighteners.

Fluorophores displaying concentration-dependent luminescence are becoming increasingly valuable in stress-sensing, tagging, and dyeing applications, including the quantification of recycled content in plastic packaging. In this work, we investigate the effects of the polymer matrix, dye structure, and crystallinity on aggregation-induced enhanced emission (AIEE). We demonstrate that the aggregation threshold required for successful quantification can be adjusted through modulation of guest-host (dye-polymer) interactions and monitored using an array of fluorescence characterization. Modification of guest-host interactions is realized through choice of host, change of guest, and tuning of the crystallinity of the host system. Increasing the number of guest-host interactions and solubility between guest and host, loosely predicted through the calculation of the solubility parameter, increases the aggregation threshold relative to other low-polarity and low-interacting systems. We demonstrate that issues, such as loading level and cost, associated with high aggregation thresholds, can be circumvented by increasing system crystallinity, improving spectral intensities, and subsequent quantification. These insights explore the fundamental understanding of supramolecular interactions that govern dye-polymer systems.

Toxicity of Three Optical Brighteners: Potential Pharmacological Targets and Effects on Caenorhabditis elegans.

Optical brighteners (OBs) have become an integral part of our daily lives and culture, with a growing number of applications in various fields. Most industrially produced OBs are derived from stilbene, which has been found in environmental matrices. The main objectives for this work are as follows: first, to identify protein targets for DAST, FB-28, and FB-71, and second, to assess their effects in some behaviors physiologic of Caenorhabditis elegans. To achieve the first objective, each OB was tested against a total of 844 human proteins through molecular docking using AutoDock Vina, and affinities were employed as the main criteria to identify potential target proteins for the OB. Molecular dynamics simulations took and validated the best 25 docking results from two protein databases. The highest affinity was obtained for the Hsp70-1/DAST, CD40 ligand/FB-71, and CD40 ligand/FB-28 complexes. The possible toxic effects that OBs could cause were evaluated using the nematode C. elegans. The lethality, body length, locomotion, and reproduction were investigated in larval stage L1 or L4 of the wild-type strain N2. In addition, transgenic green fluorescent protein (GFP) strains were employed to estimate changes in relative gene expression. The effects on the inhibition of growth, locomotion, and reproduction of C. elegans nematodes exposed to DAST, FB-71, and FB-28 OBs were more noticeable with respect to lethality. Moreover, an interesting aspect in OB was increased the expression of gpx-4 and sod-4 genes associated with oxidative stress indicating a toxic response related to the generation of reactive oxygen species (ROS). In all cases, a clear concentration-response relationship was observed. It is of special attention that the use of OBs is increasing, and their different sources, such as detergents, textiles, plastics, and paper products, must also be investigated to characterize the primary emissions of OBs to the environment and to develop an adequate regulatory framework.

An internal filtration effect-based "off-on" probe for fluorescent and visual sensing of formaldehyde.

Formaldehyde (FA) sensing in children's toys and water has great application prospects in the protection of home safety and the ecological environment. However, there has been no report heretofore addressing FA detection in children's toys. In this work, a fluorescent (FL) whitening agent (FWA), potassium dichromate, and sulfuric acid were proposed as an "off-on" probe (FPD) for FA sensing via FL and visual FL (VFL) methods. The FL emission of the FWA at 435 nm was quenched by Cr2O72- because of the internal filtration effect. The effect was interrupted after the addition of FA because Cr2O72- was reduced to Cr3+, accompanying the recovery of the FL emission of the FWA. The detection limit of FPD for FA via FL and VFL approaches was 2.03 and 85.5 μg L-1, respectively. The proposed probe was successfully utilized for FA detection in crawling mats and building blocks as well as environmental water (verified by the UV method), indicating good adaptability. The FPD-based FL method might be a potential approach for FA detection due to the merits of high selectivity, anti-interference ability, and stability.