Polymeric Dye Research Articles

Coherent Random Lasing Realized in Polymer Vesicles

We have demonstrated the realization of a coherent vesicle random lasing (VRL) from the dye doped azobenzene polymer vesicles self-assembled in the tetrahydrofuran-water system, which contains a double-walled structure: a hydrophilic and hydrophobic part. The effect of the dye and azobenzene polymer concentration on the threshold of random laser has been researched. The threshold of random laser decreases with an increase in the concentration of the pyrromethene 597 (PM597) laser and azobenzene polymer. Moreover, the scattering of small size group vesicles is attributed to providing a loop to boost the coherent random laser through the Fourier transform analysis. Due to the vesicles having the similar structure with the cell, the generation of coherent random lasers from vesicles expand random lasers to the biomedicine filed.

Waterborne polyurethane‐based dye with covalently bonded to Disperse blue 60

ABSTRACTA series of sulfonated waterborne polyurethane‐based dyes (DB60‐SWPUs) with covalently bonded to different proportions of Disperse blue 60 (DB60) were prepared by a modified acetone process. The expected structures of DB60‐SWPUs are characterized by Fourier transform infrared spectroscopy and 1H‐NMR spectra. The obtained DB60‐SWPUs show high viscosity and intriguing storage stability. The fluorescent performances, thermal properties, and mechanical properties of DB60‐SWPUs were characterized. Compared with DB60, the UV–vis spectra of DB60‐WPUs have obvious hypochromic shift, and the fluorescence intensities are obviously enhanced. The migration rates of DB60‐SWPUs are much lower than that of DB60. DB60‐SWPUs have thermal migration resistance and excellent color fastness. The polyester fiber dyed by DB60‐SWPUs has not only high color yield, good fracture strength, excellent breaking strength retention, but also good permeability and wrinkle resistance. Moreover, DB60‐SWPUs are polymeric dyes with water as a solvent, which are especially suitable for environmental protection. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48862.

Forensic Fiber Analysis by Thermal Desorption/Pyrolysis-Direct Analysis in Real Time-Mass Spectrometry.

The thermal desorption/pyrolysis-direct analysis in real time-mass spectrometry (TD/Py-DART-MS) method was developed for the analysis of fibers in this study. The fiber samples were pyrolyzed with a temperature gradient and the pyrolysis products were determined by DART-MS. The pyrogram from the TD/Py-DART-MS fiber analysis was found to be associated with the physical properties such as the melting points. At the same time, the TD/Py-DART-MS allows the analyst to obtain the chemical information such as polymeric backbone structures and dyes on the fiber. The pyrolysis profiles of common polymeric fibers in textile materials such as cotton, cellulose triacetate (CT), poly(caprolactam) (nylon-6), poly(hexamethylene adipamide) (nylon-6/6), poly(acrylonitrile) (PAN), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(propylene) (PP), and polytrimethylene terephthalate (PTT) and their respective characteristic mass spectra were reported in this study. The fibers from 40 commercial textile samples were analyzed by the TD/Py-DART-MS method, and the statistical methods including principal component analysis (PCA) and Pearson product moment correlation (PPMC) were applied to classify and associate the fibers based on their mass spectral data. The strong correlation between the reference fiber mass spectral profiles and tested fiber mass spectral profiles was observed by using the PPMC method, and the identification accuracy was 97.5%. When combined, the mass spectral and pyrogram data, the types of fibers including the blended fibers were identified effectively. The TD/Py-DART-MS method also demonstrated the promising capability for the identification of dyes on fibers. Overall, the TD/Py-DART-MS method requires small sample size and minimal sample preparation but offers reproducible and multidimensional information for the fiber evidence rapidly (i.e., ∼6.7 min). Since the proposed method is simple to perform and the data are easy to interpret, this approach may significantly contribute to the fiber identification and comparison procedures in forensic settings with high sample throughput potential.

Synthesis of new azo dye polymers based on naphthol by oxidative polycondensation: antimicrobial activity and fastness studies

Azo dye polymers were synthesized by an oxidative polycondensation reaction of naphthol based azo dyes with the oxidants NaOCl in an aqueous alkaline medium. These synthesized azo dye polymers were characterized by UV-Vis, FT-IR, 1H NMR techniques. The surface morphology of the azo dye polymers was understood by Scanning Electronic Microscopic study(SEM). The changes in weight in relation to change in temperature of synthesized compounds the was studied by TGA/DTA analysis. All the novel polymers were characterized to determine molecular weights by gel permeation chromatography(GPC). All of the azo dye monomers and polymers were researched for antibacterial (Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus Enterococcus faecalis, Acinetobacter baumannii, Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica) and antifungal (Kluyveromyces fragilis, Saccharomyces cerevisiae, Candida albicans) activities. When results of antibacterial activity of synthesized compounds was compared with standard Ampicillin, Streptomycin Sulfate, Nystatin. it is seen that the azo dye monomers had good antibacterial activity whereas the azo dye polymers did not have as good activity as the monomers. The dyes were examined in respect of their washing, water, sweat (acid and base) and frictional (dry and wet) fastness. From the results, It was found that The fastness properties of the azo dye monomers are better than the polymers. Because the bonding ability to the fabric in the monomers is better than the long chain polymers having a high molecular weight.

Interaction of conducting polymers, polyaniline and polypyrrole, with organic dyes: polymer morphology control, dye adsorption and photocatalytic decomposition

Conducting polymers, such as polyaniline and polypyrrole, have frequently been discussed in the literature due to ease of preparation and high application potential. These polymers have been observed to interact with organic dyes because of the similarity in the conjugated molecular structure of both moieties. The interaction manifests itself in three fundamental directions that have been so far treated separately. The first is represented by the conductivity enhancement and morphology control when using organic dyes as templates in polypyrrole preparation. The adsorption of dyes on conducting polymers is the second field oriented at the water pollution treatment. Finally, the photocatalytic decomposition of organic dyes aims at the similar environmental target. The last two applications do not require the presence of conductivity which, on the other hand, is a key parameter of conducting polymers. The future design of advanced adsorbents, however, has to exploit both the conductivity and electroactivity in the control of pollutant adsorption or degradation. For this reason, all these interactions and their practical impact are considered in the present review.

European JRC report on global deployment of more than 200 kW fuel cells

Near-infrared dyes are useful to monitor nanocarriers in vitro and in vivo and can serve as photosensitizers in cancer photodynamic therapy. However, strategies need to be developed to guarantee that the dye photophysical properties and loading within the drug delivery system remain stable for reliable tracking within biological systems. This work reports the facile chemical conjugation of the carbocyanine heptamethine near-infrared dye IR780 to polylactide for stable fluorescent labeling of biodegradable polyester nanocarriers. “Clickable” polylactide was synthesized via organocatalyzed ring opening polymerization of D,L-lactide with a cyclooctyne initiator. IR780 was derivatized and conjugated to polylactide via a one-pot copper-free azide-alkyne cycloaddition reaction. The synthetic strategy developed was effective to promote conjugation of the near-infrared fluorescent dye to polylactide, as confirmed by high performance liquid chromatography. Nanoparticles containing the dye–polymer conjugate were prepared by nanoprecipitation and characterized. Asymmetric flow field-flow fractionation with light scattering and fluorescence detection revealed that the near-infrared fluorescence of the nanoparticles remained stable and was not transferred to serum proteins. In contrast, significant transfer of the dye to serum proteins was evidenced when the dye was merely encapsulated in similar nanoparticles through physical entrapment. Confocal microscopy and fluorescence tomography imaging showed that the polymer-dye conjugate confers fluorescence properties to the NP suitable for further in vitro and in vivo pre-clinical studies.

Identification of Microfibers in the Environment Using Multiple Lines of Evidence.

Microfibers, characterized as small fibers shed from textiles that are less than 5 mm in size, are a prominent contaminant in the environment. Thus, it is important that we have methods to accurately quantify and characterize them, including in water, sediment, wildlife, seafood, and drinking water samples. Unfortunately, their small size and the presence of different dyes on the microfibers themselves cause difficulties in identification via conventional spectroscopic methods of total attenuated resonance-Fourier transform infrared and Raman. To help solve some of these methodological challenges, we developed a new method employing polymer-dye binding chemistry, density tests, unique surface morphological traits, and fluorescent staining to identify microfibers in environmental samples. The identification method introduced here was tested in our laboratory via trials using microfibers shed from new textiles and environmental samples. We found that the method can be successfully applied to identify the different polymer types of microfibers, which can ultimately help source apportion microfiber contamination in the environment.

IR780-polymer conjugates for stable near-infrared labeling of biodegradable polyester-based nanocarriers

Near-infrared dyes are useful to monitor nanocarriers in vitro and in vivo and can serve as photosensitizers in cancer photodynamic therapy. However, strategies need to be developed to guarantee that the dye photophysical properties and loading within the drug delivery system remain stable for reliable tracking within biological systems. This work reports the facile chemical conjugation of the carbocyanine heptamethine near-infrared dye IR780 to polylactide for stable fluorescent labeling of biodegradable polyester nanocarriers. “Clickable” polylactide was synthesized via organocatalyzed ring opening polymerization of D,L-lactide with a cyclooctyne initiator. IR780 was derivatized and conjugated to polylactide via a one-pot copper-free azide-alkyne cycloaddition reaction. The synthetic strategy developed was effective to promote conjugation of the near-infrared fluorescent dye to polylactide, as confirmed by high performance liquid chromatography. Nanoparticles containing the dye–polymer conjugate were prepared by nanoprecipitation and characterized. Asymmetric flow field-flow fractionation with light scattering and fluorescence detection revealed that the near-infrared fluorescence of the nanoparticles remained stable and was not transferred to serum proteins. In contrast, significant transfer of the dye to serum proteins was evidenced when the dye was merely encapsulated in similar nanoparticles through physical entrapment. Confocal microscopy and fluorescence tomography imaging showed that the polymer-dye conjugate confers fluorescence properties to the NP suitable for further in vitro and in vivo pre-clinical studies.

Electrochemical Polymerization-Fabricated Several Triphenylamine-Carbazolyl-Based Polymers with Improved Short-Circuit Current and High Adsorption Stability in Dye-Sensitized Solar Cells.

Polymer dyes have many potential advantages, such as high molecular weight, better light capture ability, thermal stability, film-forming ability, light resistance, and electrochemical corrosion resistance. They are expected to provide opportunities for the development of high-stability dye-sensitized solar cells (DSCs). However, polymer DSCs (PDSCs) have poor short-circuit current and filling factor (FF) due to polymer aggregation and chain-winding effect. Therefore, the energy conversion efficiency is low. In this work, we are trying to find a way to solve this problem. Herein, three polymers, polyPAC-01, polyPAC-02, and polyPAC-03 with different π-bridge chains were prepared on a titanium dioxide electrode using an “adsorption first, then electropolymerization (EP)” process. Meanwhile, as a comparison, three oligomers, PAC-01, PAC-02, and PAC-03 with the same skeleton were synthesized by the Suzuki coupling reaction and fabricated on a titanium dioxide electrode with a “first polymerization, then adsorption” process. Then, the photoanode adsorbed by those polymers or oligomers were applied to DSCs. The results show that polymers prepared by the EP method obtained a higher short-circuit (Jsc) increase, exceeding 30% and a FF increase of about 10%, and finally, the photo-to-electric conversion efficiency (PCE) increased exceeding 40%, compared to the oligomers. In addition, desorption experiments in a harsh environment show that the EP method-synthesized polymers (polyPAC-03 as a representative) have better solvent resistance and adsorption stability than the corresponding oligomers (PAC-03). The results show that the process of “adsorption first, then EP” may be an effective way to solve the bottlenecks of low energy conversion efficiency on PDSCs and provide a new way to develop stable and efficient DSCs.

Simultaneous Adsorption of Cationic Dyes from Binary Solutions by Thiourea-Modified Poly(acrylonitrile-co-acrylic acid): Detailed Isotherm and Kinetic Studies

In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.

Экспериментальное и теоретическое изучение фрагментации дихлор-3-арил-2,1-бензизоксазолов

2,1-Benzisoxazoles or anthranyls have different types of biological activity, are used to obtain monomers for polymeric materials, dyes and other heterocyclic compounds. In addition, 2,1-benzisoxazoles attract the attention of researchers due to the presence of a weak N-O bond, which is a potential place for the opening of the cycle in the reactions of reduction, oxidation, and various transformations. Therefore, it is very important to study their structure, methods of identification and reactivity in the processes taking place with their participation. One of the most effective modern research methods in chemistry is chromatography-mass spectrometry and quantum-chemical modeling. And since the fragmentation of molecules during their electron impact ionization depends on the nature of the compounds and characterizes their reactivity in various types of chemical reactions, the aim of this work was to experimentally and theoretically study the fragmentation of dichloro-3-phenyl-2,1-benzisoxazoles. For this, the corresponding dichloro-3-aryl-2,1-benzisoxazoles were synthesized by condensation of nitroarenes with arylacetonitriles in the presence of an excess of sodium hydroxide. The chromatography-mass spectrometry method was used to study the directions of fragmentation of their molecular ions. It was found that for all the compounds studied, similar fragment fragments are observed in the mass spectra, which indicates similar patterns of their fragmentation. Based on the data of quantum chemical modeling using the PC GAMESS/FireFly 8.2 software package using the density func-tional theory method, it was suggested that even before the decay of the molecular ions of dichloro-3-aryl-2,1-benzisoxazoles, they rapidly transform into the corresponding cation radicals of dichloroacridinones with the same atomic composition. Further decomposition of dichloroacridinone ions is accompanied by the release of a chlorine atom, carbon monoxide and skeletal rearrangement with the formation of the corresponding chlorocarbazole ions. Chlorocarbazole ions then eject a hydrogen chloride molecule to form a cation with m/z 164 and atomic composition C12H6N.

An A−D−Aʹ−Dʹ strategy enables perylenediimide-based polymer dyes exhibiting enhanced electron transport characteristics

In this work, we develop two new A−D−Aʹ−Dʹ type polymer dyes, namely PPDIDTBT and PPDIDTBT-2F, containing perylenediimide (PDI), thiophene, and benzothiadiazole units. Both polymer dyes have high thermal stability and broad absorption throughout the UV–vis region. More importantly, the introduction of the second electron-withdrawing units, benzothiadiazoles, endows both polymer dyes with low-lying LUMO energy levels of −3.85 eV for PPDIDTBT and −3.88 eV for PPDIDTBT-2F. The charge transport properties of the two polymer dyes were examined by fabricating organic field-effect transistors (OFETs) with top-gate/bottom-contact configuration. Both polymer dyes exhibit enhanced electron transport characteristics with the highest electron mobility of 0.070 cm2 V−1 s−1, which is among the highest values for PDI-based polymer semiconductors reported to date. Our results highlight that the A−D−Aʹ−Dʹ strategy is a useful approach in tuning orbital energetic and charge transport properties of polymer dyes for developing high-performance OFETs.

Polymer dye laser pumped with green semiconductor lasers

We report the results of experiments on quasi-longitudinal pumping of a polymer dye laser by two green ( λ = 513 nm) pulsed laser diodes. The lasing thresholds, efficiency, and photostability of pyrromethenes in various polymers are studied. The efficiency of dye lasers based on pyrromethene 567 and pyrromethene 580 with a three-mirror cavity with partial astigmatism compensation exceeds 20 %.

Dual pH/thermal-dependent coloring polymeric dye through Mannich reaction of chitosan: Synthesis and characterization

A novel polymeric dye was synthesized by one-pot Mannich reaction of chitosan (CS) and phenolphthalein (PHP). The grafting onto side chain of CS derivatives was confirmed by UV–vis, FT-IR, 1H NMR techniques. The degree of substitution (DS) calculated by 1H NMR and elemental analysis was revealed to increase with increasing mole ratio of formaldehyde and PHP. XRD analysis showed that the grafting through Mannich reaction was caused to amorphous structure in the derivatives. Covalent grafting of PHP onto CS made the grafted products showing pink color in basic conditions without leaching of dye and color fading after several weeks. Moreover, the derivatives dissolved in LiOH/urea systems could showed darker pink after heating. The results suggested that the novel CS derivatives with dual pH/thermal-dependent coloring property could potentially be prepared as pH/thermal-responsive biomaterial in a wide range of applications.

Polymerizable dye for colored particles synthesis with potential use in immunoassays

Latex-particles are suitable for diagnosis purpose since they are able to interact with biological molecules. In this work, a colored monomer was synthesized between basic fuchsine(BF) and glycidyl methacrylate(GMA). BF-GMA obtaining was verified through UV-Vis, IR, NMR and Mass spectrometry. The synthesis of colored particles by emulsion polymerization of styrene and the BF-GMA monomer was studied by measuring conversion, particle diameter, BF incorporation, surface charge densities and also in a protein binding assay. Results confirmed the production of stable particles, with controlled size and high BF incorporation, capable of interacting with proteins efficiently, and being used in an immunoagglutination test.

Preparation of Fluorescence-Encoded Microspheres Based on Hydrophobic Conjugated Polymer-Dye Combination and the Immunoassay.

Fluorescent microspheres are greatly demanded in many applications based on high-throughput suspension array technology. To realize the multiplexed assay, microspheres should be encoded to identify the interaction between analytes and spheres. This study advanced a strategy for preparing fluorescence-encoded microspheres, employing two hydrophobic fluorophores, poly(p-phenyleneethylene) (PPE), and Nile Red (NR), as well as the monodisperse amino-modified porous substrate polymeric spheres, poly(glycidyl methacrylate) microspheres (APGMA). Loading the fluorophores sequentially onto the substrate spheres via adsorption by immersing the spheres in the dipping solution of fluorophores resulted in the APGMA-PPE-NR spheres. By varying the concentration and combination of fluorophores in the solution, an array of 64-code APGMA-PPE-NR spheres was obtained and could be easily individually decoded via flow cytometry. A 2D dot plot from the flow cytometry of a set of mixed spheres with four different codes could also be differentiated, coincident with the overlaid plots of the spheres' corresponding codes but measured individually. These spheres were found to have good stability against washing, photobleaching, and thermal treatment. In addition, a sandwich immunoassay for the detection of goat IgG was performed, and the capability of the encoded spheres to be used in suspension array technology was demonstrated.

Discrimination of Tea by the Electrochemical Determination of its Antioxidant Properties by a Polyaniline – DNA – Polyphenazine Dye Modified Glassy Carbon Electrode

Voltammetric sensors have been developed on the bases of polyaniline and polymeric forms of methylene blue, methylene green, and neutral red obtained by multiple cycling of the potential. The integrity of the layers and expansion of the pH range of redox activity have been achieved by intermediate adsorption of native DNA that stabilized the oxidized polyaniline form. The formation of the coating layer was confirmed by electrochemical impedance spectroscopy and scanning electron microscopy. Model oxidants (ascorbic acid, hydroquinone, and quercetin) in the concentration range from 1 × 10−6 to 1 × 10−3 mol L−1 influenced the measured redox peaks of polymeric dyes with standard deviations from 2.4 to 5.5%. The peak currents were used for classification of tea brands using principal component analysis and linear discrimination analysis. The average discrimination of the tea brands purchased on local market was approximately 100%. The assessment of antioxidant properties of tea infusions was in agreement with results obtained using a coulometric bromine titration.

Modification of hyperbranched hemicellulose polymer and its application in adsorbing acid dyes

The paper presented a new, non-pollution macromolecule of adsorbing acid dyes, and developed the adsorption mechanism on the basis of effect between the modified groups of hyperbranched hemicellulose polymer and acid dyes. The modified hyperbranched hemicellulose polymer (HHP) with a large number of terminal carboxyl groups and hydroxyl groups was synthesized by hemicellulose maleate and dihydroxymethyl propionic acid. The degree of substitution, kinematic viscosity and thermal stability of HHP was determined. In SEM images, the HHP exhibited the pores and cross-linked structure which were good help for dye adsorption. When the HHP was applied in adsorbing Methyl red dye, Bromocresol green dye and Bromophenol blue dye, it exhibited higher adsorption capacity. The adsorption capacity changed with different adsorbent dosage, pH, temperature and ionic strength, and the optimal adsorption capacity for Methyl red dye, Bromocresol green dye and Bromophenol blue dye could reach 825 mg/g, 675 mg/g and 912 mg/g respectively. The adsorption mechanism, adsorption isotherm and adsorption diffusion mode were demonstrated by Pseudo-order model, Langmuir model, Intraparticle diffusion model and Memberance diffusion model respectively. The adsorption data possessed better correlation with Pseudo-second-order model, Langmuir model and Intraparticle diffusion model. The adsorption isotherms and thermodynamic date indicated the processes of HPP2 adsorbing three acid dyes were endothermic. The N2-adsorption/desorption isotherms of HPP2 revealed the hyperbranched hemicellulose polymer filled the pore in clusters, and its adsorption process met with monolayer adsorption.

Optimizing room temperature binder free TiO2 paste for high efficiency flexible polymer dye sensitized solar cells

Binder free TiO2 paste is prepared using tert-butyl alcohol in dilute acidic conditions at room temperature for flexible polymer dye sensitized solar cells (DSSCs). The present paper reports the detailed studies carried out to elucidate the importance of stirring times during the paste preparation on the final device performance. The maximum conversion efficiency of 4.2% was obtained for flexible DSSCs fabricated on tin doped indium oxide/polyethylene naphthalate substrates using TiO2 paste prepared with an optimum stirring time of 8 h. The effect of optimum stirring times on the device characteristics has been understood in terms of the detailed morphology and surface area measurements.

In-plane doping profile control of plate-like organic single crystals grown by a method combining electrospray and low vapor pressure liquid film

Although the molecular doping of single crystal organic semiconductors is expected as a key technology that imparts attractive functions in optical and electrical properties, the doping technology in single crystal organic material is still in the initial stages. In this study, doping profile control in the organic single crystal was examined by using an organic single crystal growth method in which a low vapor pressure liquid thin film is used as a crystal growth field and solutes are supplied by electrospray deposition. Steep doping profile control with a transition region of around 1–2 μm was demonstrated using dopants of small molecule red dye and green fluorescent polymer into plate-like single crystal of widegap fluorescent small molecule. We also evaluated the doping profile of the small molecule red dye in microwire-like single crystals of green fluorescent metal complex small molecule.