Synthesis and properties of new adducts of 2,2,6,6-tetramethylpiperidine and 2-hydroxyphenylbenzotriazole as polymer photostabilizers

The synthesis of new stabilizer type compounds (a combination between 2,2,6,6-tetramethylpiperidine and 2-hydroxyphenylbenzotriazole in one molecule) is reported. Three new polymerizable combined stabilizers as well as one unsaturated triazinyl-2,2,6,6-tetramethylpiperidine and three unsaturated triazinyl-2-hydroxyphenylbenzotriazoles as individual stabilizers were synthesized. Their copolymers and the terpolymers of the individual stabilizers with methyl methacrylate (MMA) were obtained. Chemical bonding of the stabilizers in the polymer was confirmed spectrophotometrically. The influence of these additives on the photostability of the copolymers was studied. The participation of the combined stabilizers in the polymerization did not affect considerably the rate of copolymerization, the molecular weight and polydispersity of the copolymers. A significant stabilizing effect against photodegradation was determined.     

UV and H2O2/UV degradation of a pharmaceutical intermediate in aqueous solution

The degradation of 5-methyl-1,3,4-thiadiazole-2-thiol (MMTD), a pharmaceutical intermediate found in some aquifers of Northern Italy, has been investigated by means of UV and UV/H2O2 treatments. The study has been carried out with a 17 W low pressure mercury lamp at room temperature, using a (100)/(1) (H2O2)/(MMTD) molar ratio. The results have demonstrated that: (i) with an initial MMTD concentration of 1 mg/l, 90% MMTD removal can be achieved within 1 hour or less than 5 minutes by UV or UV/H2O2 respectively; (ii) the sole UV irradiation does not cause any MMTD mineralization; (iii) with an initial MMTD concentration of 50 mg/l, 4 hours of UV/H2O2 treatment lead to an almost complete mineralization of the MMTD organic sulfur and to a partial mineralization of carbon (59%) and nitrogen (14%). The identification of degradation by-products, performed by HPLC-UV-MS analysis, revealed that the sole UV irradiation gives rise to the MMTD transformation into a single by-product that continuously accumulates in the solution. Conversely, the UV/H2O2 treatment forms seven intermediates that undergo further degradation through the breakdown of the thiadiazole ring. On the basis of the obtained results a degradation pathway has been proposed.     

Photophysics of untethered ZnTPP-fullerene complexes in solution

The spectroscopy and dynamic behavior of the self-assembled, Soret-excited zinc tetraphenylporphyrin (ZnTPP) plus fullerene (C(60)) model system in solution has been examined using steady state fluorescence quenching, nanosecond time-correlated single photon counting, picosecond fluorescence upconversion, and picosecond transient absorption methods. Evidence of ground state complexation is presented. Steady-state quenching of the S(2) and S(1) fluorescence of ZnTPP by C(60) reveals that the quenching processes only occur in the excited complexes, are ultrafast, and proceed at different rates in the two states. Only uncomplexed ZnTPP is observed by fluorescence lifetime methods; the locally excited complexes are either dark or, more likely, rapidly relax to products that do not radiate strongly. Both short-range (Dexter) energy transfer and electron transfer relaxation mechanisms are evaluated. Picosecond transient absorption data obtained from the subtle differences between the spectra of Soret-excited ZnTPP with and without a large excess of added C(60) reveal the formation, on a subpicosecond time scale, of relatively long-lived charge-separated species. Soret excitation of ZnTPP···C(60) does not produce a quantitative yield of species in the lower S(1) excited state.     

Photophysics of xanthene dyes in surfactant solution

The spectral (both absorption and fluorescence) and photoelectrochemical studies of some anionic xanthene dyes namely erythrosine B, rose bengal and eosin have been carried out in micellar solution of cationic cetyl trimethyl ammonium bromide (CTAB), anionic sodium dodecyl sulphate (SDS) and neutral triton X-100 (TX-100). The results show that all these dyes form 1:1 electron-donor-acceptor (EDA) or charge-transfer (CT) complexes with TX-100, which acts as an electron donor. There is no interaction of these dyes with SDS, whereas the interaction with CTAB is mainly electrostatic in nature. In presence of TX-100, these dyes show enhancement of fluorescence intensity with a red shift and develop photovoltage in a photoelectrochemical cell. A good correlation has been found among the photovoltage generation in the systems consisting of these dyes and TX-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Photodetector arrays directly assembled onto polymer substrates from aqueous solution

We report a simple and inexpensive approach to directly assemble arrays of cadmium sulfide (CdS) semiconductors onto transparent flexible poly(ethylene terephthalate) (PET) sheets via a polymer-mediated selective nucleation and growth process from an aqueous solution. This strategy of assembling functional materials onto plastics utilizes the surface functional molecules of the UV photooxidation patterned polymer to direct the nucleation and growth of CdS. We demonstrated that such assembled structures are viable for flexible macroelectronics, as manifested by the fabrication of CdS photodetector arrays on PET that can withstand bending. The best devices exhibited a specific detectivity of 3 x 10(11) cm Hz(1/2) W(-1) at 514-nm excitation wavelength at a modulation frequency of 90 Hz at room temperature. This direct assembly strategy eliminates additional lithography and etching steps during the deposition of the active inorganic semiconductor layer, is general to other inorganic materials and plastic substrates, and can enable low-cost, wearable, and/or disposable flexible electronics.     

Role of the UV absorber as a matrix in matrix‐assisted laser desorption/ionization mass spectrometric analysis of a mixture of a UV absorber and a stabilizer

A mixture of a UV absorber (Tinuvin 234 or Tinuvin 329) and a UV stabilizer (Tinuvin 770) was analyzed using matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) without any matrix. Fragmentation patterns of the UV absorbers and stabilizer were also investigated. The mass spectra showed the [M+H]⁺ ions and some fragment ions. Tinuvin 234, Tinuvin 329, and Tinuvin 770 generated three (m/z 119, 370, 432), one (m/z 252), and two (m/z 124 and 140) fragment ions, repectively. These fragment ions can be used to identify the chemical structures of the UV absorbers and stabilizer. Since the UV absorber performed a role as the matrix, the ion abundance of the UV stabilizer was enhanced by mixing with the UV absorber. When organic materials extracted from polypropylene (PP) containing the UV absorber and stabilizer were directly analyzed using MALDI‐MS without any matrix, the protonated molecule of the UV stabilizer was detected in abundance but the product ions of the UV absorber were not observed. When 2,5‐dihydroxybenzoic acid was used as a matrix, the protonated molecule of the UV absorber was observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Dual role of a hydroxyphenylbenzotriazole UV absorber in the photooxidation of wool

The protective effect of the UV absorber, sodium 2-(2′-hydroxy-5′-methylphenyl)benzotriazole sulfonate, on the light stability of wool has been examined. The degree of protection, as measured by the reduction in the rate of photoyellowing of the fiber, is highly dependent on both the spectral composition of the light source and the pH at which the absorber is applied to the fiber. This is due mainly to traces of the deprotonated, phosphorescent form of the absorber which can sensitize the photooxidation of wool in visible light, hence counteracting the photostabilizing influence of the UV absorber.     

Photophysics of Nile red in solution: steady state spectroscopy

Spectroscopic properties of Nile red (NR) in organic solvents, binary solvent mixtures have been studied. Remarkable shifts in the emission band positions have been observed as a function of the polarity of the medium. In solvent mixtures, these shifts can be explained by the process of specific solvation known as dielectric enrichment. The displacement of the fluorescence band was also measured as a function of temperature to obtain the thermochromic shifts (15 cm(-1) K(-1) in methyltetrahydrofuran and 13.8 cm(-1) K(-1) in butanol). Excited state dipole moments were calculated from these shifts.     

Modified polymer substrates for the formation of submicron particle ensembles from colloidal solution

Methods for targeted regulation of the surface properties of polymer film materials (substrates) by fluorination and sulfonation have been considered. It has been shown by the examples of polyethylene, polypropylene, and poly(ethylene terephthalate) films that these methods can be used for the production of polymer films with controlled values of water contact angle from 20° to 88°, adhesion force from 23 to 141 rel. units, and surface roughness parameter R_a from 35 to 382 nm. This set of substrates may be used to optimize the methods for the formation of structured functional polymer surfaces. In particular, the regularities of the formation of solid deposits of colloidal submicron particles during evaporation of droplets of their solutions have been shown to vary with variations in substrate characteristics.     

Positive and negative TiO2 micropatterns on organic polymer substrates

Ordered titanium dioxide (TiO2) films have received increasing attention because of their great potential in photocatalysis, energy conversion, and electrooptical techniques. Such films are often fabricated as coatings on various substrates such as silicon or a variety of polymers. Liquid-phase deposition (LPD) of TiO2 films is especially promising for organic substrates due to its very mild reaction conditions. In the present paper, LPD is conducted on a wettability-patterned polypropylene surface to fabricate positive and negative TiO2 micropatterns. A thin layer of ammonium persulfate in an aqueous solution was sandwiched between two biaxially oriented polypropylene (BOPP) films, and a photomask was employed to control the irradiation region. Within a short time interval, a high hydrophilicity could be obtained on the irradiation region, and an effective wettability contrast between the irradiated and unirradiated regions could be created to further induce the formation of two types of TiO2 micropatterns. Up until now, most approaches for micropatterning have been based on self-assembled monolayers on surfaces of gold (or other noble metals), silicon, and various polyesters. With the present method, however, there is no longer any limitation in the type of substrate used. Our work demonstrates that an anatase TiO2 film could be selectively deposited on a hydrophilic region, giving rise to a positive pattern with significant bonding strength and good line edge acuity, providing an effective solution toward the microfabrication on various inert polymer substrates. More surprisingly, we find, for the first time, that TiO2 could also be selectively retained on a hydrophobic region to form a negative pattern by simply adjusting the reaction conditions. Further analysis of the mechanism shows that, independent of the deposition conditions, the TiO2 deposition pattern changes gradually, from being initially negative to becoming positive as the deposition time increases. The surface functionality changes (from sulfate to hydroxyl groups) during the deposition, and the resulting difference in the affinity for TiO2 is used to interpret this negative-to-positive pattern change. Such negative patterns refute the conventional opinion that only hydrophilic regions favor the formation of TiO2 films and could be used to fabricate large areas (mm2) of interconnected TiO2 micronetworks. Such networks are difficult to obtain by conventional metallic masks, and the present method is expected to provide new strategies in the fabrication of flexible photomasks and macro/mesoporous TiO2 films. An example is given wherein a patterned photografting of poly(acrylic acid) on the surface of BOPP is achieved by using such a polymer-based photomask. The innovativeness of this method arises from its ability to provide negative patterning, whereas present related approaches have been found only to give positive patterns from an equivalent photomask. Unlike complex photolithography procedures, our irradiation and patterning process does not require the use of positive or negative photoresists, and should thus prove to be a simple, fast, and low-cost method.     

Freestanding sulfonated graphene oxide paper: a new polymer electrolyte for polymer electrolyte fuel cells

Sulfonated graphene oxide paper was fabricated by vacuum filtration of a colloidal solution of sulfonated graphite oxide. Layer by layer assembly of graphene oxide nano sheets interconnects the conduction paths and therefore sulfonated graphene oxide exhibits good proton conductivity and fuel cell performance.     

Predicting the solution morphology of a sulfonated pentablock copolymer in binary solvent mixtures

The solution morphologies of a midblock-sulfonated pentablock copolymer in miscible polar/nonpolar solvent blends were characterized as a function of solvent composition and polymer concentration using small angle X-ray scattering. Three distinct solution morphologies are observed upon changing the composition of the solvent blend. At low weight fractions of polar solvent, spherical, sulfonated-core micelles are observed, while spherical, sulfonated-corona (inverted) micelles are observed at high weight fractions of polar solvent. Polymer solution scattering is observed at intermediate concentrations of polar solvent. Additionally, the characteristic dimensions of the sulfonated-core micelles were found to change strongly upon variation of the solvent blend composition, indicating that these solutions—and correspondingly the morphology and properties of polymer membranes into which they are cast—can be tuned through simple variations in the solvent blend chemistry. We demonstrate that the solution morphologies and the characteristic micelle dimensions of these complex pentablock copolymer/binary solvent blends can be reliably predicted by considering the relative interactions of each polymer block and the solvent blend using the Hansen solubility parameters. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 254–262     

Static and dynamic light scattering of a random coil polymer in rodlike polymer solution

We have studied ternary solutions of rodlike and random coil polymers in a common solvent. In these solutions, the rods scatter weakly, and almost all scattering comes from the coil component. From light scattering measurements, we gained information about the thermodynamic and hydrodynamic properties of the coil in rodlike polymer solutions.     

Photophysics of norharmane in solution phase: From homogeneous to microheterogeneous environments

The photobehavior of norharmane (9H-pyrido[3,4-b]-indole) (NHM), one of the vastly used skeleton of drugs in therapeutic applications, has recently been the subject of increasing interest due to the finding of their phototoxic and photocarcinogenic properties. Its absorption and fluorescence behavior from different prototropic species show remarkable sensitivity towards the polarity, viscosity and local pH, exhibited by various microheterogeneous bio and biomimetic environments like micelles, reverse micelles, proteins, etc. The significant results obtained for NHM in homogeneous and a series of microheterogeneous environments is reviewed in this account. Much attention has been given to the properties of the excited states, location and biodistribution of NHM in different biological environments. The results can help in understanding the photophysics of the probe in biological environments and in assessing the correlation between different prototropic forms and biological activity.     

Chlorofluorocarbene: first UV observation of a dihalocarbene in solution

Chlorofluorocarbene (ClCF), generated by laser flash photolysis of chlorofluorodiazirine, absorbs at 368 nm in pentane. Absolute rate constants are reported for ClCF additions to several alkenes and pyridine. ClCF is less reactive toward alkenes than CCl(2), and it does not react rapidly with oxygen. Pertinent computational studies are included.     

Probing the intramolecular hydrogen bond of 2-(2-hydroxyphenyl)benzotriazoles in polar environment: a photophysical study of UV absorber efficiency

An in-depth photophysical study is presented for a series of 2-(2-hydroxyphenyl)benzotriazoles (HBzTs); the structural characteristic of all these photostabilizers is their strong intramolecular hydrogen bridge (IMHB). Tinuvin P (TIN P, 11a) and six other HBzTs, with no substituent in the 3'-position ortho to the hydroxy function, show pronounced phosphorescence already in the dark (at 77 K in a polar glass). Upon irradiation, the phosphorescence intensity rises further until an equilibrium value is attained (up to 1.5 fold the dark value). A kinetic model is given which excellently reproduces this phosphorescence evolution: it demonstrates phosphorescence to arise from open conformers where the IMHB has been broken. Phosphorescence excitation spectra match the absorption spectra of the open conformer and also that of the O-methyl homologue 11A which cannot form an IMHB. Fluorescence spectra likewise prove the equilibrium between the closed and open conformer for these HBzTs. In unpolar glasses as well as in the crystalline state, TIN P displays a long-wavelength (red) fluorescence (with an enormous Stokes shift of approximately 10.000 cm-1) which is associated with the excited singlet state of the closed form after proton transfer within the IMHB, S1'(C). In polar matrixes, on the other hand, a blue fluorescence is observed (with a regular Stokes shift) for all those HBzTs which have no 3'-substituent shielding the IMHB against being opened by the polar solvent. This blue fluorescence, just as the characteristic phosphorescence evolution for these compounds, is associated with the open conformer. For HBzTs with an (alkyl) group ortho to the bridging OH group, however, a long-wavelength (red) fluorescence is again observed. The shielding effect of the 3'-substituent shows a fine gradation, cumyl >/= 1,1,3,3-tetramethylbutyl (isooctyl) > t-butyl >/= methyl.     

Photochemical behavior of a new long-chain UV absorber derived from 4-tert-butyl-4'-methoxydibenzoylmethane

A new UV filter, the 1-(4-tert-butylphenyl)-2-decanyl-3-(4'-methoxyphenyl)-propane-1,3-dione, called C10-DBM, was prepared by grafting a 10-carbon aliphatic chain to the alpha-carbonyl position of 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM), a well-known and often used UV filter. The UV-A absorption efficiency of organic solutions containing the new filter was tested and compared with identical solutions containing BM-DBM with or without irradiation (xenon lamp). The originality of this new filter is that its UV-A absorbance appeared during irradiation of the molecule. Although the molar absorption coefficient of C10-DBM in the UV-A domain was lower than that of BM-DBM, the solutions absorption exhibited a much more photostable behavior under irradiation. In this study, we first demonstrated that C10-DBM was a precursor of BM-DBM (enol isomer) by means of high-performance liquid chromatography followed by mass spectrometry. Indeed, we showed that the UV-A absorption of C10-DBM solutions appearing during the irradiation of the molecule was due to a Norrish-II reaction (beta-cleavage), which induced the release of the BM-DBM enol form and 1-decene. Then, we established a kinetic model for the photochemistry of C10-DBM and fitted the variation of UV absorption spectra to confirm the proposed mechanism.     

Structure formation of sulfonated polyphenylquinoxalines in solution and in the solid state

Sulfonated polyphenylquinoxalines with different content of sulfo groups have been synthesized by polymer analogous reactions under different conditions. The rheological properties of these polymers in Nmethylpyrrolidone have been studied. The mechanical properties of films based on sulfonated polyphenylquinoxalines under uniaxial tension have been measured. The structures of the polymers have been examined by AFM.     

UV radiation effects on flavocytochrome b2 in dilute aqueous solution

A dilute aqueous solution of flavocytochrome b2 when exposed to inactivating doses of UV radiation at 280 nm underwent reversible loss in activity both under aerated and deaerated conditions. The active site as well as the substrate binding sites were found to be modified in the irradiated enzyme. Irradiation of the enzyme in the UV-C range resulted in partial unfolding of the polypeptide framework. Destruction and/or modification of both tryptophan and tyrosine residues as well as heme moieties took place. Preliminary laser flash photolysis studies suggest that the initial photo-ionization takes place with tryptophan and tyrosine residues with the formation of excited states and radicals, and then rapid transfer of electrons takes place to histidyl and cystinyl sites which might have eventually been altered in the process.     

Kinetics of tartrazine photodegradation by UV/H2O2 in aqueous solution

In the present work, kinetics of tartrazine decay by UV irradiation and H₂O₂ photolysis, and the removal of total organic carbon (TOC) under specific experimental conditions was explored. Irradiation experiments were carried out using a photoreactor of original design with a low-pressure Hg vapour lamp. The photodegradation rate of tartrazine was optimised with respect to the H₂O₂ concentration and temperature for the constant dye concentration of 1.035 × 10^?5 M. Tartrazine degradation and the removal of TOC followed the pseudo-first-order kinetics. The much higher k _obs value for tartrazine degradation (7.91 × 10^?4 s^?1) as compared with the TOC removal (2.3 × 10^?4 s^?1) confirmed the presence of reaction intermediates in the solution.