ABSTRACT
Poly(vinyl chloride), PVC, has many attractive properties, including low cost of manufacture, resistance to acid and alkali corrosion, and ease of molding. However, PVC suffers from aging in harsh conditions, leading to the shortening of its useful life. Stability to irradiation, for example, can be improved through the incorporation of additives to PVC. The design, synthesis, and application of new stabilizers continue to attract attention. The current work investigates the effect of three tin-cephalexin complexes on the stability of PVC on irradiation with ultraviolet (UV) light (λ = 313 nm) at 25 °C for a long duration. The PVC was blended with tin-cephalexin complexes at low concentrations (0.5% by weight), and thin films (around 40 µm) were made from the mixed materials. Various methods, including weight loss, infrared spectroscopy, and surface inspection of irradiated films were used to investigate the role played by these additives in the inhibition of PVC photodecomposition. The results confirmed that the additives led to a significant reduction in the rate of photodecomposition of the PVC blends. Tin-cephalexin complexes can absorb harmful radiation, deactivate hydrogen chloride, and scavenge high-energy species such as peroxides, therefore acting as stabilizers for PVC.
ABSTRACT
Poly(vinyl chloride) (PVC) is an important synthetic plastic that is produced in large quantities (millions of tons) annually. Additives to PVC are necessary to allow its use in many applications, particularly in harsh conditions. In regard to this, investigation of the synthesis of trimethoprim-tin complexes and their use as PVC additives is reported. Trimethoprim-tin complexes were obtained from the reaction of trimethoprim and tin chlorides using simple procedures. Trimethoprim-tin complexes (0.5% by weight) were added to PVC to produce homogenous mixtures and thin films were made. The effect of ultraviolet irradiation on the surface and properties of the PVC films was investigated. The level of both photodecomposition and photo-oxidation of PVC films containing trimethoprim-tin complexes was observed to be lower than for the blank film. The effectiveness of tin complexes as PVC photostabilizers reflects the aromaticity of the additives. The complex containing three phenyl groups attached to the tin cation showed the most stabilizing effect on PVC. The complex containing two phenyl groups was next, with the one containing butyl substituents resulting in the least stabilization of PVC. A number of mechanisms have been proposed to explain the role of the synthesized complexes in PVC photostabilization.
ABSTRACT
Poly(vinyl chloride) (PVC) undergoes photodegradation induced by ultraviolet (UV) irradiation; therefore, for outdoor applications, its photostability should be enhanced through the use of additives. Several carvedilol tin complexes were synthesized, characterized and mixed with PVC to produce thin films. These films were irradiated at 25 °C with a UV light (λ = 313 nm) for up to 300 h. The reduction in weight and changes in chemical structure and surface morphology of the PVC films were monitored. The films containing synthesized complexes showed less undesirable changes than the pure PVC film. Organotin with a high content of aromatics was particularly efficient in inhibiting photodegradation of PVC. The carvedilol tin complexes both absorbed UV light and scavenged radicals, hydrochloride, and peroxides and, therefore, photostabilized PVC.
ABSTRACT
The lifetime of poly(vinyl chloride) (PVC) can be increased through the addition of additives to provide protection against irradiation. Therefore, several new tin complexes containing atenolol moieties were synthesized and their photostabilizing effect on PVC was investigated. Reacting atenolol with a number of tin reagents in boiling methanol provided high yields of tin complexes. PVC was then mixed with the tin complexes at a low concentration, producing polymeric thins films. The films were irradiated with ultraviolet light and the resulting damage was assessed using different analytical and surface morphology techniques. Infrared spectroscopy and weight loss determination indicated that the films incorporating tin complexes incurred less damage and less surface changes compared to the blank film. In particular, the triphenyltin complex was very effective in enhancing the photostability of PVC, and this is due to its high aromaticity (three phenyl rings) compared to other complexes. Such an additive acts as a hydrogen chloride scavenger, radical absorber, and hydroperoxide decomposer.
ABSTRACT
Cis- or Z-configuration is required for the plant growth-promoting activity of cinnamic acid (CA), whereas the E-form is inactive. Herein, we describe the encapsulation of E-CA by cucurbit[7]uril (CB7) and show that photoisomerization reactions can be more efficiently controlled in aqueous solutions by utilizing this supramolecular approach. Measurements of UV-visible absorption and proton NMR spectra at different pH values confirm that E-CA and its methyl ester, methyl-E-cinnamate (MC), form stronger 1:1 host-guest complexes with CB7 compared to cucurbit[8]uril (CB8) or three cyclodextrins (α-, ß-, and γ-CD). Irradiation of (300 nm) UV light to an aqueous solution of the CB7-bound E isomers induces E to Z photoisomerization and the dissociation of the complex. When the same solution is irradiated by (254 nm) UV light, Z to E conformational changes of the unbound Z isomers are observed and are accompanied by restoring the host-guest complex formation.
Subject(s)
Bridged-Ring Compounds/chemistry , Cinnamates/chemistry , Imidazoles/chemistry , Photochemical Processes , Hydrogen-Ion Concentration , Models, Molecular , Molecular StructureABSTRACT
Aimed at further exploring the hosting properties of cucurbit[7]uril (CB7), we have exploited the spectroscopic and photophysical properties of a known fluorescent label as the guest molecule, namely, 3-cyano-6-(2-thienyl)-4-trifluoromethyl pyridine (TFP), in neat solvents. The formation of an inclusion host-guest complex with CB7 was checked by UV-vis absorption spectroscopy, and the value of binding constant (9.7 × 105 M-1) was extracted from the spectrophotometric data. The modulation of keto-enol equilibrium in TFP by the local environment is governed by the interplay between dimerization through intermolecular hydrogen bonding between individual solute molecules, favoring the enol form, and intermolecular hydrogen bonding between TFP and the surrounding solvents, favoring the keto form. Time-resolved fluorescence results established that the macromolecular CB7 host stabilizes preferentially the neutral enol form over the keto form of TFP. Unprecedentedly, our results reveal a linear dependence of the amplitudes of the extracted decay-associated spectra from the time-resolved fluorescence spectra of TFP on the sum of polarity/polarizability and hydrogen bonding parameters of the local environment, confirming that TFP at micromolar concentration in the CB7 complexes is experiencing a methanol-like environment. The results rationalized the 42-fold enhancement in the solubility of TFP in water media by complexation in CB7.
ABSTRACT
Time-resolved photoluminescence measurements were used to characterize the photophysical properties of 6-thienyllumazine (TLm) fluorophores in cellulose acetate nanofibers (NFs) in the presence and absence of mercuric acetate salts. In solution, excited-state proton transfer (ESPT) from TLm to water molecules was investigated at pH from 2 to 12. The insertion of thienyl group into lumazine introduces cis and trans conformers while keeping the same tautomerization structures. Global and target analyses were employed to resolve the true emission spectra of all prototropic, tautomeric, and rotameric species for TLm in water. The results support the premise that only the cis conformers are related to the ESPT process. However, no ESPT from TLm to a nearby water molecule was observed in NFs. The addition of NFs increases the excited-state lifetime of TLm in the solid state because of combined polarity/confinement effects. The solid-state fluorescence of TLm (in NFs) was quenched by mercuric acetate through different mechanisms-dynamic and static-depending on the applied pressure-atmospheric and vacuum, respectively. The new solid-state sensor is simple, ecofriendly, and instantly fabricated. TLM-loaded NFs can detect mercuric ions at a concentration of 50 picomolar. The formation of non-fluorescent ground-state complex between TLm molecules and mercuric ions inside the pores of NFs was achieved under vacuum condition.
