Pendant Modification of Poly(methyl methacrylate) to Enhance Its Stability against Photoirradiation.

Photostabilization of functional polymeric materials is important for protection against aging and ultraviolet (UV) irradiation. There is, therefore, the impetus to modify polymers to increase their resistance to photodegradation and photooxidation on extended exposure to UV light in harsh conditions. Various polymeric additives have been designed and synthesized in recent years, and their potential as photostabilizers has been explored. Reported here is the effect of pendant functionalization of poly(methyl methacrylate) (PMMA) through organometallic moiety incorporation into the polymer's backbone. The reaction of PMMA with ethylenediamine leads to the formation of an amino residue that can react with salicylaldehyde to produce the corresponding Schiff base. Adding metal chlorides (zinc, copper, nickel, and cobalt) led to the formation of organometallic residues on the polymeric chains. Thin films of modified and unmodified PMMA were produced and irradiated with UV light to determine the effect of pendant modification on photostability. The photostabilization of PMMA was assessed using a range of methods, including infrared spectroscopy, weight loss, decomposition rate constant, and surface morphology. The modified PMMA incorporating organic Schiff base metal complexes showed less photodecomposition than the unmodified polymer or one containing the Schiff base only. Thus, the metals significantly reduced the photodegradation of polymeric materials. The polymer containing the Schiff base-cobalt unit showed the least damage in the PMMA surface due to photoirradiation, followed by those containing nickel, zinc, and copper, in that order.

(E)-5-(4-Meth-oxy-phen-yl)-N'-(2-oxoindolin-3-yl-idene)-1-phenyl-1H-pyrazole-3-carbohydrazide.

The asymmetric unit of the title compound, C25H19N5O3, is composed of two independent mol-ecules with slightly different conformations. The extended structure features N-H⋯O hydrogen bonds as well as π-π inter-actions.

Metal Oxide Nanoparticles Containing Clotrimazole to Suppress Photodegradation of Poly(Vinyl Chloride) Thin Films.

Pol(vinyl chloride) or PVC has functional properties that enable its use in many industrial applications. It suffers from aging, however, in harsh conditions (e.g., elevated temperature or high humidity levels) if oxygen is present. One way to enhance the photostability of PVC is to blend it with additives. Thus, thin films were made by mixing PVC with clotrimazole, and five metal oxide (titanium, copper, cobalt, chromium, and nickel oxides) additives. The metal oxides and clotrimazole were added at concentrations of 0.1 and 0.5% by weight, respectively. The effect of the metal oxide nanoparticles accompanied by clotrimazole on the photodegradation of PVC was then assessed. The results indicated that the additives have a stabilizing effect and protect PVC against photodegradation significantly. The formation of polymeric fragments of small molecular weight containing carbon-carbon double bonds and carbonyl groups was lower in the blends containing metal oxide nanoparticles and clotrimazole than in unblended PVC. Similarly, the decrease in weight was much less for the films blended with additives. Additionally, surface analysis of the irradiated polymeric films showed significantly lower damage in the materials containing additives. The most effective additive in the stabilization of PVC was nickel oxide nanoparticles. The metal oxides are highly alkaline and act as scavengers for the hydrogen chloride produced during the photodegradation of PVC. They additionally act as peroxide decomposers. In contrast, clotrimazole can absorb harmful radiation and act as an ultraviolet absorber due to its heteroatom and aromatic content. Thus, the use of a combination of metal oxide nanoparticles and clotrimazole led to significant improvement in the resistance of PVC toward photodegradation.

Enhancement of Photostabilization of Poly(Vinyl Chloride) in the Presence of Tin-Cephalexin Complexes.

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.

Palladium Nanoparticles on Chitosan-Coated Superparamagnetic Manganese Ferrite: A Biocompatible Heterogeneous Catalyst for Nitroarene Reduction and Allyl Carbamate Deprotection.

Although metallic nanocatalysts such as palladium nanoparticles (Pd NPs) are known to possess higher catalytic activity due to their large surface-to-volume ratio, however, in nanosize greatly reducing their activity due to aggregation. To overcome this challenge, superparamagnetic chitosan-coated manganese ferrite was successfully prepared and used as a support for the immobilization of palladium nanoparticles to overcome the above-mentioned challenge. The Pd-Chit@MnFe2O4 catalyst exhibited high catalytic activity in 4-nitrophenol and 4-nitroaniline reductions, with respective turnover frequencies of 357.1 min-1 and 571.4 min-1, respectively. The catalyst can also be recovered easily by magnetic separation after each reaction. Additionally, the Pd-Chit@MnFe2O4 catalyst performed well in the reductive deprotection of allyl carbamate. Coating the catalyst with chitosan reduced the Pd leaching and its cytotoxicity. Therefore, the catalytic activity of Pd-Chit@MnFe2O4 was proven to be unrestricted in biology conditions.

Effect of Zinc Oxide Nanoparticles on Capsular Gene Expression in Klebsiella pneumoniae Isolated from Clinical Samples.

Klebsiella pneumoniae is an opportunistic pathogen with various virulence factors that give it the capability to invade a host. Nevertheless, the treatment of bacterial infection is gradually complicated as the bacteria can develop resistance to antimicrobial agents. As nanotechnology is a prosperous field for researchers, we employed zinc oxide (ZnO) nanoparticles (NPs) on isolates of Klebsiella pneumoniae. Here, we studied the effect of three NP concentrations-0.25, 0.50, and 0.75 mM-on the gene expression of Klebsiella pneumoniae capsules in isolates collected from different samples. After conducting an anti-bacterial test, the highest nine types of bacteria that resisted the antibacterial agent were chosen for further examination. The gene expression of four genes responsible for capsule manufacturing, namely magA, k2A, rmpA, and kfu, were investigated. When the NP concentration was 0.25 mM, the lowest efficiency was obtained. However, when the concentration increased to 0.50 mM, a noticeable effect on gene expression was detected; consequently, at a concentration of 0.75 Mm, the highest impact was achieved and the gene expression was stopped.

Synthesis of Methyldopa-Tin Complexes and Their Applicability as Photostabilizers for the Protection of Polyvinyl Chloride against Photolysis.

Polyvinyl chloride (PVC) is a ubiquitous thermoplastic that is produced on an enormous industrial scale to meet growing global demand. PVC has many favorable properties and is used in various applications. However, photodecomposition occurs when harsh conditions, such as high temperatures in the presence of oxygen and moisture, are encountered. Thus, PVC is blended with additives to increase its resistance to deterioration caused by exposure to ultraviolet light. In the current research, five methyldopa-tin complexes were synthesized and characterized. The methyldopa-tin complexes were mixed with PVC at a concentration of 0.5% by weight, and thin films were produced. The capability of the complexes to protect PVC from irradiation was shown by a reduction in the formation of small residues containing alcohols, ketones, and alkenes, as well as in weight loss and in the molecular weight of irradiated polymeric blends. In addition, the use of the new additives significantly reduced the roughness factor of the irradiated films. The additives containing aromatic substituents (phenyl rings) were more effective compared to those comprising aliphatic substituents (butyl and methyl groups). Methyldopa-tin complexes have the ability to absorb radiation, coordinate with polymeric chains, and act as radical, peroxide, and hydrogen chloride scavengers.

Synthesis and Application of Levofloxacin-Tin Complexes as New Photostabilizers for Polyvinyl Chloride.

Polyvinyl chloride (PVC) is a synthetic polymer with a wide range of applications with impact on our daily life. It can undergo photodegradation with toxic products that are hazardous to both human health and the environment. In addition, photodegradation shortens the useful lifetime of the material. Elongation of the effective lifespan of PVC is, therefore, a salient area of research. Recently, a lot of attention has been directed toward the design, preparation, and usage of new additives that are capable of reducing the photodecomposition of PVC. This work investigates the synthesis of new levofloxacin-tin complexes and their potential exploitation against the photodecomposition of PVC. Several levofloxacin-tin complexes have been synthesized, in high yields, by a simple procedure and characterized. The potential use of the additives as photostabilizers for PVC has been investigated through the determination of weight loss, molecular weight depression, formation of fragments containing carbonyl and alkene groups, and surface morphology of irradiated PVC films. The results show that the new additives are effective in reducing the photodegradation of PVC. The new levofloxacin-tin complexes act as absorbers of ultraviolet light and quenchers of highly reactive species such as free radicals produced during photodegradation. They are more effective photostabilizers compared with organotin complexes previously reported. The complexes containing aromatic substituents were more effective than those counterparts having aliphatic residues.

Synthesis of New Norfloxacin-Tin Complexes to Mitigate the Effect of Ultraviolet-Visible Irradiation in Polyvinyl Chloride Films.

Polyvinyl chloride is used in the manufacturing of a wide range of products, but it is susceptible to degradation if exposed to high temperatures and sunlight. There is therefore a need to continuously explore the design, synthesis, and application of new and improved additives to reduce the photodegradation of polyvinyl chloride in harsh environments and for outdoor applications. This research investigates the use of new norfloxacin-tin complexes as additives to inhibit the photodegradation of polyvinyl chloride to make it last longer. Reactions between norfloxacin and substituted tin chlorides, in different molar ratios and in methanol under reflux conditions, gave the corresponding organotin complexes in high yields. The chemical structures of the synthesized complexes were established, and their effect on the photodegradation of polyvinyl chloride due to ultraviolet-visible irradiation was investigated. Norfloxacin-tin complexes were added to polyvinyl chloride at very low concentrations and homogenous thin films were made. The films were irradiated for a period of up to 300 h, and the damage that occurred was assessed using infrared spectroscopy, polymeric materials weight loss, depression in molecular weight, and surface inspection. The degree of photodegradation in the polymeric materials was much less in the blends containing norfloxacin-tin complexes compared to the case where no additives were used. The use of the additives leads to a reduction in photodegradation (e.g., a reduction in the formation of short-chain polymeric fragments, weight loss, average molecular weight depletion, and roughness factor) of irradiated polyvinyl chloride. The norfloxacin-tin complexes contain aromatic moieties (aryl and heterocycle), heteroatoms (nitrogen, oxygen, and fluorine), and an acidic center (tin atom). Therefore, they act as efficient photostabilizers by absorbing the ultraviolet radiation and scavenging hydrogen chloride, peroxides, and radical species, thereby slowing the photodegradation of polyvinyl chloride.

Fabrication of Highly Photostable Polystyrene Films Embedded with Organometallic Complexes.

Polystyrene is a common thermoplastic and is produced in different shapes and forms. The scale of manufacture of polystyrene has grown over the years because of its numerous applications and low cost of production. However, it is flammable, brittle, has low resistance to chemicals, and is susceptible to photodegradation on exposure to ultraviolet radiation. There is therefore scope to improve the properties of polystyrene and to extend its useful lifetime. The current work reports the synthesis of organometallic complexes and investigates their use as photostabilizers for polystyrene. The reaction of excess ibuprofen sodium salt and appropriate metal chlorides in boiling methanol gave the corresponding complexes excellent yields. The organometallic complexes (0.5% by weight) were added to polystyrene and homogenous thin films were made. The polystyrene films blended with metal complexes were irradiated with ultraviolet light for extended periods of time and the stabilizing effects of the additives were assessed. The infrared spectroscopy, weight loss, depression in molecular weight, and surface morphology of the irradiated blends containing organometallic complexes were investigated. All the synthesized organometallic complexes acted as photostabilizers for polystyrene. The damage (e.g., formation of small polymeric fragments, decrease in weight and molecular weight, and irregularities in the surface) that took place in the polystyrene blends was much lower in comparison to the pure polystyrene film. The manganese-containing complex was very effective in stabilizing polystyrene and was superior to cobalt and nickel complexes.

Substituted Organotin Complexes of 4-Methoxybenzoic Acid for Reduction of Poly(vinyl Chloride) Photodegradation.

Poly(vinyl chloride) suffers from degradation through oxidation and decomposition when exposed to radiation and high temperatures. Stabilizers are added to polymeric materials to inhibit their degradation and enable their use for a longer duration in harsh environments. The design of new additives to stabilize poly(vinyl chloride) is therefore desirable. The current study includes the synthesis of new tin complexes of 4-methoxybenzoic acid and investigates their potential as photostabilizers for poly(vinyl chloride). The reaction of 4-methoxybenzoic acid and substituted tin chlorides gave the corresponding substituted tin complexes in good yields. The structures of the complexes were confirmed using analytical and spectroscopic methods. Poly(vinyl chloride) was doped with a small quantity (0.5%) of the tin complexes and homogenous thin films were made. The effects of the additives on the stability of the polymeric material on irradiation with ultraviolet light were assessed using different methods. Weight loss, production of small polymeric fragments, and drops in molecular weight were lower in the presence of the additives. The surface of poly(vinyl chloride), after irradiation, showed less damage in the films containing additives. The additives, in particular those containing aromatic (phenyl groups) substitutes, inhibited the photodegradation of polymeric films significantly. Such additives act as efficient ultraviolet absorbers, peroxide quenchers, and hydrogen chloride scavengers.

FTIR, Weight, and Surface Morphology of Poly(vinyl chloride) Doped with Tin Complexes Containing Aromatic and Heterocyclic Moieties.

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.

Microporous activated carbon developed from KOH activated biomass waste: surface mechanistic study of methylene blue dye adsorption.

In this work, sugarcane bagasse waste (SBW) was used as a lignocellulosic precursor to develop a high-surface-area activated carbon (AC) by thermal treatment of the SBW impregnated with KOH. This SBW activated carbon (SBWAC) was characterized by crystallinity, porosity, surface morphology and functional groups availability. The SBWAC exhibited Type I isotherm which corresponds to microporosity with high specific surface area of 709.3 m2/g and 6.6 nm of mean pore diameter. Further application of SBWAC as an adsorbent for methylene blue (MB) dye removal demonstrated that the adsorption process closely followed the pseudo-second order kinetic and Freundlich isotherm models. Conversely, a thermodynamic study revealed the endothermic nature and spontaneity of MB dye adsorption on SBWAC with high acquired adsorption capacity (136.5 mg/g). The MB dye adsorption onto SBWAC possibly involved electrostatic interaction, H-bonding and π-π interaction. This work demonstrates SBW as a potential lignocellulosic precursor to produce high-surface-area AC that can potentially remove more cationic dyes from the aqueous environment.

Effect of Ultraviolet Irradiation on Polystyrene Containing Cephalexin Schiff Bases.

The scale of production of polystyrene has escalated in the recent past in order to meet growing demand. As a result, a large quantity of polystyrene waste continues to be generated along with associated health and environmental problems. One way to tackle such problems is to lengthen the lifetime of polystyrene, especially for outdoor applications. Our approach is the synthesis and application of new ultraviolet photostabilizers for polystyrene and this research is focused on four cephalexin Schiff bases. The reaction of cephalexin and 3-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-methoxybenzaldehyde, and 4-bromobanzaldehyde under acidic condition afforded the corresponding Schiff bases in high yields. The Schiff bases were characterized and their surfaces were examined. The Schiff bases were mixed with polystyrene to form homogenous blends and their effectiveness as photostabilizers was explored using different methods. The methods included monitoring the changes in the infrared spectra, weight loss, depression in molecular weight, and surface morphology on irradiation. In the presence of the Schiff bases, the formation of carbonyl group fragments, weight loss, and decrease in molecular weight of polystyrene were lower when compared with pure polystyrene. In addition, undesirable changes in the surface such as the appearance of dark spots, cracks, and roughness were minimal for irradiated polystyrene containing cephalexin Schiff bases. Mechanisms by which cephalexin Schiff bases stabilize polystyrene against photodegradation have also been suggested.

Tin Complexes of 4-(Benzylideneamino)benzenesulfonamide: Synthesis, Structure Elucidation and Their Efficiency as PVC Photostabilizers.

Poly(vinyl chloride) (PVC) suffers from photo-oxidation and photodegradation when exposed to harsh conditions. Application of PVC thus relies on the development of ever more efficient photostabilizers. The current research reports the synthesis of new complexes of tin and their assessment as poly(vinyl chloride) photostabilizers. The three new complexes were obtained in high yields from reaction of 4-(benzylideneamino)benzenesulfonamide and tin chlorides. Their structures were elucidated using different tools. The complexes were mixed with poly(vinyl chloride) at a very low concentration and thin films were made from the blends. The effectiveness of the tin complexes as photostabilizers has been established using a variety of methods. The new tin complexes led to a decrease in weight loss, formation of small residues, molecular weight depression, and surface alteration of poly(vinyl chloride) after irradiation. The additives act by absorption of ultraviolet light, removal the active chlorine produced through a dehydrochlorination process, decomposition of peroxides, and coordination with the polymeric chains. The triphenyltin complex showed the greatest stabilizing effect against PVC photodegradation as a result of its high aromaticity.

Tin-Naphthalene Sulfonic Acid Complexes as Photostabilizers for Poly(vinyl chloride).

Poly(vinyl chloride) degrades when exposed to ultraviolet light for long durations; therefore, the photostability of polymeric materials should be enhanced through the application of additives. New organotin complexes containing 4-aminonaphthalene-1-sulfonic acid were synthesized and their role as poly(vinyl chloride) photostabilizers were evaluated. The reaction of 4-amino-3-hydroxynaphthalene-1-sulfonic acid and appropriate di- or trisubstituted tin chloride (triphenyltin chloride, tributyltin chloride, dibutyltin dichloride, and dimethyltin dichloride) in methanol under reflux gave the corresponding tin-naphthalene complexes with yields of 75%-95%. Elemental analyses and spectroscopic techniques including infrared and nuclear magnetic resonance (proton and tin) were used to confirm their structures. The tin complexes were added to poly(vinyl chloride) to produce thin films that irradiated with ultraviolet light. Various parameters were assessed, such as the weight loss, formation of specific functional groups, changes in the surface due to photoirradiation, and rate constant of photodegradation, to test the role played by the organotin complexes to reduce photodegradation in polymeric films. The results proved that organotin complexes acted as photostabilizers in these circumstances. The weight loss, formation of fragments containing specific functional groups, and undesirable changes in the surface of polymeric films were limited in the presence of organotin complexes. Organotin complexes containing three phenyl groups showed the most desirable stabilization effect. These act as efficient primary and secondary photostabilizers, and as decomposers for peroxides. In addition, such an additive inhibits the dehydrochlorination process, which is the main cause of poly(vinyl chloride) photodegradation.

Synthesis of Carvedilol-Organotin Complexes and Their Effects on Reducing Photodegradation of Poly(Vinyl Chloride).

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.

Modifications of Polymers through the Addition of Ultraviolet Absorbers to Reduce the Aging Effect of Accelerated and Natural Irradiation.

The photooxidative degradation process of plastics caused by ultraviolet irradiation leads to bond breaking, crosslinking, the elimination of volatiles, formation of free radicals, and decreases in weight and molecular weight. Photodegradation deteriorates both the mechanical and physical properties of plastics and affects their predicted life use, in particular for applications in harsh environments. Plastics have many benefits, while on the other hand, they have numerous disadvantages, such as photodegradation and photooxidation in harsh environments and the release of toxic substances due to the leaching of some components, which have a negative effect on living organisms. Therefore, attention is paid to the design and use of safe, plastic, ultraviolet stabilizers that do not pose a danger to the environment if released. Plastic ultraviolet photostabilizers act as efficient light screeners (absorbers or pigments), excited-state deactivators (quenchers), hydroperoxide decomposers, and radical scavengers. Ultraviolet absorbers are cheap to produce, can be used in low concentrations, mix well with polymers to produce a homogenous matrix, and do not alter the color of polymers. Recently, polyphosphates, Schiff bases, and organometallic complexes were synthesized and used as potential ultraviolet absorbers for polymeric materials. They reduced the damage caused by accelerated and natural ultraviolet aging, which was confirmed by inspecting the surface morphology of irradiated polymeric films. For example, atomic force microscopy revealed that the roughness factor of polymers' irradiated surfaces was improved significantly in the presence of ultraviolet absorbers. In addition, the investigation of the surface of irradiated polymers using scanning electron microscopy showed a high degree of homogeneity and the appearance of pores that were different in size and shape. The current work surveys for the first time the use of newly synthesized, ultraviolet absorbers as additives to enhance the photostability of polymeric materials and, in particular, polyvinyl chloride and polystyrene, based mainly on our own recent work in the field.

2-(2,4-Di-chloro-phen-oxy)-N'-[2-(2,4-di-chloro-phen-oxy)acet-yl]acetohydrazide.

The complete mol-ecule of the title compound, C16H12Cl4N2O4, is generated by a crystallographic centre of symmetry. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into [010] chains featuring R 2 2(10) loops. The chains are cross-linked by short Cl⋯N contacts [3.224 (2) Å].

2-(Naphthalen-2-yl-oxy)-N'-[2-(naphthalen-2-yl-oxy)acet-yl]acetohydrazide monohydrate.

The title compound, C24H20N2O4·H2O, crystallizes with half a mol-ecule of 2-(naphthalen-2-yl-oxy)-N'-[2-(naphthalen-2-yl-oxy)acet-yl]acetohydrazide and half a water mol-ecule in the asymmetric unit. In the crystal, mol-ecules form planes parallel to (011). Two mol-ecules are connected by water mol-ecules via O-H⋯O and N-H⋯O hydrogen bonds.