Mechanisms of antioxidant action: autosynergistic antioxidants containing chain-breaking and peroxidolytic functions

Antioxidant activities, both in model substrate oxidation and in polypropylene under technological conditions, have been examined for a series of alkyl (3,5-di-tert-butyl-4-hydroxybenzyl) sulphides (I). They were found to be intrinsically much more active than typical commercial chain-breaking antioxidants in a closed system. This higher activity is attributed to an additional antioxidant function resulting from the presence of the sulphur atom. The latter is the precursor for a highly active peroxidolytic species which leads to autosynergism. In a thermal-oxidative (air-oven) test I (R, C₂—C₁₈) increases in activity with decreasing volatility but effectiveness as melt stabilizer during the processing of polypropylene and as u.v. stabilizer appears to depend more on the physical state of the additive in the polymer than on its volatility.     

Mechanisms of antioxidant action: Synergism between tin stabilizers and polymer-bound antioxidants in the u.v. stabilization of PVC

It is shown that a conventional tin stabilizer (dibutyltin maleate) (DBTM) forms an effective synergistic u.v. stabilizing combination when used in conjunction with a bound phenolic antioxidant (BHBM) and a bound u.v. stabilizer (EBHPT). These additives become bound to the polymer through sulphur during processing in the presence of DBTM and it is suggested that the sulphide of the adduct makes its own contribution to u.v. stabilization by acting as a peroxide decomposing (PD-C) antioxidant during photo-oxidation. However, the 2-hydroxybenzophenone function appears to be an essential part of the system and is probably involved in quenching of excited states of the intermediate sulphoxides which precede the formation of the PD-C antioxidant.     

The effects of thermal processing on PVC—X. The interaction between bound antioxidants and tin stabilizers

It is shown that a thiol u.v. stabilizer and a thiol heat stabilizer can be effectively bound to PVC during processing in the presence of an alkyltin stabilizer. Thiol u.v. stabilizer interferes with the processing stability of PVC to a lesser extent than does a conventional u.v. stabilizer (2-hydroxy-4-octoxybenzophenone).     

The effects of thermal processing on PVC—IX. A polymer reactive u.v. stabilizer as a thermal stabilizer for PVC

It is shown that a thiol u.v. stabilizer (4-ethoxymercaptoaceto-2-hydroxybenzophenone, EBHPT) becomes efficiently bound to PVC during normal processing at 170° in the presence of dibutyltin maleate (DBTM). This combination is an effective melt stabilizer and shows synergism as a heat stabilizer at 140°. This is shown to be due to the protection of DBTM by the PD antioxidant function in EBHPT and a synergistic optimum is observed. In the absence of DBTM or in the presence of a thiotin stabilizer binding of the u.v. stabilizer is incomplete.     

Dihydromyricetin

A study on the efficiency of bio-based compound as stabilizer for linear low density polyethylene (LLDPE) is reported. A water extract from Ampelopsis grossedentata (Dihydromyricetin) is used. Its stabilizing activity is compared with two commercial phenolic antioxidants: methyl gallate (MG) and Irganox 1010. Based on the measurement of the oxidation onset temperature (OOT) of LLDPE/antioxidant samples, it is found that the antioxidant ability of the three kinds of antioxidants is in the following order: DMY > 1010 > MG. The antioxidant ability and thermal decomposition activation energy (E _a) of antioxidants are further examined by thermal gravimetric analysis. The effects of water extraction on the migration resistance of LLDPE/antioxidants are also evaluated by monitoring the OOT change, demonstrating that DMY retained high stability against migration.     

The effect of processing on the light stability of stabilized and unstabilized polyethylene

It is shown that antioxidants previously reported to be u.v. stabilizers can be distinguished by their mode of action into two categories. These are melt stabilizers, which destroy hydroperoxides during the processing operation, and u.v. stabilizers, which have the additional ability to destroy hydroperoxides during u.v. exposure. The interdependence of the chemical changes occurring during processing and on u.v. exposure are demonstrated.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XIII: Eugenol (4-allyl-2-methoxy-phenol)

Eugenol (4-allyl-2-methoxy-phenol) has been examined as a thermal stabilizer and co-stabilizer for rigid PVC in air, at 180 °C. Its high stabilizing efficiency is detected by its high thermal stability value (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide.Blending this organic stabilizer with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate together with the longer extent of discolouration of PVC stabilized by eugenol as compared with the blank and the samples stabilized with reference commercial stabilizers.A probable mechanism for the stabilizing action of eugenol has been proposed. The stabilizing efficiency is attributed partially to the stabilizer's ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Polarographic investigation of the stability of tin(II) solutions in the presence of some stabilizing agents

The stability of acidic tin(II) solutions was investigated polarographically in the presence of substances with mild antioxidant properties. The best stabilizing action is exerted by pyrogallol, hydrazine or phenolsulphonic acid. In methanolic solutions containing perchloric acid, the stability improves whereas chloride ions hasten the oxidation of tin(II). It is shown that the enhanced stability is due neither to complexation of tin(II) nor to reduction of oxygen by the antioxidants used. The fact that some of the reagents tested exert a powerful stabilizing action even in very small concentrations supports an earlier suggestion that the reaction between tin(II) and oxygen is a chain reaction which is inhibited by the stabilizer.     

Synthesis of stable cadmium sulfide nanoparticles using surfactin produced by Bacillus amyloliquifaciens strain KSU-109

In this study, a surfactin was extracted from a novel surfactant producing bacterial strain Bacillus amyloliquifaciens KSU-109, isolated from rhizosphere of date palm (Phoenix dactylifera), and characterized based on 16Sr RNA and sfp genes using Blastn, Blastx and phylogenetic analyses. The study was performed to obtain a renewable bioresource for surfactin production, and its application in nanotechnology as a non-hazardous and environmentally compatible nanoparticle (NP) stabilizer. The strain KSU-109 produced the surfactin with an average yield of 160 mg/L with strong surfactant activity, reducing the surface tension of the medium from 72 mN/m to 29.3 mN/m. The surfactin preparation was used for synthesizing the cadmium sulfide nanoparticles (CdS-NPs) by mixing 0.005% surfactin with 1mM Cd(NO(3))(2) in 1:1 ratio (v/v) and 10mM Na(2)S solution at pH 7.2 and ambient temperature, which were stable up to 120 days. The surfactin stabilized CdS-NPs were characterized using XRD, TEM, and spectroscopic techniques. The data revealed a significant role of surfactin as a stabilizer and capping agent, which also causes phase transition to yield the cubic/hexagonal CdS-NPs of average size of 3-4 nm. The results elucidated the significance of biocompatible and biodegradable surfactin as an effective and inexpensive stabilizing agent for developing stable CdS nanoparticles.     

Mechanisms of antioxidant action: the role of 2-hydroxybenzophenones in photo-oxidizing media

A study of the photo-stability of 2-hydroxy-4-octyloxybenzophenone (HOBP) in the presence of possible photo-sensitizers present in polymers shows that this u.v. stabilizer is readily destroyed by them in the presence of light. HOBP is destroyed by carbonyl compounds and therefore appears to interfere with their photolysis at least partly by a sacrificial quenching process.     

Synthesis, characterization and application of enrofloxacin complexes as thermal stabilizers for rigid poly(vinyl chloride)

Synthesis and characterization of both binary Co(II)- (1), Ni(II)- (2) complexes with enrofloxacin drug (HL(1)) and ternary Co(II)- (3), Ni(II)- (4) complexes in presence of DL-alanine (H(2)L(2)) are reported using physico-chemical techniques. The antimicrobial activity of these complexes has been screened against two gram-positive and two gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)-complexes exhibited higher potency as compared to the parent drug against bacterial and fungal strain. In addition, it was of interest to investigate the reported complexes as thermal stabilizers and co-stabilizers for rigid PVC in air at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (T(s)) compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate (DBLC) and calcium-zinc soap. Blending these complexes with some of the reference stabilizers in different ratios had a synergistic effect on both induction period as it gave better thermal stability and lower extent of discoloration. The stabilizing efficiency is attributed at least partially to the ability of the metal complex stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation and replace the labile chlorine atoms on PVC chains by a relatively more s moiety of the inorganic stabilizer. Their amenability to use as a biomedical additives for PVC, has afforded them great potential for various medical applications.     

Mechanisms of antioxidant action: polymer grafted antioxidants

It is shown that the antioxidant 3,5-di-tert-butyl-4-hydroxybenzyl acrylate, may be grafted to the surface of polymer artefacts. The antioxidant activity of the resulting “efficiently dispersed” antioxidant is very much higher than that of low molecular weight antioxidants containing the same functional group. Even after extraction with an effective solvent for the antioxidant-monomer and derived polymer, the oxidative stability of the polymer films is very much greater than that of polymer containing the antioxidant-monomer or antioxidant-polymer incorporated by a conventional melt technique without extraction. Optimum activity is believed to be associated with the formation of frequent short chain grafts in the surface of the polymer and is achieved by the use of a polymerization photo-activator such as benzophenone which also terminates kinetic chains.Surface grafted antioxidants are also found to be effective u.v. stabilizers for polypropylene in contrast to the normal ineffectiveness of chain terminating antioxidants incorporated into the polymer by conventional techniques.     

Mechanisms of antioxidant action. Effect of the polymer medium on the antioxidant efficiency of the dithiolates

Peroxide decomposing antioxidants (e.g. nickel dithiophosphates and thiophosphoryl disulphides) control hydroperoxide formation during processing and on exposure to light. However, these additives are more efficient u.v. stabilizers in polypropylene (PP) than in low density polyethylene (LDPE). It is suggested that this difference results from the more rapid formation of hydroperoxides in the more oxidisable substrate under normal processing conditions. In contrast, nickel xanthates are completely destroyed in PP under the same processing conditions and the transformation products obtained in this case are less effective u.v. stabilizers than the original xanthates. Nickel dialkyl dithiophosphates stabilise both LDPE and PP very effectively, while nickel alkyl xanthates are much less effective u.v. stabilisers in both matrices. However, the difference between the efficiencies of the two dithiolates is much less in the case of LDPE. The nickel dithiophosphates and xanthates effectively synergise with the commercial u.v. absorber Cyasorb u.v. 531 (HOBP) but they show antagonism towards a typical chain breaking antioxidant, Irganox 1076, during u.v. exposure. They are however synergists under thermal oxidative conditions.     

Multi‐criteria optimization for ultrasonic‐assisted extraction of antioxidants from Pericarpium Citri Reticulatae using response surface methodology,an activity‐based approach

An activity‐based approach to optimize the ultrasonic‐assisted extraction of antioxidants from Pericarpium Citri Reticulatae (Chenpi in Chinese) was developed. Response surface optimization based on a quantitative composition‐activity relationship model showed the relationships among product chemical composition, antioxidant activity of extract, and parameters of extraction process. Three parameters of ultrasonic‐assisted extraction, including the ethanol/water ratio, Chenpi amount, and alkaline amount, were investigated to give optimum extraction conditions for antioxidants of Chenpi: ethanol/water 70:30 v/v, Chenpi amount of 10 g, and alkaline amount of 28 mg. The experimental antioxidant yield under the optimum conditions was found to be 196.5 mg/g Chenpi, and the antioxidant activity was 2023.8 μmol Trolox equivalents/g of the Chenpi powder. The results agreed well with the second‐order polynomial regression model. This presented approach promised great application potentials in both food and pharmaceutical industries.     

Effect of stabilizer and pigment on photodegradation of polypropylene as revealed by macromolecule scission and crosslinking measurements

Photodegradation depth-profiles have been generated using computer-aided molecular weight distribution analysis for 3 mm thick polypropylene injection moldings containing (i) a stabilizing package that included hindered amine light stabilizers and a phenolic stabilizer, (ii) titanium dioxide pigment and (iii) both the pigment and the stabilizing package. The inhibiting effect of the additives has been determined quantitatively by comparing macromolecule scission and crosslinking rates with those in samples containing no stabilizer or pigment. TiO₂ pigment gave more effective protection against molecular degradation than the stabilizer package; there was very little advantage to be gained by adding stabilizer when the pigment was present. The inhibition caused by having pigment or stabilizer present was measured to be very large: degradation was reduced by at least a factor of 10 and often by a factor of several hundred times. The relative amount of scission and crosslinking differed according to the additives present and the depth from the exposed surface: high reaction rates favoured scission and lower reaction rates resulted in a higher relative crosslinking concentration.     

Effects of reprocessing on polymers—V. Effects of antioxidants in polyethylene based blends containing solid phase dipsersants

The effects of commercial antioxidants and u.v. stabilisers are examined for two typical polyethylene based polyblends containing solid phase dispersants. Both were found to be effectively stabilised against the effects of light and heat by nickel dibutyl dithiocarbamate, a u.v. stable catalytic peroxide decomposer.     

The antioxidant role of α-tocopherol in polymers. I. The nature of transformation products of α-tocopherol formed during melt processing of LDPE

The antioxidant role of α-tocopherol (vitamin E) in low-density polyethylene (LDPE), and the nature of its transformation products formed during extrusion of the polymer are investigated. The melt stabilizing effectiveness of α-tocopherol was found to be very high, higher than that of the commercial hindered phenol antioxidants, Irganox 1076 and 1010, after single and multiple extrusion. The high antioxidant activity of α-tocopherol as a melt stabilizer is due, at least in part, to its transformation products. The importance of the processing history and the parent antioxidant concentration on the transformation products is discussed. Transformation products of α-tocopherol were analyzed after each of the four extrusion passes of the polymer. These were fractionated, analyzed, and characterized by HPLC and spectroscopy, respectively. The main products formed are diastereoisomers of dimers and trimers, as well as aldehydes; the relative concentration of each was shown to depend on processing severity (number of extrusion passes) and the initial concentration of α-tocopherol. The dihydroxydimer was found to be formed at a high concentration relative to the other products and proportional with the initial concentration of tocopherol. Based on both the identity and distribution of transformation products, a mechanism is proposed for the melt stabilization effect of α-tocopherol in LDPE. © 1994 John Wiley & Sons, Inc.     

Stabilization of low density polyethylene with sterically hindered derivatives of 4-hydroxybenzoic acid

In comparison with other commercial light stabilizers, sterically hindered 4-hydroxybenzoates are found to possess only a weak power, if they are used for low density polyethylene (LDPE). It is known that these benzoates exhibit significant synergistic effects together with 2-hydroxybenzophenones and hindered amine light stabilizers in light stabilization of high-density and linear low-density polyethylene. The light stabilizing efficiencies of the above mentioned stabilizers and mixtures of them in different weight ratios are determined by weathering in a Xenotest 150 unit. Only small synergistic effects of about 15 −30% are found for light stabilizing LDPE. The effects can be explained by the stabilizing efficiency of sterically hindered 4-hydroxybenzoates during processing. Combining of light stabilizing structure components like 2-hydroxy-benzophenone resp. 2, 2, 6, 6-tetramethylpiperidine with sterically hindered 4-hydroxybenzoates in one stabilizer molecule only, from the first mentioned combination, results a powerful light stabilizer. Its efficiency is the sum of the powers of the single structure components.     

Effect of l-Arginine treatment on the in vitro stability of electrospun aligned chitosan nanofiber mats

Chitosan (Cs) mats obtained by electrospinning are potentially ideal scaffolds for tissue engineering. This technique allows obtaining nanometric fibrous structures with preferred orientation, which in turn enable cells to align themselves and produce extracellular matrix along desired orientations. In this study, we fabricated aligned Cs electrospun nanofiber mats and investigated the role of the amino acid l-Arginine (L-Arg) as stabilizing agent. Morphological, chemical, mechanical and biological characterizations were performed on untreated and L-Arg treated nanofibrous mats showing the role of L-Arg as biomimetic stabilizer. L-Arg acts as chemical stabilizer of nanofibrous mats, providing improved wettability behavior, mechanical properties and stability even after 60 days in aqueous medium in comparison to untreated mats. Moreover, preliminary biological tests demonstrated favorable cell-material interactions implying physiological responses in terms of viability and proliferation. The proposed L-Arg-treated Cs mats can be considered as potential scaffolds for highly oriented tissue patterning.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Part II. Polypropylene matrix

In our previous study we have found the synergistic combinations of stabilizers which follow different mechanisms of stabilization and are approved for food contact and biomedical applications. The present attempt is to test the potentials of those systems in stabilizing γ-sterilized isotactic polypropylene (i-PP). Isotactic polypropylene was melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer) and sterilized with different doses of γ-radiation. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. The trend in stabilizing the efficiency of binary (1:1), ternary (1:1:1) and quaternary (1:1:1:1) additive systems was confirmed by comparing the stabilizing efficiency of mixtures with and without phenol system as well as with their counter parts of EP copolymer matrix. The binary system of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect even at higher doses of γ-sterilization. Due to the oxidation of hindered phenol, phenol systems have shown discoloration and it was reduced by mixing with secondary HAS, tertiary HAS and organo-phosphite. The response of the stabilizer systems is better to ethylene-propylene (EP) copolymer than to i-PP in terms of stabilization.