Thermal oxidation and molding feasibility of cycloolefin copolymers (COCs) with high glass transition temperature

Cycloolefin copolymers (COCs) with high glass transition temperature (T_g = 203 °C) have been synthesized and pelletized by extrusion molding. However, their colors change from transparent to yellow during extrusion molding because of thermal oxidation and generation of alkene groups. We have successfully blended several antioxidants (Irganox 1010, Irgafos 168, Irganox HP2225 and Irganox HP2921) into lab-made COCs to avoid the discoloration. The experimental results show that Irganox HP2921 is the best antioxidant among the antioxidants used and can effectively not only suppress thermal oxidation but also eliminate the color stain.     

Theoretical and experimental studies on the structure-antioxidant activity relationship of synthetic 4-methylcoumarins

The development of antioxidants as useful drugs for the treatment of neurodegenerative diseases such as Alzheimer??s is extremely challenging in medicinal chemistry. Coumarins have attracted great attention as possible therapeutic tools against oxygen radicals in human degenerative diseases. In order to establish the possible structure-antioxidant activity relationship, a series of twenty four 4-methylcoumarin derivatives were examined by employing reducing power measurements, and comparison with bond dissociation enthalpy and ionization potential calculations. Based on the reducing potency of 4-methylcoumarin derivatives with respect to trolox, these compounds were classified into five groups as ??most active??, ??more active??, ??moderately active??, ??less active?? and ??inactive?? derivatives. The presence of hydroxyl groups is an essential requirement for the activity, and substitution of hydroxyl groups by methoxy groups leads to non-active derivatives. The results revealed that dihydroxyl groups in the ortho position show a better antioxidant activity with respect to dihydroxyl groups in the meta position. This is ascribed to the ability to construct more stable 4-methylcoumarin radical intermediates by rearrangement of intra-molecular hydrogen bonding. Our findings indicate that other important factors to enhance the antioxidant activity of coumarins are the number of hydroxyl groups, the presence of ester substitutions and a thiono functional group on the pyrone ring. However, bond dissociation enthalpy and ionization potential calculations alone are not sufficient to identify the best antioxidant structures. As a result, chemical and functional properties of molecules such as 4-methylcoumarins should be examined as a whole entity, considering all substitutions versus a single substitution to design functional compounds with good antioxidant activity.     

HALS和抗氧剂对PE辐射致色的影响

聚乙烯;稳定剂;HALS和抗氧剂对PE辐射致色的影响     

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.     

Functional group requirements within the peptide H-Pro-Pro-Asp-NH2 as a catalyst for aldol reactions

H-Pro-Pro-Asp-NH₂1 is a versatile catalyst for asymmetric aldol reactions. In this work, the functional group tolerance within the catalyst structure has been examined. Several analogs of H-Pro-Pro-Asp-NH₂ in which the N-terminal secondary amine or the carboxylic acid in the side chain of the aspartic acid residue is replaced by different functional groups were prepared. Evaluation of their catalytic properties revealed that both the N-terminal secondary amine and the carboxylic acid are important for catalysis. The implications for the reaction mechanism are discussed.     

Extraction and quantification of antioxidants from low-density polyethylene by microwave energy and liquid chromatography

In this paper a experimental design is applied to optimize the quantification of hindered phenol Irganox 1076, phosphite antioxidant Irgafos 168 and their oxidized product tri[2,4-di-tert-butylphenyl]phosphate from low-density polyethylene (LDPE). The developed analytical method consists of two steps: microwave-assisted extraction and reversed-phase liquid chromatography (LC) coupled with ultraviolet diode-array detector. A Plackett-Burman design was carried out in order to find the significant experimental parameters affecting the antioxidants extraction by microwave energy. These parameters were subsequently optimized by a central composite design. The performed method allows extracting the studied antioxidants at low temperature in a short time without degradation of phosphite antioxidant Irgafos 168.     

LC Separation of para and meta Isomers of Zafirlukast in Bulk Drug Samples and Pharmaceutical Dosage Forms Using a Chiral Stationary Phase

A simple, rapid and sensitive high performance liquid chromatographic method was developed for the separation and quantification of positional isomers of zafirlukast in bulk drugs and dosage forms using a chiral column. Elution time was 20 min in normal phase mode and ultra violet detection was carried out at 240 nm. Efficient separation was achieved on an immobilized amylose-based Chiralpak-IA column using n-hexane/ethanol/trifluoroacetic acid/diethyl amine (65:35:0.1:0.1, v/v) as the mobile phase. Resolutions between ortho, meta and para isomers of zafirlukast were found to be >3.0. The active pharmaceutical ingredient was extracted from tablets using tetrahydrofuran. The calibration graphs for meta and para isomers of zafirlukast were linear (r ² > 0.999) when ranging from the limit of quantitation to 0.3%. The method showed excellent recoveries for both zafirlukast isomers identified in bulk and formulated products. The test solution was found to be stable in the mobile phase for 48 h after preparation. The developed LC method was validated with respect to linearity, accuracy, precision and robustness.     

Determination of total antioxidant capacity by a new spectrophotometric method based on Ce(IV) reducing capacity measurement

Dietary antioxidants widely found in fruits and vegetables may serve the task of reducing oxidative damage in humans induced by free radicals and reactive oxygen species under ‘oxidative stress’ conditions. The aim of this work is to develop a simple, low-cost, sensitive, and diversely applicable indirect spectrophotometric method for the determination of total antioxidant capacity of several plants. The method is based on the oxidation of antioxidants with cerium(IV) sulfate in dilute sulfuric acid at room temperature. The Ce(IV) reducing capacity of the sample is measured under carefully adjusted conditions of oxidant concentration and pH such that only antioxidants and not other organic compounds would be oxidized. The spectrophotometric determination of the remaining Ce(IV) was performed after completion of reaction with antioxidants. Quercetin and gallic acid were used as standards for flavonoids and phenolic acids, respectively, and results of antioxidant measurements were reported as trolox equivalents. The developed procedure was successfully applied to the assay of total antioxidant capacity due to simple compounds such as trolox, quercetin, gallic acid, ascorbic acid, catechin, naringin, naringenin, caffeic acid, chlorogenic acid, ferulic acid, and p-coumaric acid, and due to phenolic acids and flavonoids in the arieal parts of nettle (Urtica Dioica L.). Blank correction of significantly absorbing plant extracts at 320 nm could be made with the aid of spectrophotometric titration. Plant selection was made in respect to high antioxidant content, and extraction was made with water. The proposed method was reproducible, and the trolox equivalent antioxidant capacities (TEAC coefficients) of the tested antioxidant compounds were correlated to those found by reference methods such as ABTS and CUPRAC. Since the TEAC coefficients found with the proposed method of naringin-naringenin and rutin-catechin pairs were close to each other, this Ce(IV)-based assay probably caused the simultaneous hydrolysis of flavonoid glycosides to the corresponding aglycones and their subsequent oxidation such that the hydrolysis products exhibed antioxidant capacities roughly proportional the number of -OH groups contained in a molecule.     

Investigation of antioxidant and electron beam radiation effects on the thermal oxidation stability of low-density polyethylene

Effect of various antioxidants on the thermal oxidation stability of LDPE and X-LDPE has been investigated. To achieve this purpose, miscellaneous commercial grade antioxidants such as Irganox 1010, Irganox1076, Irgafos168, Irganox B225, and Chimassorb 944 were selected. Then, formulations based on different content of antioxidant were prepared. The samples were crosslinked by exposure to electron beam irradiation. To assess the thermal oxidation stability of samples, oxidation induction time (OIT) test was accomplished on both the irradiated and unirradiated specimens. Ageing tests were carried out in order to evaluate the thermal oxidation stability of irradiated X-LDPE. The results indicate that Irganox 1010 is the most effective antioxidant amongst the selected ones, concerning thermal oxidation stability of LDPE, before and after aging test.     

Hydroxylation of ionized aromatics including carboxylic acid or amine using recombinant Streptomyces lividans cells expressing modified biphenyl dioxygenase genes

The bphA1(2072)A2A3A4 gene cluster codes for a shuffled biphenyl dioxygenase holoenzyme with broad substrate specificity. These bphA1(2072)A2A3A4 genes were expressed in the actinomycetes Streptomyces lividans using a thiostrepton-inducible promoter P_tipA. Biotransformation experiments of various aromatics including carboxylic acid or amine in their molecular structure, such as 1-naphthoic acid, 2-(1-naphthyl)acetic acid, diphenylamine, and 1-benzyl-4-piperidone, were performed using the recombinant S. lividans cells. These ionized aromatics were converted to the corresponding 1,2-dihydrodiol, mono- or tri-hydroxy forms in 48 h. The structure of the converted products was determined by their EI-MS, ¹H- and ¹³C NMR analysis, and several products were found to be novel compounds.     

The oxidation of the tolyl-anthranilic acids

1. The methyl-group in the ortho position results in an increase in the redox potential. 2. The methyl group in the meta position results in an decrease in the redox potential besides yielding an instable oxidation product. 3. The methyl group in the para position prevent oxidation to the diphenyl benzidine blue derivative, indicating that the oxidation of these compounds results in the formation of compounds of the type.

and not

4. Of the three tolyl-anthranilic acids, the ortho acid is the only one suitable as a redox indicator, its oxidation being a reversible reaction, and yielding a relatively stable product. The colour produced is a purple, almost identical with that of oxidised phenyl-anthranilic acid.The meta-tolyl anthranilic acid produces a blue colour on oxidation but as this fades almost at once, it is quite unsuitable as a redox indicator.     

Novel crown ethers with pendant,proton-ionizable,chromogenic groups

Synthesis of fifteen new chromogenic crown ethers is described in which one phenyl group of diphenylamine has been substituted at the 2-, 4-, and 6-positions with strongly electron-withdrawing groups and the other phenyl group bears an oxymethyl crown ether substituent. Structural variations include the crown ether ring size, identity of the electron-withdrawing groups, acidity of the amine function, and positioning of the oxymethyl crown ether substituent ortho, meta, and para to the amine nitrogen. Preparation of a structurally-related chromogenic bis(crown ether) is also reported.     

Ligand-Enabled [3+2] Annulation of Aromatic Acids with Maleimides by C(sp3)−H and C(sp2)−H Bond Activation

A palladium-catalyzed [3+2] annulation of substituted benzoic acids with maleimides leading to tricyclic heterocyclic molecules having a free carboxylic group in a high atom- and step-economical manner is described. The reaction proceeds via a dual C−H bond activation such as C(sp³)−H at the benzylic position and C(sp²)−H bond activation at the meta position of substituted aromatics. An external ligand (MPAA) is crucial for the success of present protocol. Further, the decarboxylation and esterification of the free carboxylic acid group of observed products were carried out.     

A new strategy for synthesis of polymeric supports with triazene linkers

A new strategy based on the use of diethylamine triazenes for stabilization and generation of polymer supported diazonium ions was described. New economical syntheses of four new polymeric supports with 3- and 6-carbon atom spacers and triazene linkers derived from meta- and para-aminophenol were described and compared to the traditional methods. The possible application of the polymer bound triazene masked diazonium salts as supports for immobilization of secondary amines (nortropine and 4-piperidinole and their esterification and oxidation), and as amine scavengers was shown. The new supports with meta-C₃-T2 and para-C₃-T2 linkers showed higher loadings and typically gave products with good yields and purities.     

Acyl iodides in organic synthesis: XI. Unusual N-C bond cleavage in tertiary amines

Acyl iodides reacted with excess primary and secondary amines in a way similar to acyl chlorides, yielding the corresponding carboxylic acid amide and initial amine hydroiodide. Reactions of tertiary amines with acyl iodides were accompanied by cleavage of the N-C bond with formation of the corresponding N,N-di(hydrocarbyl)carboxamide and alkyl iodide. In the presence of excess tertiary amine the latter was converted into quaternary tetra(hydrocarbyl)ammonium iodide.     

Reductive carboxylation of aromatic esters by electron transfer from magnesium metal

Magnesium-promoted reductive carboxylation of ethyl benzoate in the presence of chlorotrimethylsilane in N,N-dimethylformamide brought about a new carbon-carbon bond formation between the carbonyl carbon atom and carbon dioxide to give the corresponding benzoylformic acid in good yield. It is noteworthy that only ethyl benzoates with substituents at the meta-position were converted into benzoylformic acid derivatives. Moreover, no mandelic acid was detected even under the reductive conditions. This result indicates that benzoylformic acid was obtained after hydrolysis of a carboxylated intermediate, which would be alive as a stabilized structure in the reaction media.     

Hydrogen bonding networks controllable by the substitution position of tetrathiafulvalene on the pyridine ring

Because of the effect of pyridine on the substituent position on the TTF group, TTF derivatives exhibit different assembly structures at the interface, which will be of great significance to the construction of functional nanostructures from the molecular design point of view.     

五氯亚硝酰合铱酸根与二苯胺反应的研究

本文主要用分光光度法研究[Ir(NO)Cl_5]-与二苯胺的反应。在6M盐酸溶液中,生成1:1及2:1配合物,吸收峰分别在515nm及571nm,摩尔吸光系数为2.3×10~4及3.8×10~4。实验表明,新配合物是由[Ir(NO)Cl_5]-的NO~+基在二苯胺氨基的对位发生亲电取代反应而生成。     

Determination of antioxidants in polyolefins by pressurized liquid extraction prior to high performance liquid chromatography

The effect that a high amount of mineral filler might have on the extraction process of antioxidants from polyethylene and polypropylene was investigated. Extraction of Irganox 1010, Irganox 1076 and Irgafos 168, along with its oxidation product 2,4-di-tert-butylphenol, from freeze ground polyethylene–based (PE–based) and polypropylene–based (PP–based) mineral concentrates of 85 w/w calcium carbonate (CaCO₃) and 75 w/w talc was carried out by pressurized fluid extraction (PLE) prior to high performance liquid chromatography (HPLC). Results indicate that 85 w/w CaCO₃ did not affect the extraction process from PE or PP. For talc concentrates, additive recovery from PE and PP was considerably lower. The relation of recovery yield and mixing time was investigated for the talc concentrates and it was concluded that the presence of talc seemed to accelerate the rate of antioxidant consumption during sample processing, thus, less antioxidant was left to be extracted from the polyolefin; rather than talc has limited the extraction process. The method developed in this work has been applied to determine these compounds in several commercial samples.     

Substituted quinolinones. 31. Some new pyrano[3,2‐c]quinoline‐3‐carboxamides and their antioxidant activity

1‐Ethyl‐4‐hydroxy‐2‐oxo‐1,2‐dihydroquinoline‐3‐carbaldehyde ( 1 ) was annulated using malonic acid and/or its ethyl ester to furnish pyrano[3,2‐c]quinoline‐3‐carboxylic acid 2 and its ester 3 . Interconversions between acid 2 and ester 3 were successfully carried out. The anticipated pyrano[3,2‐c]quinoline‐3‐carboxamides 5–12 were conveniently attained via condensation of ester 3 with the proper amine. Surprisingly, treatment of ester 3 with dimethylformamide (DMF) in acidic media led to the carboxamide 5 . All attempts to convert ester 3 to its corresponding acid hydrazides by interaction with the proper hydrazine derivative led to formation of pyrazolidinediones 15 and 17 . Ester 3 underwent cyclo‐condensation with malononitrile dimer affording pyrido[3′,4′:5,6]pyrano[3,2‐c]quinoline derivative 18 . The new compounds revealed significant antioxidant effect, which suggests that most of them are possible potent antioxidant agents.