Effect of chemical parameters on pyrene degradation in soil in a pulsed discharge plasma system

Degradation of pyrene in soil in a net-to-net pulsed discharge plasma (PDP) system was reviewed. Effect of main chemical parameters, including air flow rate, pyrene concentration, initial pH and soil moisture content on pyrene degradation was examined. The obtained results show that 87.9% of pyrene could be removed under the condition of 60 min reaction; increasing of air flow rate within 1 L min⁻¹ was favorable for degradation; pyrene removal was decreased with the increase of initial pyrene concentration; oxidation of pyrene was more evident in acidic soil; enhancement of soil moisture content has no benefit on pyrene degradation.     

Decomposition of 1-(ω-aminoalkanoyl)guanidines under alkaline conditions

The decomposition of some N^G-(ω-aminoalkanoyl)argininamides, which are key intermediates for the preparation of radiolabeled and fluorescent neuropeptide Y receptor ligands, prompted us to synthesize a small series of simple 1-(ω-aminoalkanoyl)guanidines, and to investigate these model compounds for stability in alkaline buffers. The degradation of acylguanidines was monitored by time resolved UV spectroscopy. The most labile compound, 1-(5-aminopentanoyl)guanidine, decomposed with a half life of 19 s to yield piperidin-2-one (pH 10.4 at 25 °C). In contrast the half life of 1-(6-aminohexanoyl)guanidine is 7.7 h, which is comparable to the hydrolysis of acetylguanidine (t_1/2 = 9.6 h) in alkaline solution.     

Kinetics of the degradation of polystyrene in supercritical acetone

The kinetic analysis of the degradation of polystyrene (PS) in supercritical acetone has been studied using the nonisothermal weight loss technique with heating rates of 3, 5 and 7 °C/min. The weight loss data according to degradation temperature have been analyzed using the integral method based on Arrhenius form to obtain the kinetic parameters such as apparent activation energy and overall reaction order. The kinetic parameters obtained from this work were also compared with those of the thermal degradation of PS in nitrogen atmosphere. From this work, it was found that the activation energies of PS degradation in supercritical acetone were 73.3-200.7 kJ/mol and lower than those of the thermal degradation in nitrogen atmosphere.     

Analysis of neem oils by LC–MS and degradation kinetics of azadirachtin-A in a controlled environment

Since it was first isolated, the oil extracted from seeds of neem (Azadirachtin indica A juss) has been extensively studied in terms of its efficacy as an insecticide. Several industrial formulations are produced as emulsifiable solutions containing a stated titer of the active ingredient azadirachtin-A (AZ-A). The work reported here is the characterization of a formulation of this insecticide marketed under the name of Neem-azal T/S and kinetic studies of the major active ingredient of this formulation. We initially performed liquid–liquid extraction to isolate the neem oil from other ingredients in the commercial mixture. This was followed by a purification using flash chromatography and semi-preparative chromatography, leading to ¹³C NMR identification of structures such as azadirachtin-A, azadirachtin-B, and azadirachtin-H. The neem extract was also characterized by HPLC–MS using two ionization sources, APCI (atmospheric pressure chemical ionization) and ESI (electrospray ionization) in positive and negative ion modes of detection. This led to the identification of other compounds present in the extract—azadirachtin-D, azadirachtin-I, deacetylnimbin, deacetylsalannin, nimbin, and salannin. The comparative study of data gathered by use of the two ionization sources is discussed and shows that the ESI source enables the largest number of structures to be identified. In a second part, kinetic changes in the main product (AZ-A) were studied under precise conditions of pH (2, 4, 6, and 8), temperature (40 to 70 °C), and light (UV, dark room and in daylight). This enabled us to determine the degradation kinetics of the product (AZ-A) over time. The activation energy of the molecule (75±9 kJ mol^–1) was determined by examining thermal stability in the range 40 to 70 °C. The degradation products of this compound were identified by use of HPLC–MS and HPLC–MS–MS. The results enabled proposal of a chemical degradation reaction route for AZ-A under different conditions of pH and temperature. The data show that at room temperature and pH between 4 and 5 the product degrades into two preferential forms that are hydrolyzed to a single product over time and as a function of pH change.     

聚丙烯共混物反应挤出过程中的降解抑制

聚丙烯／（丙烯腈－苯乙烯）共聚物在过氧化二异丙苯存在下反应共混挤出时，加入亚油酸三甘酯可以有效地抑制过程的降解，从挤出物中分离出聚丙烯组分测试熔体流动速率表明，加入亚油酸三甘酯后，其熔体流动速率有很大下降，扫描电子显微镜的观察表明，调节过氧化二异丙苯和亚油酸三甘酯的加入量，可有效控制降解并生成较多的接枝物相容性，显著改善相形态。     

The absolute configuration of peroxisomicines A1 and A2

Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, ¹H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer.     

Synergetic degradation of chitosan with gamma radiation and hydrogen peroxide

Chitosan samples were irradiated by ⁶⁰Co γ-rays in the presence of hydrogen peroxide with radiation dose from 10 kGy to 100 kGy. The degradation was monitored by gel permeation chromatography (GPC), revealing the existence of a synergetic effect on the degradation. Structures of the degraded products were characterized with Fourier-transform infrared spectra (FT-IR), ultraviolet-visible spectral (UV-vis) analysis, and X-ray diffraction (XRD). Results showed that the crystallinity of chitosan decreases with degradation, and the crystalline state of water-soluble chitosan is entirely different from that of water-insoluble chitosan. An elemental analysis method was employed to investigate changes in the element content of chitosan after degradation. Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed.     

Preservation of sensitive CRMs and monitoring their stability at IRMM

Over the years, the nature of CRMs has changed considerably. Recently, more and more CRMs have been certified in their "natural" form, that is processed as little as possible, with analytes at their natural concentration level. This and the trend towards certified properties other than the concentrations of clearly defined molecules/elements have made guaranteeing stability of CRMs and estimating a shelf life an even more important issue for reference material producers than it has been before. One way to meet this challenge is to take more care in processing, storage and dispatch of CRMs. At IRMM, approximately 20 % of the RMs are stored at –20 °C or below and about 10% require cooled transportation. In addition, increased efforts for assessing stability are needed. Shelf lives are estimated using addition of an uncertainty component based on real-temperature stability studies rather than by accelerated stability studies. These pre-certification efforts are complemented by a stability-monitoring program, which at IRMM includes 80 % of the non-nuclear and non-isotopic materials. Although the costs for these efforts are high in absolute terms, they are only a minor and indispensable contribution to the total costs of CRM production.     

四甲基对联苯二胺光敏化聚苯乙烯砜及其模型化合物二苄基砜分解机理的研究

N、N、 N’、N’-四平基对联苯二胺(NTMB)和 3、3’、5、5’-四甲基对联苯二胺(TMB)可以有效地光敏化二苄基砜(DBS)分解和聚苯乙烯砜(PSS)降解。敏化作用是按电子转移机理进行的,电子转移过程可以由NTMB的单重激发态,也可以由三重激发态发生。由三重态电子转移产生的三重态离子自由基对进一步反应生成产物的效率比单重态离子自由基对的效率高10倍。     

Mechanical properties decay and morphological behaviour of biodegradable films for agricultural mulching in real scale experiment

The use of plastic materials in agriculture causes the serious drawback of huge quantities of waste. The introduction of biodegradable materials, which can be disposed directly into the soil, can be one possible solution to this problem. Biodegradable materials are actually innovative materials; therefore, their physical properties must be evaluated in relation to their functionality during the use in field. In the present research results of experimental tests carried out on biodegradable films used in strawberries protected cultivation are presented. The decay of some relevant physical parameters of biodegradable films during the cultivation period was monitored by laboratory tests (SEM analysis, mechanical tensile tests and infrared reflectance spectroscopy). Infrared spectroscopy clearly indicated that the mechanical degradation starts from the starch component of the material. Tensile tests showed that the value of elongation at break of biodegradable materials decreased in some cases by 300% after 10 days of field application.