Erroneous or Arrhenius: A Degradation Rate-Based Model for EPDM during Homogeneous Ageing.

To improve the predictive capability of long-term stress relaxation of elastomers during thermo-oxidative ageing, a method to separate reversible and irreversible processes was adopted. The separation is performed through the analysis of compression set after tempering. On the basis of this separation, a numerical model for long-term stress relaxation during homogeneous ageing is proposed. The model consists of an additive contribution of physical and chemical relaxation. Computer simulations of compression stress relaxation were performed for long ageing times and the results were validated with the Arrhenius treatment, the kinetic study and the time-temperature superposition technique based on experimental data. For chemical relaxation, two decay functions are introduced each with an activation energy and a degradative process. The first process with the lower activation energy dominates at lower ageing times, while the second one with the higher activation energy at longer ageing times. A degradation-rate based model for the evolution of each process and its contribution to the total system during homogeneous ageing is proposed. The main advantage of the model is the possibility to quickly validate the interpolation at lower temperatures within the range of slower chemical processes without forcing a straight-line extrapolation.

Scission, Cross-Linking, and Physical Relaxation during Thermal Degradation of Elastomers.

Elastomers are susceptible to chemical ageing, i.e., scission and cross-linking, at high temperatures. This thermally driven ageing process affects their mechanical properties and leads to limited operating time. Continuous and intermittent stress relaxation measurements were conducted on ethylene propylene diene rubber (EPDM) and hydrogenated nitrile butadiene rubber (HNBR) samples for different ageing times and an ageing temperature of 125 °C. The contributions of chain scission and cross-linking were analysed for both materials at different ageing states, elucidating the respective ageing mechanisms. Furthermore, compression set experiments were performed under various test conditions. Adopting the two-network model, compression set values were calculated and compared to the measured data. The additional effect of physical processes to scission and cross-linking during a long-term thermal exposure is quantified through the compression set analysis. The characteristic times relative to the degradation processes are also determined.

How does iron deficiency disrupt the electron flow in photosystem I of lettuce leaves?

The changes observed photosystem I activity of lettuce plants exposed to iron deficiency were investigated. Photooxidation/reduction kinetics of P700 monitored as ΔA820 in the presence and absence of electron transport inhibitors and acceptors demonstrated that deprivation in iron decreased the population of active photo-oxidizable P700. In the complete absence of iron, the addition of plant inhibitors (DCMU and MV) could not recover the full PSI activity owing to the abolition of a part of P700 centers. In leaves with total iron deprivation (0µM Fe), only 15% of photo-oxidizable P700 remained. In addition, iron deficiency appeared to affect the pool size of NADP(+) as shown by the decline in the magnitude of the first phase of the photooxidation kinetics of P700 by FR-light. Concomitantly, chlorophyll content gradually declined with the iron concentration added to culture medium. In addition, pronounced changes were found in chlorophyll fluorescence spectra. Also, the global fluorescence intensity was affected. The above changes led to an increased rate of cyclic electron transport around PSI mainly supported by stromal reductants.

Salt effect on phenolics and antioxidant activities of Tunisian and Canadian sweet marjoram (Origanum majorana L.) shoots.

BACKGROUND: Two varieties of Origanum majorana (Canadian and Tunisian) were evaluated for their phenolic, flavonoid and tannin contents, individual phenolic compounds and antioxidant activities under NaCl constraint. RESULTS: The results showed a significant variability in phenolic composition and antioxidant behavior between the two varieties under salt stress. The phenolic composition of methanolic extracts was determined by reversed-phase high-performance liquid chromatography. Amentoflavone was the predominant flavonoid compound; in addition, trans-2-hydrocinnamic acid became the major phenolic acid with salt treatment of the Tunisian variety. In the control, Canadian variety extract was characterized by high levels of gallic acid and amentoflavone. However, under 75 mmol L(-1) NaCl, gallic acid content doubled, whereas amentoflavone content was maintained in the Canadian variety. Stimulation of phenolic acid biosynthesis was observed in these two varieties under salt treatment despite the fact that shoots of the Tunisian variety showed higher antioxidant activities compared to those from the Canadian variety. Tunisian O. majorana might have developed tolerance to salinity and avoided tissue damage by activating enzymes involved in the galactosylation of quercetin into quercetin-3-galactoside and quercetin-3-rhamnoside. CONCLUSION: Our results confirmed the tolerance of Tunisian O. majorana plants.

Inhibition of photosystems I and II activities in salt stress-exposed Fenugreek (Trigonella foenum graecum).

Fenugreek (Trigonella foenum graecum) seedlings were exposed to increasing NaCl concentrations in the growth medium to examine the effect of salt stress on the electron transport reactions of photosynthesis. Activities of both photosystem II (PSII), measured by chlorophyll fluorescence, and photosystem I (PSI), measured by P700 photooxidation, were decreased by salt stress. The inhibition proceeded in a two step manner. At the lower salt concentrations used and shorter exposition periods, electron transfer between the quinone acceptors of PSII, Q(A) and Q(B), was strongly retarded as shown by an increased amplitude of the OJ phase of the OJIP chlorophyll fluorescence induction traces and slowed chlorophyll fluorescence relaxation kinetics following a single turn-over flash. The above indicated a disturbance of the Q(B) binding site likely associated with the first step of photoinhibition. In the second step, strong photoinhibition was observed as manifested by increased F(0) values, declined F(v)/F(0) and loss of photoactive P700.

Inhibition of photosynthetic oxygen evolution and electron transfer from the quinone acceptor QA- to QB by iron deficiency.

The effect of iron deficiency on photosynthetic electron transport in Photosystem II (PS II) was studied in leaves and thylakoid membranes of lettuce (Lactuca sativa, Romaine variety) plants. PS II electron transport was characterized by oxygen evolution and chlorophyll fluorescence parameters. Iron deficiency in the culture medium was shown to affect water oxidation and the advancement of the S-states. A decrease of maximal quantum yield of PS II and an increase of fluorescence intensity at step J and I of OJIP kinetics were also observed. Thermoluminescence measurements revealed that charge recombination between the quinone acceptor of PS II, Q(B), and the S(2) state of the Mn-cluster was strongly perturbed. Also the dark decay of Chl fluorescence after a single turnover white flash was greatly retarded indicating a slower rate of Q(A)(-) reoxidation.