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Sample records for aging degradation mechanisms

  1. Degradation mechanisms and accelerated aging test design

    SciTech Connect

    Clough, R L; Gillen, K T

    1985-01-01

    The fundamental mechanisms underlying the chemical degradation of polymers can change as a function of environmental stress level. When this occurs, it greatly complicates any attempt to use accelerated tests for predicting long-term material degradation behaviors. Understanding how degradation mechanisms can change at different stress levels facilitates both the design and the interpretation of aging tests. Oxidative degradation is a predominant mechanism for many polymers exposed to a variety of different environments in the presence of air, and there are two mechanistic considerations which are widely applicable to material oxidation. One involves a physical process, oxygen diffusion, as a rate-limiting step. This mechanism can predominate at high stress levels. The second is a chemical process, the time-dependent decomposition of peroxide species. This leads to chain branching and can become a rate-controlling factor at lower stress levels involving time-scales applicable to use environments. The authors describe methods for identifying the operation of these mechanisms and illustrate the dramatic influence they can have on the degradation behaviors of a number of polymer types. Several commonly used approaches to accelerated aging tests are discussed in light of the behaviors which result from changes in degradation mechanisms. 9 references, 4 figures.

  2. Aging Effects and Estimating Degradation Mechanisms of Thermally Upgraded Paper in Mineral Oil

    NASA Astrophysics Data System (ADS)

    Miyagi, Katsunori; Oe, Etsuo; Yamagata, Naoki

    The life of a transformer is limited to the deterioration of its solid insulation. Winding conductors and other solid insulation materials in oil-immersed transformers have been insulated using cellulose products. For many years, manufacturers have met the needs of special applications by designing transformers using thermally upgraded materials to achieve lighter weight, higher power density and increased life. Recently, the effect of thermally upgraded insulation on diagnostic techniques such as gas-in oil analysis, and their indication of insulation degradation have been reviewed. This paper describes evaluations of the thermal degradation characteristics and decomposition reactions in mineral transformer oil of amine-impregnated thermally upgraded paper insulation. The thermal resistance of the thermally upgraded paper is evaluated by comparison with Kraft paper insulation. Further, aging degradation mechanisms of decompositional degradation of the thermally upgraded paper due to aging in mineral transformer oil are proposed.

  3. MECHANISMS OF PESTICIDE DEGRADATION

    EPA Science Inventory

    This research project was initiated with the overall objective of determining (1) the chemical structures of toxic components of toxaphene, (2) to study anaerobic metabolism to degrade toxaphene and other pesticides, and (3) to understand toxic action mechanism of chlordimeform. ...

  4. Degradation mechanism of LiCoO2/mesocarbon microbeads battery based on accelerated aging tests

    NASA Astrophysics Data System (ADS)

    Guan, Ting; Zuo, Pengjian; Sun, Shun; Du, Chunyu; Zhang, Lingling; Cui, Yingzhi; Yang, Lijie; Gao, Yunzhi; Yin, Geping; Wang, Fuping

    2014-12-01

    A series of LiCoO2/mesocarbon microbeads (MCMB) commercial cells cycled at different rates (0.6C, 1.2C, 1.5C, 1.8C, 2.4C and 3.0C) are disassembled and the capacity fade mechanism is proposed by analyzing the structure, morphology and electrochemical performance evolution at the capacity retention of 95%, 90%, 85%, 80%. The capacity deterioration of the commercial cell is mainly caused by the decay of the reversible capacity of LiCoO2 cathode, the irreversible loss of active lithium and the lithium remaining in anode. The proportions of effects by the above three factors are calculated accurately. The consumption of the active lithium leads to a cell imbalance between the anode and the cathode. The electrochemical test results indicate that the capacity fade of the active materials at the low rate is more obvious than that at the high rate. The influence of the active lithium is gradually increscent with the increasing rate. The rate of 1.5C is the optimal value to accelerate the aging of the full cell by comparing the testing results at different capacity retentions in the specific condition of low charge/discharge rate and shallow depth of discharge.

  5. Degradation of mechanical properties of stainless steel cladding due to neutron irradiation and thermal aging

    SciTech Connect

    Haggag, F.M.

    1994-09-01

    Thermal aging of three-wire series-arc stainless steel weld overlay cladding at 288{degrees}C for 1605 h resulted in an appreciable decrease (16%) in the Charpy V-notch (CVN) upper-shelf energy (USE), but the effect on the 41-J transition temperature shift was very small (3{degrees}C). The combined effect following neutron irradiation at 288{degrees}C to a fluence of 5 X 10{sup 19} neutrons/cm{sup 2} (>1 MeV) was a 22% reduction in the USE and a 29{degrees}C shift in the 41-J transition temperature. The effect of thermal aging on tensile properties was very small. However, the combined effect of irradiation and aging was an increase in the yield strength (6 to 34% at test temperatures from 288 to -125{degrees}C) and no apparent change in ultimate tensile strength or total elongation. Neutron irradiation reduced the initiation fracture toughness (J{sub {kappa}}) much more than did thermal aging alone. However, irradiation slightly decreased the tearing modulus but no reduction was caused by thermal aging alone. The effects of long-term thermal exposure times (20,000 and 50,000 h) will be investigated when the specimens become available. Also, long-term thermal exposure of the three-wire cladding as well as type 308 stainless steel weld materials at 343{degrees}C is in progress.

  6. Thermal battery degradation mechanisms

    SciTech Connect

    Missert, Nancy A.; Brunke, Lyle Brent

    2015-09-01

    Diffuse reflectance IR spectroscopy (DRIFTS) was used to investigate the effect of accelerated aging on LiSi based anodes in simulated MC3816 batteries. DRIFTS spectra showed that the oxygen, carbonate, hydroxide and sulfur content of the anodes changes with aging times and temperatures, but not in a monotonic fashion that could be correlated to phase evolution. Bands associated with sulfur species were only observed in anodes taken from batteries aged in wet environments, providing further evidence for a reaction pathway facilitated by H2S transport from the cathode, through the separator, to the anode. Loss of battery capacity with accelerated aging in wet environments was correlated to loss of FeS2 in the catholyte pellets, suggesting that the major contribution to battery performance degradation results from loss of active cathode material.

  7. Aging/tenderization mechanisms

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Postmortem aging of meat is an effective postharvest technique for improving meat tenderness. Improvements in tenderness when meat is stored at refrigerated temperatures for an extended time postmortem are due to changes in the muscle ultrastructure brought on by the degradation of key myofibrillar...

  8. Cellular ageing mechanisms in osteoarthritis.

    PubMed

    Sacitharan, P K; Vincent, T L

    2016-08-01

    Age is the strongest independent risk factor for the development of osteoarthritis (OA) and for many years this was assumed to be due to repetitive microtrauma of the joint surface over time, the so-called 'wear and tear' arthritis. As our understanding of OA pathogenesis has become more refined, it has changed our appreciation of the role of ageing on disease. Cartilage breakdown in disease is not a passive process but one involving induction and activation of specific matrix-degrading enzymes; chondrocytes are exquisitely sensitive to changes in the mechanical, inflammatory and metabolic environment of the joint; cartilage is continuously adapting to these changes by altering its matrix. Ageing influences all of these processes. In this review, we will discuss how ageing affects tissue structure, joint use and the cellular metabolism. We describe what is known about pathways implicated in ageing in other model systems and discuss the potential value of targeting these pathways in OA. PMID:27215642

  9. O-atom degradation mechanisms of materials

    NASA Technical Reports Server (NTRS)

    Coulter, Daniel R.; Liang, Ranty H.; Chung, Shirley Y.; Smith, Keri Oda; Gupta, Amitava

    1987-01-01

    The low Earth orbit environment is described and the critical issues relating to oxygen atom degradation are discussed. Some analytic techniques for studying the problem and preliminary results on the underlying degradation mechanisms are presented.

  10. Degradation Characteristics of O-rings on Highly Aged GIS

    NASA Astrophysics Data System (ADS)

    Minagawa, Tadao; Nagao, Eiichi; Tsuchie, Ei; Yonezawa, Hiroshi; Takayama, Daisuke; Yamakawa, Yutaka

    Owing to increasing number of highly aged GIS, the investigation of the remaining lifetimes of those systems are becoming more important. Because a lot of O-rings are used in GIS, the study of degradation mechanism and lifetime estimation method of O-ring is essential. In this paper, the information about O-ring degradation mechanism is described, and the statistical method for estimating the remaining lifetime of O-ring is proposed. The degradation of O-ring is mainly subject to chemical reactions triggered by oxygen. Because there are many factors influencing those chemical reactions, the dispersion of degradation rates of O-rings in GIS is very large. Consequently the statistical analysis is one of the effective techniques for lifetime estimation of O-rings in GIS.

  11. Durability Improvements Through Degradation Mechanism Studies

    SciTech Connect

    Borup, Rodney L.; Mukundan, Rangachary; Spernjak, Dusan; Baker, Andrew M.; Lujan, Roger W.; Langlois, David Alan; Ahluwalia, Rajesh; Papadia, D. D.; Weber, Adam Z.; Kusoglu, Ahmet; Shi, Shouwnen; More, K. L.; Grot, Steve

    2015-08-03

    The durability of polymer electrolyte membrane (PEM) fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. By investigating cell component degradation modes and defining the fundamental degradation mechanisms of components and component interactions, new materials can be designed to improve durability. To achieve a deeper understanding of PEM fuel cell durability and component degradation mechanisms, we utilize a multi-institutional and multi-disciplinary team with significant experience investigating these phenomena.

  12. Mechanical strain and degradation of laser heterostructures

    NASA Astrophysics Data System (ADS)

    Ptashchenko, Alexander A.; Ptashchenko, Fedor A.; Maslejeva, Natalia V.; Sadova, Galina V.

    2001-02-01

    The effect of mechanical strain on degradation processes in GaAs-AlGaAs laser heterostructures (LHS) with stripe geometry and in light emitting diodes (LED) was experimentally studied. The strain was produced either by axial pressure or by indentation with a Wickers pyramid. We show that degradation affects the degree of polarization and the far-field distribution of laser emission. The effect of strain on the degradation intensity is estimated.

  13. Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 1, aging mechanisms and life estimation

    NASA Astrophysics Data System (ADS)

    Wang, John; Purewal, Justin; Liu, Ping; Hicks-Garner, Jocelyn; Soukazian, Souren; Sherman, Elena; Sorenson, Adam; Vu, Luan; Tataria, Harshad; Verbrugge, Mark W.

    2014-12-01

    We examine the aging and degradation of graphite/composite metal oxide cells. Non-destructive electrochemical methods were used to monitor the capacity loss, voltage drop, resistance increase, lithium loss, and active material loss during the life testing. The cycle life results indicated that the capacity loss was strongly impacted by the rate, temperature, and depth of discharge (DOD). Lithium loss and active electrode material loss were studied by the differential voltage method; we find that lithium loss outpaces active material loss. A semi-empirical life model was established to account for both calendar-life loss and cycle-life loss. For the calendar-life equation, we adopt a square root of time relation to account for the diffusion limited capacity loss, and an Arrhenius correlation is used to capture the influence of temperature. For the cycle life, the dependence on rate is exponential while that for time (or charge throughput) is linear.

  14. Multiscale Concrete Modeling of Aging Degradation

    SciTech Connect

    Hammi, Yousseff; Gullett, Philipp; Horstemeyer, Mark F.

    2015-07-31

    In this work a numerical finite element framework is implemented to enable the integration of coupled multiscale and multiphysics transport processes. A User Element subroutine (UEL) in Abaqus is used to simultaneously solve stress equilibrium, heat conduction, and multiple diffusion equations for 2D and 3D linear and quadratic elements. Transport processes in concrete structures and their degradation mechanisms are presented along with the discretization of the governing equations. The multiphysics modeling framework is theoretically extended to the linear elastic fracture mechanics (LEFM) by introducing the eXtended Finite Element Method (XFEM) and based on the XFEM user element implementation of Giner et al. [2009]. A damage model that takes into account the damage contribution from the different degradation mechanisms is theoretically developed. The total contribution of damage is forwarded to a Multi-Stage Fatigue (MSF) model to enable the assessment of the fatigue life and the deterioration of reinforced concrete structures in a nuclear power plant. Finally, two examples are presented to illustrate the developed multiphysics user element implementation and the XFEM implementation of Giner et al. [2009].

  15. Kinetic study and mechanism of Niclosamide degradation.

    PubMed

    Zaazaa, Hala E; Abdelrahman, Maha M; Ali, Nouruddin W; Magdy, Maimana A; Abdelkawy, M

    2014-11-11

    A spectrophotometric kinetic study of Niclosamide alkaline degradation as a function of drug concentration, alkaline concentration and temperature has been established utilizing double divisor-ratio spectra spectrophotometric method. The developed method allowed determination of Niclosamide in presence of its alkaline degradation products; namely; 2-chloro-4-nitro aniline (DEG I) and 5-chloro salicylic acid (DEG II) with characterization of its degradation mechanism. It was found that degradation kinetic of Niclosamide followed pseudo-first order under the established experimental conditions with a degradation rate constant (k) of 0.0829 mol/h and half life (t1/2) of 8.35 h. The overall degradation rate constant as a function of the temperature under the given conditions obeyed Arrhenius equation where the activation energy was calculated to be 3.41 kcal/mol. PMID:24892546

  16. Kinetic study and mechanism of Niclosamide degradation

    NASA Astrophysics Data System (ADS)

    Zaazaa, Hala E.; Abdelrahman, Maha M.; Ali, Nouruddin W.; Magdy, Maimana A.; Abdelkawy, M.

    2014-11-01

    A spectrophotometric kinetic study of Niclosamide alkaline degradation as a function of drug concentration, alkaline concentration and temperature has been established utilizing double divisor-ratio spectra spectrophotometric method. The developed method allowed determination of Niclosamide in presence of its alkaline degradation products; namely; 2-chloro-4-nitro aniline (DEG I) and 5-chloro salicylic acid (DEG II) with characterization of its degradation mechanism. It was found that degradation kinetic of Niclosamide followed pseudo-first order under the established experimental conditions with a degradation rate constant (k) of 0.0829 mol/h and half life (t1/2) of 8.35 h. The overall degradation rate constant as a function of the temperature under the given conditions obeyed Arrhenius equation where the activation energy was calculated to be 3.41 kcal/mol.

  17. Mechanisms of humic substances degradation by fungi

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Hadar, Y.; Grinhut, T.

    2012-04-01

    Humic substances (HS) are formed by secondary synthesis reactions (humification) during the decay process and transformation of biomolecules originating from plants and other dead organisms. In nature, HS are extremely resistant to biological degradation. Thus, these substances are major components in the C cycle and in the biosphere and therefore, the understanding of the process leading to their formation and transformation and degradation is vital. Fungi active in the decomposition process of HS include mainly ascomycetes and basidiomycetes that are common in the upper layer of forest and grassland soils. Many basidiomycetes belong to the white-rot fungi (WRF) and litter-decomposing fungi (LDF). These fungi are considered to be the most efficient lignin degraders due to their nonspecific oxidizing enzymes: manganese peroxidase (MnP), lignin peroxidase (LiP) and laccase. Although bacteria dominate compost and participate in the turnover of HS, their ability to degrade stable macromolecules such as lignin and HS is limited. The overall objectives of this research were to corroborate biodegradation processes of HS by WRF. The specific objectives were: (i) To isolate, identify and characterize HS degrading WRF from biosolids (BS) compost; (ii) To study the biodegradation process of three types of HS, which differ in their structure, by WRF isolated from BS compost; and (iii) To investigate the mechanisms of HA degradation by WRF using two main approaches: (a) Study the physical and chemical analyses of the organic compounds obtained from direct fungal degradation of HA as well as elucidation of the relevant enzymatic reactions; and (b) Study the enzymatic and biochemical mechanisms involved during HA degradation. In order to study the capability of fungi to degrade HS, seventy fungal strains were isolated from biosolids (BS) compost. Two of the most active fungal species were identified based on rDNA sequences and designated Trametes sp. M23 and Phanerochaetesp., Y6

  18. Perceptual restoration of degraded speech is preserved with advancing age.

    PubMed

    Saija, Jefta D; Akyürek, Elkan G; Andringa, Tjeerd C; Başkent, Deniz

    2014-02-01

    Cognitive skills, such as processing speed, memory functioning, and the ability to divide attention, are known to diminish with aging. The present study shows that, despite these changes, older adults can successfully compensate for degradations in speech perception. Critically, the older participants of this study were not pre-selected for high performance on cognitive tasks, but only screened for normal hearing. We measured the compensation for speech degradation using phonemic restoration, where intelligibility of degraded speech is enhanced using top-down repair mechanisms. Linguistic knowledge, Gestalt principles of perception, and expectations based on situational and linguistic context are used to effectively fill in the inaudible masked speech portions. A positive compensation effect was previously observed only with young normal hearing people, but not with older hearing-impaired populations, leaving the question whether the lack of compensation was due to aging or due to age-related hearing problems. Older participants in the present study showed poorer intelligibility of degraded speech than the younger group, as expected from previous reports of aging effects. However, in conditions that induce top-down restoration, a robust compensation was observed. Speech perception by the older group was enhanced, and the enhancement effect was similar to that observed with the younger group. This effect was even stronger with slowed-down speech, which gives more time for cognitive processing. Based on previous research, the likely explanations for these observations are that older adults can overcome age-related cognitive deterioration by relying on linguistic skills and vocabulary that they have accumulated over their lifetime. Alternatively, or simultaneously, they may use different cerebral activation patterns or exert more mental effort. This positive finding on top-down restoration skills by the older individuals suggests that new cognitive training methods

  19. AGE-RELATED DEGRADATION OF NUCLEAR POWER PLANT STRUCTURES AND COMPONENTS.

    SciTech Connect

    BRAVERMAN,J.

    1999-03-29

    This paper summarizes and highlights the results of the initial phase of a research project on the assessment of aged and degraded structures and components important to the safe operation of nuclear power plants (NPPs). A review of age-related degradation of structures and passive components at NPPs was performed. Instances of age-related degradation have been collected and reviewed. Data were collected from plant generated documents such as Licensing Event Reports, NRC generic communications, NUREGs and industry reports. Applicable cases of degradation occurrences were reviewed and then entered into a computerized database. The results obtained from the review of degradation occurrences are summarized and discussed. Various trending analyses were performed to identify which structures and components are most affected, whether degradation occurrences are worsening, and what are the most common aging mechanisms. The paper also discusses potential aging issues and degradation-susceptible structures and passive components which would have the greatest impact on plant risk.

  20. Age-Related Degradation of Nuclear Power Plant Structures and Components

    SciTech Connect

    Braverman, J.; Chang, T.-Y.; Chokshi, N.; Hofmayer, C.; Morante, R.; Shteyngart, S.

    1999-03-29

    This paper summarizes and highlights the results of the initial phase of a research project on the assessment of aged and degraded structures and components important to the safe operation of nuclear power plants (NPPs). A review of age-related degradation of structures and passive components at NPPs was performed. Instances of age-related degradation have been collected and reviewed. Data were collected from plant generated documents such as Licensing Event Reports, NRC generic communications, NUREGs and industry reports. Applicable cases of degradation occurrences were reviewed and then entered into a computerized database. The results obtained from the review of degradation occurrences are summarized and discussed. Various trending analyses were performed to identify which structures and components are most affected, whether degradation occurrences are worsening, and what was the most common aging mechanisms. The paper also discusses potential aging issues and degradation-susceptible structures and passive components which would have the greatest impact on plant risk.

  1. Reliability Degradation Due to Stockpile Aging

    SciTech Connect

    Robinson, David G.

    1999-04-01

    The objective of this reseach is the investigation of alternative methods for characterizing the reliability of systems with time dependent failure modes associated with stockpile aging. Reference to 'reliability degradation' has, unfortunately, come to be associated with all types of aging analyes: both deterministic and stochastic. In this research, in keeping with the true theoretical definition, reliability is defined as a probabilistic description of system performance as a funtion of time. Traditional reliability methods used to characterize stockpile reliability depend on the collection of a large number of samples or observations. Clearly, after the experiments have been performed and the data has been collected, critical performance problems can be identified. A Major goal of this research is to identify existing methods and/or develop new mathematical techniques and computer analysis tools to anticipate stockpile problems before they become critical issues. One of the most popular methods for characterizing the reliability of components, particularly electronic components, assumes that failures occur in a completely random fashion, i.e. uniformly across time. This method is based primarily on the use of constant failure rates for the various elements that constitute the weapon system, i.e. the systems do not degrade while in storage. Experience has shown that predictions based upon this approach should be regarded with great skepticism since the relationship between the life predicted and the observed life has been difficult to validate. In addition to this fundamental problem, the approach does not recognize that there are time dependent material properties and variations associated with the manufacturing process and the operational environment. To appreciate the uncertainties in predicting system reliability a number of alternative methods are explored in this report. All of the methods are very different from those currently used to assess stockpile

  2. Mechanical Properties of Degraded PMR-15 Resin

    NASA Technical Reports Server (NTRS)

    Tsuji, Luis C.; McManus, Hugh L.; Bowles, Kenneth J.

    1998-01-01

    Thermo-oxidative aging produces a non-uniform degradation state in PMR-15 resin. A surface layer, usually attributed to oxidative degradation, forms. This surface layer has different properties from the inner material. A set of material tests was designed to separate the properties of the oxidized surface layer from the properties of interior material. Test specimens were aged at 316 C in either air or nitrogen, for durations of up to 800 hours. The thickness of the oxidized surface layer in air aged specimens, and the shrinkage and Coefficient of Thermal Expansion (CTE) of nitrogen aged specimens were measured directly. Four-point-bend tests were performed to determine modulus of both the oxidized surface layer and the interior material. Bimaterial strip specimens consisting of oxidized surface material and unoxidized interior material were constructed and used to determine surface layer shrinkage and CTE. Results confirm that the surface layer and core materials have substantially different properties.

  3. Interface degradation in CAS/Nicalon during elevated temperature aging

    SciTech Connect

    Plucknett, K.P.; Cain, R.L.; Lewis, M.H.

    1995-03-01

    A CaO-Al{sub 2}O{sub 3}-SiO{sub 2} (CAS)/Nicalon glass-ceramic matrix composite has been subjected to elevated temperature oxidation heat-treatments between 375 and 1200{degrees}C, for up to 100 hours. Micro- and macro-mechanical properties have been determined by fiber push-down, using a mechanical properties microprobe, and flexure testing, respectively. Aging between 450 and 800{degrees}C results in significant property degradation, with reduced bending modulus and flexure strength, increased fiber sliding stress, and a transition to a purely brittle failure mode. Aging degradation is due to oxidative removal of the carbon interlayer, with the subsequent formation of a silica bond between fiber and matrix. At higher temperatures, carbon is retained due to the formation of a protective silica plug at exposed fiber ends, with the subsequent retention of composite properties. Short duration pre-treatment schedules, at 1000 or 1100{degrees}C, were developed to prevent intermediate temperature property degradation.

  4. Radiation Degradation Mechanisms in Laser Diodes

    NASA Technical Reports Server (NTRS)

    Johston, A. H.; Miyahira, T. F.

    2004-01-01

    Degradation mechanisms are investigated for laser diodes fabricated with different materials and wavelengths between 660 and 1550 nm. A new approach is developed that evaluates degradation below the laser threshold to determine the radiation-induced recombination density. This allows mechanisms at high injection, such as Auger recombination, to be separated from low-injection damage. New results show that AlGaInP lasers in the visible region are nearly an order of magnitude more resistant to radiation than devices fabricated with AlGaAs or AlGaAsP at longer wavelengths.

  5. Pressurized-water reactor internals aging degradation study. Phase 1

    SciTech Connect

    Luk, K.H.

    1993-09-01

    This report documents the results of a Phase I study on the effects of aging degradations on pr internals. Primary stressers for internals an generated by the primary coolant flow in the they include unsteady hydrodynamic forces and pump-generated pressure pulsations. Other stressors are applied loads, manufacturing processes, impurities in the coolant and exposures to fast neutron fluxes. A survey of reported aging-related failure information indicates that fatigue, stress corrosion cracking (SCC) and mechanical wear are the three major aging-related degradation mechanisms for PWR internals. Significant reported failures include thermal shield flow-induced vibration problems, SCC in guide tube support pins and core support structure bolts, fatigue-induced core baffle water-jet impingement problems and excess wear in flux thimbles. Many of the reported problems have been resolved by accepted engineering practices. Uncertainties remain in the assessment of long-term neutron irradiation effects and environmental factors in high-cycle fatigue failures. Reactor internals are examined by visual inspections and the technique is access limited. Improved inspection methods, especially one with an early failure detection capability, can enhance the safety and efficiency of reactor operations.

  6. Mechanical Properties of Degraded PMR-15 Resin

    NASA Technical Reports Server (NTRS)

    Tsuji, Luis C.

    2000-01-01

    Thermo-oxidative aging produces a nonuniform degradation state in PMR-15 resin. A surface layer, usually attributed to oxidative degradation, forms. This surface layer has different properties from the inner material. A set of material tests was designed to separate the properties of the oxidized surface layer from the properties of interior material. Test specimens were aged at 316 C in either air or nitrogen, for durations of up to 800 hr. The thickness of the oxidized surface layer in air aged specimens, and the shrinkage and coefficient of thermal expansion (CTE) of nitrogen aged specimens were measured directly. The nitrogen-aged specimens were assumed to have the same properties as the interior material in the air-aged specimens. Four-point-bend tests were performed to determine modulus of both the oxidized surface layer and the interior material. Bimaterial strip specimens consisting of oxidized surface material and unoxidized interior material were constructed and used to determine surface layer shrinkage and CTE. Results confirm that the surface layer and core materials have substantially different properties.

  7. Investigation of degradation mechanisms in composite matrices

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.

    1982-01-01

    Degradation mechanisms were investigated for graphite/polysulfone and graphite/epoxy laminates exposed to ultraviolet and high-energy electron radiations in vacuum up to 960 equivalent sun hours and 10 to the ninth power rads respectively. Based on GC and combined GC/MS analysis of volatile by-products evolved during irradiation, several free radical mechanisms of composite degradation were identified. The radiation resistance of different matrices was compared in terms of G values and quantum yields for gas formation. All the composite materials evaluated show high electron radiation stability and relatively low ultraviolet stability as indicated by low G values and high quantum for gas formation. Mechanical property measurements of irradiated samples did not reveal significant changes, with the possible exception of UV exposed polysulfone laminates. Hydrogen and methane were identified as the main by-products of irradiation, along with unexpectedly high levels of CO and CO2.

  8. Evaluation of aging degradation of structural components

    SciTech Connect

    Chopra, O.K.; Shack, W.J.

    1992-03-01

    Irradiation embrittlement of the neutron shield tank (NST) A212 Grade B steel from the Shippingport reactor, as well as thermal embrittlement of CF-8 cast stainless steel components from the Shippingport and KRB reactors, has been characterized. Increases in Charpy transition temperature (CTT), yield stress, and hardness of the NST material in the low-temperature low-flux environment are consistent with the test reactor data for irradiations at < 232{degrees}C. The shift in CTT is not as severe as that observed in surveillance samples from the High Flux Isotope Reactor (HFIR): however, it shows very good agreement with the results for HFIR A212-B steel irradiated in the Oak Ridge Research Reactor. The results indicate that fluence rate has not effect on radiation embrittlement at rates as low as 2 {times} 10{sup 8} n/cm{sup 2}{center dot}s at the low operating temperature of the Shippingport NST, i.e., 55{degrees}C. This suggest that radiation damage in Shippingport NST and HFIR surveillance samples may be different because of the neutron spectra and/or Cu and Ni content of the two materials. Cast stainless steel components show relatively modest decreases in fracture toughness and Charpy-impact properties and a small increase in tensile strength. Correlations for estimating mechanical properties of cast stainless steels predict accurate or slightly conservative values for Charpy-impact energy, tensile flow stress, fracture toughness J-R curve, and J{sub IC} of the materials. The kinetics of thermal embrittlement and degree of embrittlement at saturation, i.e., the minimum impact energy achieved after long-term aging, were established from materials that were aged further in the laboratory. The results were consistent with the estimates. The correlations successfully predict the mechanical properties of the Ringhals 2 reactor hot- and crossover-leg elbows (CF-8M steel) after service of {approx}15 y.

  9. Evaluation of aging degradation of structural components

    SciTech Connect

    Chopra, O.K.; Shack, W.J.

    1992-03-01

    Irradiation embrittlement of the neutron shield tank (NST) A212 Grade B steel from the Shippingport reactor, as well as thermal embrittlement of CF-8 cast stainless steel components from the Shippingport and KRB reactors, has been characterized. Increases in Charpy transition temperature (CTT), yield stress, and hardness of the NST material in the low-temperature low-flux environment are consistent with the test reactor data for irradiations at < 232{degrees}C. The shift in CTT is not as severe as that observed in surveillance samples from the High Flux Isotope Reactor (HFIR): however, it shows very good agreement with the results for HFIR A212-B steel irradiated in the Oak Ridge Research Reactor. The results indicate that fluence rate has not effect on radiation embrittlement at rates as low as 2 {times} 10{sup 8} n/cm{sup 2}{center_dot}s at the low operating temperature of the Shippingport NST, i.e., 55{degrees}C. This suggest that radiation damage in Shippingport NST and HFIR surveillance samples may be different because of the neutron spectra and/or Cu and Ni content of the two materials. Cast stainless steel components show relatively modest decreases in fracture toughness and Charpy-impact properties and a small increase in tensile strength. Correlations for estimating mechanical properties of cast stainless steels predict accurate or slightly conservative values for Charpy-impact energy, tensile flow stress, fracture toughness J-R curve, and J{sub IC} of the materials. The kinetics of thermal embrittlement and degree of embrittlement at saturation, i.e., the minimum impact energy achieved after long-term aging, were established from materials that were aged further in the laboratory. The results were consistent with the estimates. The correlations successfully predict the mechanical properties of the Ringhals 2 reactor hot- and crossover-leg elbows (CF-8M steel) after service of {approx}15 y.

  10. Seepage into drifts with mechanical degradation.

    PubMed

    Li, Guomin; Tsang, Chin-Fu

    2003-01-01

    Seepage into drifts in unsaturated tuff is an important issue for the long-term performance of the proposed nuclear waste repository at Yucca Mountain, Nevada. Drifts in which waste packages will be emplaced are subject to degradation in the form of rockfall from the drift ceiling, induced by stress-relief, seismic, or thermal effects. The objective of this study is to calculate seepage rates, for various drift-degradation scenarios and for different values of percolation flux, in the Topopah Spring middle nonlithophysal (Tptpmn) and the Topopah Spring lower lithophysal (Tptpll) units at Yucca Mountain. Seepage calculations are conducted by (1) defining a heterogeneous drift-scale permeability model with field data, (2) selecting calibrated parameters associated with the Tptpmn and Tptpll units, and (3) simulating seepage, based on detailed degraded-drift profiles obtained from a separate rock mechanics engineering analysis. The simulation results indicate (1) that the seepage threshold (i.e., the percolation flux at which seepage first occurs) is not significantly changed by drift degradation and (2) the degradation-induced increase in seepage above the threshold is influenced probably more by the shape of the cavity created by rockfall than by rockfall volume. PMID:12714289

  11. Mechanisms of Glucagon Degradation at Alkaline pH

    PubMed Central

    Caputo, Nicholas; Castle, Jessica R.; Bergstrom, Colin P.; Carroll, Julie M.; Bakhtiani, Parkash A.; Jackson, Melanie A.; Roberts, Charles T.; David, Larry L.; Ward, W. Kenneth

    2014-01-01

    Glucagon is unstable and undergoes degradation and aggregation in aqueous solution. For this reason, its use in portable pumps for closed loop management of diabetes is limited to very short periods. In this study, we sought to identify the degradation mechanisms and the bioactivity of specific degradation products. We studied degradation in the alkaline range, a range at which aggregation is minimized. Native glucagon and analogs identical to glucagon degradation products were synthesized. To quantify biological activity in glucagon and in the degradation peptides, a protein kinase A-based bioassay was used. Aged, fresh, and modified peptides were analyzed by liquid chromatography with mass spectrometry (LCMS). Oxidation of glucagon at the Met residue was common but did not reduce bioactivity. Deamidation and isomerization were also common and were more prevalent at pH 10 than 9. The biological effects of deamidation and isomerization were unpredictable; deamidation at some sites did not reduce bioactivity. Deamidation of Gln 3, isomerization of Asp 9, and deamidation with isomerization at Asn 28 all caused marked potency loss. Studies with molecular-weight-cutoff membranes and LCMS revealed much greater fibrillation at pH 9 than 10. Further work is necessary to determine formulations of glucagon that minimize degradation and fibrillation. PMID:23651991

  12. Boiling-Water Reactor internals aging degradation study. Phase 1

    SciTech Connect

    Luk, K.H.

    1993-09-01

    This report documents the results of an aging assessment study for boiling water reactor (BWR) internals. Major stressors for BWR internals are related to unsteady hydrodynamic forces generated by the primary coolant flow in the reactor vessel. Welding and cold-working, dissolved oxygen and impurities in the coolant, applied loads and exposures to fast neutron fluxes are other important stressors. Based on results of a component failure information survey, stress corrosion cracking (SCC) and fatigue are identified as the two major aging-related degradation mechanisms for BWR internals. Significant reported failures include SCC in jet-pump holddown beams, in-core neutron flux monitor dry tubes and core spray spargers. Fatigue failures were detected in feedwater spargers. The implementation of a plant Hydrogen Water Chemistry (HWC) program is considered as a promising method for controlling SCC problems in BWR. More operating data are needed to evaluate its effectiveness for internal components. Long-term fast neutron irradiation effects and high-cycle fatigue in a corrosive environment are uncertainty factors in the aging assessment process. BWR internals are examined by visual inspections and the method is access limited. The presence of a large water gap and an absence of ex-core neutron flux monitors may handicap the use of advanced inspection methods, such as neutron noise vibration measurements, for BWR.

  13. Final Report Inspection of Aged/Degraded Containments Program.

    SciTech Connect

    Naus, Dan J; Ellingwood, B R; Oland, C Barry

    2005-09-01

    The Inspection of Aged/Degraded Containments Program had primary objectives of (1) understanding the significant factors relating corrosion occurrence, efficacy of inspection, and structural capacity reduction of steel containments and liners of reinforced concrete containments; (2) providing the United States Nuclear Regulatory Commission (USNRC) reviewers a means of establishing current structural capacity margins or estimating future residual structural capacity margins for steel containments, and concrete containments as limited by liner integrity; (3) providing recommendations, as appropriate, on information to be requested of licensees for guidance that could be utilized by USNRC reviewers in assessing the seriousness of reported incidences of containment degradation; and (4) providing technical assistance to the USNRC (as requested) related to concrete technology. Primary program accomplishments have included development of a degradation assessment methodology; reviews of techniques and methods for inspection and repair of containment metallic pressure boundaries; evaluation of high-frequency acoustic imaging, magnetostrictive sensor, electromagnetic acoustic transducer, and multimode guided plate wave technologies for inspection of inaccessible regions of containment metallic pressure boundaries; development of a continuum damage mechanics-based approach for structural deterioration; establishment of a methodology for reliability-based condition assessments of steel containments and liners; and fragility assessments of steel containments with localized corrosion. In addition, data and information assembled under this program has been transferred to the technical community through review meetings and briefings, national and international conference participation, technical committee involvement, and publications of reports and journal articles. Appendix A provides a listing of program reports, papers, and publications; and Appendix B contains a listing of

  14. Mechanical degradation temperature of waste storage materials

    SciTech Connect

    Fink, M.C.; Meyer, M.L.

    1993-05-13

    Heat loading analysis of the Solid Waste Disposal Facility (SWDF) waste storage configurations show the containers may exceed 90{degrees}C without any radioactive decay heat contribution. Contamination containment is primarily controlled in TRU waste packaging by using multiple bag layers of polyvinyl chloride and polyethylene. Since literature values indicate that these thermoplastic materials can begin mechanical degradation at 66{degrees}C, there was concern that the containment layers could be breached by heating. To better define the mechanical degradation temperature limits for the materials, a series of heating tests were conducted over a fifteen and thirty minute time interval. Samples of a low-density polyethylene (LDPE) bag, a high-density polyethylene (HDPE) high efficiency particulate air filter (HEPA) container, PVC bag and sealing tape were heated in a convection oven to temperatures ranging from 90 to 185{degrees}C. The following temperature limits are recommended for each of the tested materials: (1) low-density polyethylene -- 110{degrees}C; (2) polyvinyl chloride -- 130{degrees}C; (3) high-density polyethylene -- 140{degrees}C; (4) sealing tape -- 140{degrees}C. Testing with LDPE and PVC at temperatures ranging from 110 to 130{degrees}C for 60 and 120 minutes also showed no observable differences between the samples exposed at 15 and 30 minute intervals. Although these observed temperature limits differ from the literature values, the trend of HDPE having a higher temperature than LDPE is consistent with the reference literature. Experimental observations indicate that the HDPE softens at elevated temperatures, but will retain its shape upon cooling. In SWDF storage practices, this might indicate some distortion of the waste container, but catastrophic failure of the liner due to elevated temperatures (<185{degrees}C) is not anticipated.

  15. Multisensory integration mechanisms during aging

    PubMed Central

    Freiherr, Jessica; Lundström, Johan N.; Habel, Ute; Reetz, Kathrin

    2013-01-01

    The rapid demographical shift occurring in our society implies that understanding of healthy aging and age-related diseases is one of our major future challenges. Sensory impairments have an enormous impact on our lives and are closely linked to cognitive functioning. Due to the inherent complexity of sensory perceptions, we are commonly presented with a complex multisensory stimulation and the brain integrates the information from the individual sensory channels into a unique and holistic percept. The cerebral processes involved are essential for our perception of sensory stimuli and becomes especially important during the perception of emotional content. Despite ongoing deterioration of the individual sensory systems during aging, there is evidence for an increase in, or maintenance of, multisensory integration processing in aging individuals. Within this comprehensive literature review on multisensory integration we aim to highlight basic mechanisms and potential compensatory strategies the human brain utilizes to help maintain multisensory integration capabilities during healthy aging to facilitate a broader understanding of age-related pathological conditions. Further our goal was to identify where further research is needed. PMID:24379773

  16. Scarp degraded by linear diffusion: inverse solution for age.

    USGS Publications Warehouse

    Andrews, D.J.; Hanks, T.C.

    1985-01-01

    Under the assumption that landforms unaffected by drainage channels are degraded according to the linear diffusion equation, a procedure is developed to invert a scarp profile to find its 'diffusion age'. The inverse procedure applied to synthetic data yields the following rules of thumb. Evidence of initial scarp shape has been lost when apparent age reaches twice its initial value. A scarp that appears to have been formed by one event may have been formed by two with an interval between them as large as apparent age. The simplicity of scarp profile measurement and this inversion makes profile analysis attractive. -from Authors

  17. Lithium battery aging model based on Dakin's degradation approach

    NASA Astrophysics Data System (ADS)

    Baghdadi, Issam; Briat, Olivier; Delétage, Jean-Yves; Gyan, Philippe; Vinassa, Jean-Michel

    2016-09-01

    This paper proposes and validates a calendar and power cycling aging model for two different lithium battery technologies. The model development is based on previous SIMCAL and SIMSTOCK project data. In these previous projects, the effect of the battery state of charge, temperature and current magnitude on aging was studied on a large panel of different battery chemistries. In this work, data are analyzed using Dakin's degradation approach. In fact, the logarithms of battery capacity fade and the increase in resistance evolves linearly over aging. The slopes identified from straight lines correspond to battery aging rates. Thus, a battery aging rate expression function of aging factors was deduced and found to be governed by Eyring's law. The proposed model simulates the capacity fade and resistance increase as functions of the influencing aging factors. Its expansion using Taylor series was consistent with semi-empirical models based on the square root of time, which are widely studied in the literature. Finally, the influence of the current magnitude and temperature on aging was simulated. Interestingly, the aging rate highly increases with decreasing and increasing temperature for the ranges of -5 °C-25 °C and 25 °C-60 °C, respectively.

  18. Stabilization and Degradation Mechanisms of Cytoplasmic Ataxin-1

    PubMed Central

    Kohiyama, Mayumi F.; Lagalwar, Sarita

    2015-01-01

    Aggregation-prone proteins in neurodegenerative disease disrupt cellular protein stabilization and degradation pathways. The neurodegenerative disease spinocerebellar ataxia type 1 (SCA1) is caused by a coding polyglutamine expansion in the Ataxin-1 gene (ATXN1), which gives rise to the aggregation-prone mutant form of ATXN1 protein. Cerebellar Purkinje neurons, preferentially vulnerable in SCA1, produce ATXN1 protein in both cytoplasmic and nuclear compartments. Cytoplasmic stabilization of ATXN1 by phosphorylation and 14-3-3-mediated mechanisms ultimately drive translocation of the protein to the nucleus where aggregation may occur. However, experimental inhibition of phosphorylation and 14-3-3 binding results in rapid degradation of ATXN1, thus preventing nuclear translocation and cellular toxicity. The exact mechanism of cytoplasmic ATXN1 degradation is currently unknown; further investigation of degradation may provide future therapeutic targets. This review examines the present understanding of cytoplasmic ATXN1 stabilization and potential degradation mechanisms during normal and pathogenic states. PMID:27168726

  19. Hygrothermal ageing effect on mechanical properties of FRP laminates

    NASA Astrophysics Data System (ADS)

    Larbi, S.; Bensaada, R.; Bilek, A.; Djebali, S.

    2015-03-01

    The aim of this work is to study the effect of hygrothermal aging on mechanical properties of two composite materials (carbon fiber / epoxy and glass fiber E / vinylester). Two stratifications are studied for each material. Both materials are exposed to two different environments, the sea water and the deionized water at a temperature of 40°C. The kinetic of material absorption is plotted. We see an irreversible degradation of material caused by exposure time. The characterization of samples in the virgin state and the aged condition is achieved with three points bending tests. We can see significant loss of mechanical properties due to hygrothermal aging.

  20. Characterization of Thermally Degraded Energetic Materials: Mechanical and Chemical Behavior

    SciTech Connect

    Miller, J.C.; Renlund, A.M.; Schmitt, R.G.; Wellman, G.W.

    1998-12-04

    We report the results of recent experiments on thermally degraded HMX and HMX/binder materials. Small-scale samples were heated confined in either constant-volume or load- controlled configurations. A main emphasis of the work reported here is developing an understanding of the complex coupling of the mechanical and chemical responses during thermal degradation.

  1. Hierarchical and serial processing in the spatial auditory cortical pathway is degraded by natural aging

    PubMed Central

    Juarez-Salinas, Dina L.; Engle, James R.; Navarro, Xochi O.; Recanzone, Gregg H.

    2010-01-01

    The compromised abilities to localize sounds and to understand speech are two hallmark deficits in aged individuals. The auditory cortex is necessary for these processes, yet we know little about how normal aging affects these early cortical fields. In this study, we recorded the spatial tuning of single neurons in primary (area A1) and secondary (area CL) auditory cortical areas in young and aged alert rhesus macaques. We found that the neurons of aged animals had greater spontaneous and driven activity, and broader spatial tuning compared to those of younger animals. Importantly, spatial tuning was not sharpened between A1 and CL in aged monkeys as it is in younger monkeys. This implies that a major effect of normal aging is a degradation of the hierarchical processing between serially connected cortical areas, which could be a key contributing mechanism of the general cognitive decline that is commonly observed in normal aging. PMID:21048138

  2. Degradation mechanisms of ceramic thermal barrier coatings in corrosive environments

    NASA Technical Reports Server (NTRS)

    Lau, S. K.; Bratton, R. J.

    1984-01-01

    Chemical as well as thermal-mechanical interactions between the ceramics and gas turbine combustion gases/condensates are found to play critical roles in the degradation of porous plasma-sprayed ceramic thermal barrier coatings. The detailed degradation mechanisms of several state-of-the-art ceramic thermal barrier coatings, including several zirconia compositions and a calcium silicate, in corrosive environments are examined in this paper. Approaches to extend coating lifetime are also described.

  3. Identification of degradation mechanisms of blue InGaN/GaN laser diodes

    NASA Astrophysics Data System (ADS)

    Wen, P. Y.; Zhang, S. M.; Li, D. Y.; Liu, J. P.; Zhang, L. Q.; Zhou, K.; Feng, M. X.; Tian, A. Q.; Zhang, F.; Gao, X. D.; Zeng, C.; Yang, H.

    2015-10-01

    A comprehensive analysis of the degradation mechanism of blue InGaN/GaN laser diodes (LDs) is carried out by investigating the electrical and optical characteristics. The increase in the leakage current as well as decrease in the slope efficiency is observed. The luminescence properties of the active region at different aging stages are studied by means of cathodoluminescence. Significant degradation of the active region is observed on the room temperature cathodoluminescence while the low temperature cathodoluminescence shows almost no degradation, indicating that the degradation of the LDs is due to generation of low temperature frozen point defects. Furthermore, the generation of the defects follows a kinetic mechanism enhanced by electron-hole non-radiative recombination which explains the acceleration of time degradation in our LDs.

  4. INTERIM REPORT ON CONCRETE DEGRADATION MECHANISMS AND ONLINE MONITORING TECHNIQUES

    SciTech Connect

    Mahadevan, Sankaran; Agarwal, Vivek; Neal, Kyle; Kosson, David; Adams, Douglas

    2014-09-01

    The existing fleets of nuclear power plants in the United States have initial operating licenses of 40 years, though most these plants have applied for and received license extensions. As plant structures, systems, and components age, their useful life—considering both structural integrity and performance—is reduced as a result of deterioration of the materials. The online monitoring of concrete structure conducted under the Advanced Instrumentation, Information, and Control Technologies Pathway of the Light Water Reactor Sustainability program at Idaho National Laboratory will develop and demonstrate concrete structures health monitoring capabilities. Assessment and management of aging concrete structures in nuclear plants require a more systematic approach than simple reliance on existing code margins of safety. Therefore, the structural health monitoring is required to produce actionable information regarding structural integrity that supports operational and maintenance decisions. Through this research project, several national laboratories and Vanderbilt University proposes to develop a framework of research activities for the health monitoring of nuclear power plant concrete structures that includes integration of four elements—damage modeling, monitoring, data analytics, and uncertainty quantification. This report briefly discusses available techniques and ongoing challenges in each of the four elements of the proposed framework with emphasis on degradation mechanisms and online monitoring techniques.

  5. Aging mechanisms and service life of lead-acid batteries

    NASA Astrophysics Data System (ADS)

    Ruetschi, Paul

    In lead-acid batteries, major aging processes, leading to gradual loss of performance, and eventually to the end of service life, are: Anodic corrosion (of grids, plate-lugs, straps or posts). Positive active mass degradation and loss of adherence to the grid (shedding, sludging). Irreversible formation of lead sulfate in the active mass (crystallization, sulfation). Short-circuits. Loss of water. Aging mechanisms are often inter-dependent. For example, corrosion of the grids will lead to increased resistance to current flow, which will in turn impede proper charge of certain parts of the active mass, resulting in sulfation. Active mass degradation may lead to short-circuits. Sulfation may be the result of a loss of water, and so forth. The rates of the different aging processes strongly depend on the type of use (or misuse) of the battery. Over-charge will lead to accelerated corrosion and also to accelerated loss of water. With increasing depth-of-discharge during cycling, positive active mass degradation is accelerated. Some aging mechanisms are occurring only upon misuse. Short-circuits across the separators, due to the formation of metallic lead dendrites, for example, are usually formed only after (excessively) deep discharge. Stationary batteries, operated under float-charge conditions, will age typically by corrosion of the positive grids. On the other hand, service life of batteries subject to cycling regimes, will typically age by degradation of the structure of the positive active mass. Starter batteries are usually aging by grid corrosion, for instance in normal passenger car use. However, starter batteries of city buses, making frequent stops, may age (prematurely) by positive active mass degradation, because the batteries are subject to numerous shallow discharge cycles. Valve-regulated batteries often fail as a result of negative active mass sulfation, or water loss. For each battery design, and type of use, there is usually a characteristic

  6. Mechanisms balancing skeletal matrix synthesis and degradation.

    PubMed Central

    Blair, Harry C; Zaidi, Mone; Schlesinger, Paul H

    2002-01-01

    Bone is regulated by evolutionarily conserved signals that balance continuous differentiation of bone matrix-producing cells against apoptosis and matrix removal. This is continued from embryogenesis, where the skeleton differentiates as a solid mass and is shaped into separate bones by cell death and proteolysis. The two major tissues of the skeleton are avascular cartilage, with an extracellular matrix based on type II collagen and hydrophilic proteoglycans, and bone, a stronger and lighter material based on oriented type I collagen and hydroxyapatite. Both differentiate from the same mesenchymal stem cells. This differentiation is regulated by a family of related signals centred on bone morphogenic proteins. Fibroblast growth factors, Indian hedgehog and parathyroid hormone-related protein are important in determining the type of matrix and the relation of skeletal and non-skeletal structures. Removal of mineralized matrix involves apoptosis of matrix cells and differentiation of acid-secreting cells (osteoclasts) from macrophage precursors. Key regulators of matrix removal are signals in the tumour-necrosis-factor family. Osteoclasts dissolve bone by isolating a region of the matrix and secreting HCl and proteinases at that site. Successive cycles of removal and replacement allow growth, repair and remodelling. The signals for bone turnover are predominantly cell-membrane-associated, allowing very specific spatial regulation. In addition to its support function, bone is a reservoir of Ca2+, PO3-(4) and OH-. Secondary modulation of mineral secretion and bone degradation are mediated by humoral signals, including parathyroid hormone and vitamin D, as well as the cytokines that also regulate the underlying cell differentiation. PMID:12023876

  7. Drug Release Kinetics and Transport Mechanisms of Non-degradable and Degradable Polymeric Delivery Systems

    PubMed Central

    Fu, Yao; Kao, Weiyuan John

    2010-01-01

    Importance of the field The advancement in material design and engineering has led to the rapid development of novel materials with increasing complexity and functions. Both non-degradable and degradable polymers have found wide applications in the controlled delivery field. Studies on drug release kinetics provide important information into the function of material systems. To elucidate the detailed transport mechanism and the structure-function relationship of a material system, it is critical to bridge the gap between the macroscopic data and the transport behavior at the molecular level. Areas covered in this review The structure and function information of selected non-degradable and degradable polymers have been collected and summarized from literatures published after 1990s. The release kinetics of selected drug compounds from various material systems will be discussed in case studies. Recent progresses in the mathematical models based on different transport mechanisms will be highlighted. What the reader will gain This article aims to provide an overview of structure-function relationships of selected non-degradable and degradable polymers as drug delivery matrices. Take home message Understanding the structure-function relationship of the material system is key to the successful design of a delivery system for a particular application. Moreover, developing complex polymeric matrices requires more robust mathematical models to elucidate the solute transport mechanisms. PMID:20331353

  8. Preparation and degradation mechanisms of biodegradable polymer: a review

    NASA Astrophysics Data System (ADS)

    Zeng, S. H.; Duan, P. P.; Shen, M. X.; Xue, Y. J.; Wang, Z. Y.

    2016-07-01

    Polymers are difficult to degrade completely in Nature, and their catabolites may pollute the environment. In recent years, biodegradable polymers have become the hot topic in people's daily life with increasing interest, and a controllable polymer biodegradation is one of the most important directions for future polymer science. This article presents the main preparation methods for biodegradable polymers and discusses their degradation mechanisms, the biodegradable factors, recent researches and their applications. The future researches of biodegradable polymers are also put forward.

  9. Analytical markers for silk degradation: comparing historic silk and silk artificially aged in different environments.

    PubMed

    Vilaplana, Francisco; Nilsson, Johanna; Sommer, Dorte V P; Karlsson, Sigbritt

    2015-02-01

    Suitable analytical markers to assess the degree of degradation of historic silk textiles at molecular and macroscopic levels have been identified and compared with silk textiles aged artificially in different environments, namely (i) ultraviolet (UV) exposure, (ii) thermo-oxidation, (iii) controlled humidity and (iv) pH. The changes at the molecular level in the amino acid composition, the formation of oxidative moieties, crystallinity and molecular weight correlate well with the changes in the macroscopic properties such as brightness, pH and mechanical properties. These analytical markers are useful to understand the degradation mechanisms that silk textiles undergo under different degradation environments, involving oxidation processes, hydrolysis, chain scission and physical arrangements. Thermo-oxidation at high temperatures proves to be the accelerated ageing procedure producing silk samples that most resembled the degree of degradation of early seventeenth-century silk. These analytical markers will be valuable to support the textile conservation tasks currently being performed in museums to preserve our heritage. PMID:25492090

  10. Formation of free radicals during mechanical degradation of elastomers.

    NASA Technical Reports Server (NTRS)

    Devries, K. L.; Williams, M. L.; Roylance, D. K.

    1971-01-01

    Solithane 113 (an amorphous polyurethane elastomer) was prepared by curing equal proportions of castor oil and trifunctional isocyanate for 6 hr 45 min at 170 F. The sample material was mechanically degraded by grinding below and above its glass transition point at liquid nitrogen and room temperatures. The EPR spectra of ground samples were recorded and the number of free radicals were determined by a computer double-integration of the recorded spectra and by a comparison of the values with those of a standard material. Curves of EPR spectra suggest that different molecular mechanisms may be active in degradation of this material below and above its glass transition temperature.

  11. Epigenetic Mechanisms of Longevity and Aging.

    PubMed

    Sen, Payel; Shah, Parisha P; Nativio, Raffaella; Berger, Shelley L

    2016-08-11

    Aging is an inevitable outcome of life, characterized by progressive decline in tissue and organ function and increased risk of mortality. Accumulating evidence links aging to genetic and epigenetic alterations. Given the reversible nature of epigenetic mechanisms, these pathways provide promising avenues for therapeutics against age-related decline and disease. In this review, we provide a comprehensive overview of epigenetic studies from invertebrate organisms, vertebrate models, tissues, and in vitro systems. We establish links between common operative aging pathways and hallmark chromatin signatures that can be used to identify "druggable" targets to counter human aging and age-related disease. PMID:27518561

  12. Mechanism-based Modeling of Long-term Degradation

    NASA Technical Reports Server (NTRS)

    McManus, H. L.; Foch, B. J.; Cunningham, R. A.

    1998-01-01

    The use of composites in high temperature, long lifetime applications requires a basic understanding of composite degradation mechanisms, advances in analytical capabilities, and accurate accelerated and scaled tests. To advance all of these goals, models are proposed based on a variety of fundamental material mechanisms. Thermal, oxygen, and moisture diffusion, chemical reactions, composite micromechanics; modified laminated plate theory, and future mechanics based damage models are used. All models attempt to stay as simple and fundamental as possible. All are coupled, so that interactions between various effects are modeled implicitly. Ongoing efforts at MIT are reviewed here, with some reference to other work, but no attempt is made to do a comprehensive review. Mechanism based models are yielding understanding of the mechanisms behind observed degradation phenomena, are helping to design accelerated tests, and are the first steps towards a predictive capability.

  13. Product analysis for polyethylene degradation by radiation and thermal ageing

    NASA Astrophysics Data System (ADS)

    Sugimoto, Masaki; Shimada, Akihiko; Kudoh, Hisaaki; Tamura, Kiyotoshi; Seguchi, Tadao

    2013-01-01

    The oxidation products in crosslinked polyethylene for cable insulation formed during thermal and radiation ageing were analyzed by FTIR-ATR. The products were composed of carboxylic acid, carboxylic ester, and carboxylic anhydride for all ageing conditions. The relative yields of carboxylic ester and carboxylic anhydride increased with an increase of temperature for radiation and thermal ageing. The carboxylic acid was the primary oxidation product and the ester and anhydride were secondary products formed by the thermally induced reactions of the carboxylic acids. The carboxylic acid could be produced by chain scission at any temperature followed by the oxidation of the free radicals formed in the polyethylene. The results of the analysis led to formulation of a new oxidation mechanism which was different from the chain reactions via peroxy radicals and peroxides.

  14. Physical and mechanical properties of degraded waste surrogate material

    SciTech Connect

    Hansen, F.D.; Mellegard, K.D.

    1998-03-01

    This paper discusses rock mechanics testing of surrogate materials to provide failure criteria for compacted, degraded nuclear waste. This daunting proposition was approached by first assembling all known parameters such as the initial waste inventory and rock mechanics response of the underground setting after the waste is stored. Conservative assumptions allowing for extensive degradation processes helped quantify the lowest possible strength conditions of the future state of the waste. In the larger conceptual setting, computations involve degraded waste behavior in transient pressure gradients as gas exits the waste horizon into a wellbore. Therefore, a defensible evaluation of tensile strength is paramount for successful analyses and intentionally provided maximal failed volumes. The very conservative approach assumes rampant degradation to define waste surrogate composition. Specimens prepared from derivative degradation product were consolidated into simple geometries for rock mechanics testing. Tensile strength thus derived helped convince a skeptical peer review panel that drilling into the Waste Isolation Pilot Plant (WIPP) would not likely expel appreciable solids via the drill string.

  15. Degradation Mechanisms and Accelerated Testing in PEM Fuel Cells

    SciTech Connect

    Borup, Rodney L.

    2011-01-01

    The durability of PEM fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. Although there has been recent progress in improving durability, further improvements are needed to meet the commercialization targets. Past improvements have largely been made possible because of the fundamental understanding of the underlying degradation mechanisms. By investigating component and cell degradation modes; defining the fundamental degradation mechanisms of components and component interactions new materials can be designed to improve durability. Various factors have been shown to affect the useful life of PEM fuel cells. Other issues arise from component optimization. Operational conditions (such as impurities in either the fuel or oxidant stream), cell environment, temperature (including subfreezing exposure), pressure, current, voltage, etc.; or transient versus continuous operation, including start-up and shutdown procedures, represent other factors that can affect cell performance and durability.

  16. Degradation and mechanism of the mechanics and durability of reinforced concrete slab in a marine environment

    NASA Astrophysics Data System (ADS)

    Wu, Sheng-xing; Liu, Guan-guo; Bian, Han-bing; Lv, Wei-bo; Jiang, Jian-hua

    2016-04-01

    An experimental research was conducted to determine the corrosion and bearing capacity of a reinforced concrete (RC) slab at different ages in a marine environment. Results show that the development of corrosion-induced cracks on a slab in a marine environment can be divided into three stages according to crack morphology at the bottom of the slab. In the first stage, cracks appear. In the second stage, cracks develop from the edges to the middle of the slab. In the third stage, longitudinal and transverse corrosion-induced cracks coexist. The corrosion ratio of reinforcements nonlinearly increases with the age, and the relationship between the corrosion ratio of the reinforcements and the corrosion-induced crack width of the concrete is established. The flexural capacity of the corroded RC slab nonlinearly decreases with the age, and the model for the bearing capacity factor of the corroded RC slab is established. The mid-span deflection of the corroded RC slab that corresponds to the yield of the reinforcements linearly increases with the increase in corrosion ratio. Finally, the mechanisms of corrosion morphology and the degradation of the mechanical properties of an RC slab in a marine environment are discussed on the basis of the basic theories of steel corrosion in concrete and concrete structure design.

  17. Neural mechanisms of ageing and cognitive decline

    PubMed Central

    Bishop, Nicholas A.; Lu, Tao; Yankner, Bruce A.

    2010-01-01

    During the past century, treatments for the diseases of youth and middle age have helped raise life expectancy significantly. However, cognitive decline has emerged as one of the greatest health threats of old age, with nearly 50% of adults over the age of 85 afflicted with Alzheimer’s disease. Developing therapeutic interventions for such conditions demands a greater understanding of the processes underlying normal and pathological brain ageing. Recent advances in the biology of ageing in model organisms, together with molecular and systems-level studies of the brain, are beginning to shed light on these mechanisms and their potential roles in cognitive decline. PMID:20336135

  18. Aging degradation of cast stainless steel: status and program

    SciTech Connect

    Chopra, O.K.; Ayrault, G.

    1983-10-01

    A program has been initiated to investigate the significance of in-service embrittlement of cast duplex stainless steels under light-water reactor operating conditions. The existing data are reviewed to determine the critical parameters that control the aging behavior and to define the objectives and scope of the investigation. The test matrices for microstructural studies and mechanical property measurements are presented. The initial experimental effort is focussed on characterizing the microstructure of long-term, low-temperature aged material. Specimens from three heats of cast CF-8 and CF-8M stainless steel aged for up to 70,000 h at 300, 350, and 400/sup 0/C were obtained from George Fisher Ltd., of Switzerland. Initial analyses reveal the formation of three different types of precipitates which are not ..cap alpha..'. An FCC phase, similar to the M/sub 23/C/sub 6/ precipitates, was present in all the long-term aged material. 15 references, 10 figures, 2 tables.

  19. Silk Fibroin Degradation Related to Rheological and Mechanical Properties.

    PubMed

    Partlow, Benjamin P; Tabatabai, A Pasha; Leisk, Gary G; Cebe, Peggy; Blair, Daniel L; Kaplan, David L

    2016-05-01

    Regenerated silk fibroin has been proposed as a material substrate for biomedical, optical, and electronic applications. Preparation of the silk fibroin solution requires extraction (degumming) to remove contaminants, but results in the degradation of the fibroin protein. Here, a mechanism of fibroin degradation is proposed and the molecular weight and polydispersity is characterized as a function of extraction time. Rheological analysis reveals significant changes in the viscosity of samples while mechanical characterization of cast and drawn films shows increased moduli, extensibility, and strength upon drawing. Fifteen minutes extraction time results in degraded fibroin that generates the strongest films. Structural analysis by wide angle X-ray scattering (WAXS) and Fourier transform infrared spectroscopy (FTIR) indicates molecular alignment in the drawn films and shows that the drawing process converts amorphous films into the crystalline, β-sheet, secondary structure. Most interesting, by using selected extraction times, films with near-native crystallinity, alignment, and molecular weight can be achieved; yet maximal mechanical properties for the films from regenerated silk fibroin solutions are found with solutions subjected to some degree of degradation. These results suggest that the regenerated solutions and the film casting and drawing processes introduce more complexity than native spinning processes. PMID:26756449

  20. Mechanical properties and in vitro degradation of bioresorbable knitted stents.

    PubMed

    Nuutinen, Juha-Pekka; Välimaa, Tero; Clerc, Claude; Törmälä, Pertti

    2002-01-01

    The aim of this study was to characterize the mechanical properties and in vitro degradation of bioresorbable knitted stents. Each stent was knitted using a single self-reinforced fibre made out of either PLLA or 96L/4D PLA or 80L/20G PLGA. The mechanical and physical properties of the fibres and stents were measured before and after gamma sterilization, as well as during in vitro degradation. The mechanical properties of the knitted stents made out of bioresorbable fibres were similar to those of commercially available metallic stents. The knitting geometry (loop height) had a marked effect on the mechanical properties of the stents. The rate of in vitro degradation in mechanical and physical properties for the PLLA and 96L/4D PLA stents was similar and significantly lower than that of the 80L/20G PLGA stents. The 80L/20G PLGA stents lost about 35% of their initial weight at 11 weeks. At this time, they had lost all their compression resistance strength. These data can be used as a guideline in planning further studies in vivo. PMID:12555898

  1. Environment assisted degradation mechanisms in aluminum-lithium alloys

    NASA Technical Reports Server (NTRS)

    Gangloff, Richard P.; Stoner, Glenn E.; Swanson, Robert E.

    1988-01-01

    Section 1 of this report records the progress achieved on NASA-LaRC Grant NAG-1-745 (Environment Assisted Degradation Mechanisms in Al-Li Alloys), and is based on research conducted during the period April 1 to November 30, 1987. A discussion of work proposed for the project's second year is included. Section 2 provides an overview of the need for research on the mechanisms of environmental-mechanical degradation of advanced aerospace alloys based on aluminum and lithium. This research is to provide NASA with the basis necessary to permit metallurgical optimization of alloy performance and engineering design with respect to damage tolerance, long term durability and reliability. Section 3 reports on damage localization mechanisms in aqueous chloride corrosion fatigue of aluminum-lithium alloys. Section 4 reports on progress made on measurements and mechanisms of localized aqueous corrosion in aluminum-lithium alloys. Section 5 provides a detailed technical proposal for research on environmental degradation of Al-Li alloys, and the effect of hydrogen in this.

  2. Photooxidation of cellulose nitrate: new insights into degradation mechanisms.

    PubMed

    Berthumeyrie, Sebastien; Collin, Steeve; Bussiere, Pierre-Olivier; Therias, Sandrine

    2014-05-15

    Cellulose nitrate (or nitrocellulose) has received considerable interest due to its uses in various applications, such as paints, photographic films and propellants. However, it is considered as one of the primary pollutants in the energetic material industries because it can be degraded to form polluting chemical species. In this work, the UV light degradation of cellulose nitrate films was studied under conditions of artificially accelerated photooxidation. To eliminate the reactivity of nitro groups, the degradation of ethylcellulose was also investigated. Infrared spectroscopy analyses of the chemical modifications caused by the photooxidation of cellulose nitrate films and the resulting formation of volatile products revealed the occurrence of de-nitration and the formation of oxidation photoproducts exhibiting lactone and anhydride functions. The impact of these chemical modifications on the mechanical and thermal properties of cellulose nitrate films includes embrittlement and lower temperatures of ignition when used as a propellant. PMID:24685530

  3. Mechanisms of polymer degradation using an oxygen plasma generator

    NASA Technical Reports Server (NTRS)

    Colony, Joe A.; Sanford, Edward L.

    1987-01-01

    An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

  4. Delaying aging and the aging-associated decline in protein homeostasis by inhibition of tryptophan degradation.

    PubMed

    van der Goot, Annemieke T; Zhu, Wentao; Vázquez-Manrique, Rafael P; Seinstra, Renée I; Dettmer, Katja; Michels, Helen; Farina, Francesca; Krijnen, Jasper; Melki, Ronald; Buijsman, Rogier C; Ruiz Silva, Mariana; Thijssen, Karen L; Kema, Ido P; Neri, Christian; Oefner, Peter J; Nollen, Ellen A A

    2012-09-11

    Toxicity of aggregation-prone proteins is thought to play an important role in aging and age-related neurological diseases like Parkinson and Alzheimer's diseases. Here, we identify tryptophan 2,3-dioxygenase (tdo-2), the first enzyme in the kynurenine pathway of tryptophan degradation, as a metabolic regulator of age-related α-synuclein toxicity in a Caenorhabditis elegans model. Depletion of tdo-2 also suppresses toxicity of other heterologous aggregation-prone proteins, including amyloid-β and polyglutamine proteins, and endogenous metastable proteins that are sensors of normal protein homeostasis. This finding suggests that tdo-2 functions as a general regulator of protein homeostasis. Analysis of metabolite levels in C. elegans strains with mutations in enzymes that act downstream of tdo-2 indicates that this suppression of toxicity is independent of downstream metabolites in the kynurenine pathway. Depletion of tdo-2 increases tryptophan levels, and feeding worms with extra L-tryptophan also suppresses toxicity, suggesting that tdo-2 regulates proteotoxicity through tryptophan. Depletion of tdo-2 extends lifespan in these worms. Together, these results implicate tdo-2 as a metabolic switch of age-related protein homeostasis and lifespan. With TDO and Indoleamine 2,3-dioxygenase as evolutionarily conserved human orthologs of TDO-2, intervening with tryptophan metabolism may offer avenues to reducing proteotoxicity in aging and age-related diseases. PMID:22927396

  5. Delaying aging and the aging-associated decline in protein homeostasis by inhibition of tryptophan degradation

    PubMed Central

    van der Goot, Annemieke T.; Zhu, Wentao; Vázquez-Manrique, Rafael P.; Seinstra, Renée I.; Dettmer, Katja; Michels, Helen; Farina, Francesca; Krijnen, Jasper; Melki, Ronald; Buijsman, Rogier C.; Ruiz Silva, Mariana; Thijssen, Karen L.; Kema, Ido P.; Neri, Christian; Oefner, Peter J.; Nollen, Ellen A. A.

    2012-01-01

    Toxicity of aggregation-prone proteins is thought to play an important role in aging and age-related neurological diseases like Parkinson and Alzheimer’s diseases. Here, we identify tryptophan 2,3-dioxygenase (tdo-2), the first enzyme in the kynurenine pathway of tryptophan degradation, as a metabolic regulator of age-related α-synuclein toxicity in a Caenorhabditis elegans model. Depletion of tdo-2 also suppresses toxicity of other heterologous aggregation-prone proteins, including amyloid-β and polyglutamine proteins, and endogenous metastable proteins that are sensors of normal protein homeostasis. This finding suggests that tdo-2 functions as a general regulator of protein homeostasis. Analysis of metabolite levels in C. elegans strains with mutations in enzymes that act downstream of tdo-2 indicates that this suppression of toxicity is independent of downstream metabolites in the kynurenine pathway. Depletion of tdo-2 increases tryptophan levels, and feeding worms with extra l-tryptophan also suppresses toxicity, suggesting that tdo-2 regulates proteotoxicity through tryptophan. Depletion of tdo-2 extends lifespan in these worms. Together, these results implicate tdo-2 as a metabolic switch of age-related protein homeostasis and lifespan. With TDO and Indoleamine 2,3-dioxygenase as evolutionarily conserved human orthologs of TDO-2, intervening with tryptophan metabolism may offer avenues to reducing proteotoxicity in aging and age-related diseases. PMID:22927396

  6. The mitochondrial theory of aging: do damaged mitochondria accumulate by delayed degradation?

    PubMed

    Kowald, A

    1999-08-01

    The mitochondrial theory of aging states that the slow accumulation of impaired mitochondria is the driving force of the aging process. In recent years, this theory has gained new support with the discovery of age-related mitochondrial DNA deletions. However, the underlying mechanism of the accumulation of defective mitochondria remained unclear. This has changed recently with the proposal of de Grey that damaged mitochondria have a decreased degradation rate. The resulting increase in biological half-life would be a strong selection advantage leading to the accumulation of defective mitochondria. In this article, I summarize current ideas on how damaged organelles can build up in a cell as well as the shortcomings of these ideas. Then the new hypothesis and its justification are described. It appears that de Grey's hypothesis is a very promising concept that elegantly solves inconsistencies of current models and is in accordance with experimental findings. PMID:10530786

  7. Cellular Mechanisms of Somatic Stem Cell Aging

    PubMed Central

    Jung, Yunjoon

    2014-01-01

    Tissue homeostasis and regenerative capacity rely on rare populations of somatic stem cells endowed with the potential to self-renew and differentiate. During aging, many tissues show a decline in regenerative potential coupled with a loss of stem cell function. Cells including somatic stem cells have evolved a series of checks and balances to sense and repair cellular damage to maximize tissue function. However, during aging the mechanisms that protect normal cell function begin to fail. In this review, we will discuss how common cellular mechanisms that maintain tissue fidelity and organismal lifespan impact somatic stem cell function. We will highlight context-dependent changes and commonalities that define aging, by focusing on three age-sensitive stem cell compartments: blood, neural, and muscle. Understanding the interaction between extrinsic regulators and intrinsic effectors that operate within different stem cell compartments is likely to have important implications for identifying strategies to improve health span and treat age-related degenerative diseases. PMID:24439814

  8. Cellular mechanisms of somatic stem cell aging.

    PubMed

    Jung, Yunjoon; Brack, Andrew S

    2014-01-01

    Tissue homeostasis and regenerative capacity rely on rare populations of somatic stem cells endowed with the potential to self-renew and differentiate. During aging, many tissues show a decline in regenerative potential coupled with a loss of stem cell function. Cells including somatic stem cells have evolved a series of checks and balances to sense and repair cellular damage to maximize tissue function. However, during aging the mechanisms that protect normal cell function begin to fail. In this review, we will discuss how common cellular mechanisms that maintain tissue fidelity and organismal lifespan impact somatic stem cell function. We will highlight context-dependent changes and commonalities that define aging, by focusing on three age-sensitive stem cell compartments: blood, neural, and muscle. Understanding the interaction between extrinsic regulators and intrinsic effectors that operate within different stem cell compartments is likely to have important implications for identifying strategies to improve health span and treat age-related degenerative diseases. PMID:24439814

  9. Degradation mechanism of planar perovskite solar cells (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Qin, Chuanjiang; Matsushima, Toshinori; Adachi, Chihaya

    2015-10-01

    Organic-inorganic hybrid halide perovskites are an interesting class of materials that have excellent semiconductor properties, and demonstrated promising applications on many fields, such as solar cells, water photolysis, light emitting diodes, and amplified spontaneous emission. So far, the device lifetime is still short, and this is an important key issue faced for all researchers in this field.[1] The deep understanding of their durability and degradation mechanism is critical and necessary toward future applications. Towards development of efficient and long-term stable perovskite solar cells (PSCs), we firstly studied the relationship between crystallization, morphology, device architecture, efficiency and durability of encapsulated PSCs. Furthermore, the degradation mechanism of the devices was elucidated by different experimental methods. The well crystallized and fully covered perovskite layer improves not only power conversion efficiency but also long-time durability. Compared to a widely used silver counter electrode, lithium fluoride/aluminum and gold electrode-based PSCs demonstrated better durability owing to less chemical degradation and interface changing. We also confirmed that the amount of accumulated charge carriers induces the degradation of the PSCs, which was proved by a thermally stimulated current technique. Finally, we realized a planar PSC with excellent durability by improving device encapsulation and optimizing device structures. Reference: 1. M. Grätzel, Nature Materials 2014, 13, 838-842.

  10. Molecular mechanisms of ageing and related diseases.

    PubMed

    Liu, Jun-Ping

    2014-07-01

    Human and other multicellular life species age, and ageing processes become dominant during the late phase of life. Recent studies challenge this dogma, suggesting that ageing does not occur in some animal species. In mammals, cell replicative senescence occurs as early as before birth (i.e. in embryos) under physiological conditions. How the molecular machinery operates and why ageing cells dominate under some circumstances are intriguing questions. Recent studies show that cell ageing involves extensive cellular remodelling, including telomere attrition, heterochromatin formation, endoplasmic reticulum stress, mitochondrial disorders and lysosome processing organelles and chromatins. This article provides an update on the molecular mechanisms underlying the ageing of various cell types, the newly described developmental and programmed replicative senescence and the critical roles of cellular organelles and effectors in Parkinson's disease, diabetes, hypertension and dyskeratosis congenita. PMID:24798238

  11. High Temperature Degradation Mechanisms in Polymer Matrix Composites

    NASA Technical Reports Server (NTRS)

    Cunningham, Ronan A.

    1996-01-01

    Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects

  12. Degradation mechanisms and accelerated testing in PEM fuel cells

    SciTech Connect

    Borup, Rodney L; Mukundan, Rangachary

    2010-01-01

    The durability of PEM fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. Although there has been recent progress in improving durability, further improvements are needed to meet the commercialization targets. Past improvements have largely been made possible because of the fundamental understanding of the underlying degradation mechanisms. By investigating component and cell degradation modes; defining the fundamental degradation mechanisms of components and component interactions new materials can be designed to improve durability. Various factors have been shown to affect the useful life of PEM fuel cells. Other issues arise from component optimization. Operational conditions (such as impurities in either the fuel and oxidant stream), cell environment, temperature (including subfreezing exposure), pressure, current, voltage, etc.; or transient versus continuous operation, including start-up and shutdown procedures, represent other factors that can affect cell performance and durability. The need for Accelerated Stress Tests (ASTs) can be quickly understood given the target lives for fuel cell systems: 5000 hours ({approx} 7 months) for automotive, and 40,000 hrs ({approx} 4.6 years) for stationary systems. Thus testing methods that enable more rapid screening of individual components to determine their durability characteristics, such as off-line environmental testing, are needed for evaluating new component durability in a reasonable turn-around time. This allows proposed improvements in a component to be evaluated rapidly and independently, subsequently allowing rapid advancement in PEM fuel cell durability. These tests are also crucial to developers in order to make sure that they do not sacrifice durability while making improvements in costs (e.g. lower platinum group metal [PGM] loading) and performance (e.g. thinner membrane or a GDL with better water management properties). To

  13. AGING MANAGEMENT USING PROACTIVE MANAGEMENT OF MATERIALS DEGRADATION

    SciTech Connect

    Doctor, S. R.; Bond, L. J.; Cumblidge, S. E.; Bruemmer, S. M.; Taylor, W. B.; Carpenter, C. E.; Hull, A. B.; Malik, S. N.

    2010-02-22

    The U.S. Nuclear Regulatory Commission (NRC) has undertaken a program to lay the technical foundations for defining proactive actions to manage degradation of materials in light water reactors. The current focus is existing plants; however, if applied to new construction, there is potential to better monitor and manage plants throughout their life cycle. This paper discusses the NRC's Proactive Management of Materials Degradation program and its application to nuclear power plant structures, systems, and components.

  14. Aging Management using Proactive Management of Materials Degradation

    SciTech Connect

    Doctor, Steven R.; Bond, Leonard J.; Cumblidge, Stephen E.; Bruemmer, Stephen M.; Taylor, W Boyd; Carpenter, C. E.; Hull, Amy B.; Malik, Shah

    2010-10-01

    The U.S. Nuclear Regulatory Commission (NRC) has undertaken a program to lay the technical foundations for defining proactive actions to manage degradation of materials in light water reactors (LWRs). The current focus is existing plants; however, if applied to new construction, there is potential to better monitor and manage plants throughout their life cycle. This paper discusses the NRC’s Proactive Management of Materials Degradation (PMMD) program and its application to nuclear power plant structures, systems, and components (SSC).

  15. Aging Management Using Proactive Management of Materials Degradation

    NASA Astrophysics Data System (ADS)

    Doctor, S. R.; Bond, L. J.; Cumblidge, S. E.; Bruemmer, S. M.; Taylor, W. B.; Carpenter, C. E.; Hull, A. B.; Malik, S. N.

    2010-02-01

    The U.S. Nuclear Regulatory Commission (NRC) has undertaken a program to lay the technical foundations for defining proactive actions to manage degradation of materials in light water reactors. The current focus is existing plants; however, if applied to new construction, there is potential to better monitor and manage plants throughout their life cycle. This paper discusses the NRC's Proactive Management of Materials Degradation program and its application to nuclear power plant structures, systems, and components.

  16. Mechanisms of Aβ Clearance and Degradation by Glial Cells.

    PubMed

    Ries, Miriam; Sastre, Magdalena

    2016-01-01

    Glial cells have a variety of functions in the brain, ranging from immune defense against external and endogenous hazardous stimuli, regulation of synaptic formation, calcium homeostasis, and metabolic support for neurons. Their dysregulation can contribute to the development of neurodegenerative disorders, including Alzheimer's disease (AD). One of the most important functions of glial cells in AD is the regulation of Amyloid-β (Aβ) levels in the brain. Microglia and astrocytes have been reported to play a central role as moderators of Aβ clearance and degradation. The mechanisms of Aβ degradation by glial cells include the production of proteases, including neprilysin, the insulin degrading enzyme, and the endothelin-converting enzymes, able to hydrolyse Aβ at different cleavage sites. Besides these enzymes, other proteases have been described to have some role in Aβ elimination, such as plasminogen activators, angiotensin-converting enzyme, and matrix metalloproteinases. Other relevant mediators that are released by glial cells are extracellular chaperones, involved in the clearance of Aβ alone or in association with receptors/transporters that facilitate their exit to the blood circulation. These include apolipoproteins, α2macroglobulin, and α1-antichymotrypsin. Finally, astrocytes and microglia have an essential role in phagocytosing Aβ, in many cases via a number of receptors that are expressed on their surface. In this review, we examine all of these mechanisms, providing an update on the latest research in this field. PMID:27458370

  17. Mechanisms of Aβ Clearance and Degradation by Glial Cells

    PubMed Central

    Ries, Miriam; Sastre, Magdalena

    2016-01-01

    Glial cells have a variety of functions in the brain, ranging from immune defense against external and endogenous hazardous stimuli, regulation of synaptic formation, calcium homeostasis, and metabolic support for neurons. Their dysregulation can contribute to the development of neurodegenerative disorders, including Alzheimer’s disease (AD). One of the most important functions of glial cells in AD is the regulation of Amyloid-β (Aβ) levels in the brain. Microglia and astrocytes have been reported to play a central role as moderators of Aβ clearance and degradation. The mechanisms of Aβ degradation by glial cells include the production of proteases, including neprilysin, the insulin degrading enzyme, and the endothelin-converting enzymes, able to hydrolyse Aβ at different cleavage sites. Besides these enzymes, other proteases have been described to have some role in Aβ elimination, such as plasminogen activators, angiotensin-converting enzyme, and matrix metalloproteinases. Other relevant mediators that are released by glial cells are extracellular chaperones, involved in the clearance of Aβ alone or in association with receptors/transporters that facilitate their exit to the blood circulation. These include apolipoproteins, α2macroglobulin, and α1-antichymotrypsin. Finally, astrocytes and microglia have an essential role in phagocytosing Aβ, in many cases via a number of receptors that are expressed on their surface. In this review, we examine all of these mechanisms, providing an update on the latest research in this field. PMID:27458370

  18. Mechanisms of folate losses during processing: diffusion vs. heat degradation.

    PubMed

    Delchier, Nicolas; Ringling, Christiane; Maingonnat, Jean-François; Rychlik, Michael; Renard, Catherine M G C

    2014-08-15

    Though folates are sensitive to heat treatments, leaching appears to be a major mechanism involved in folate losses in vegetables during processing. The aim of our study was to study folate diffusivity and degradation from spinach and green beans, in order to determine the proportion of each mechanism involved in folate losses. Folate diffusivity constant, calculated according to Fick's second law (Crank, 1975), was 7.4×10(-12) m(2)/s for spinach and 5.8×10(-10) m(2)/s for green beans, which is the same order of magnitude as for sugars and acids for each vegetable considered. Folate thermal degradation kinetics was not monotonous in spinach and green beans especially at 45 °C and did not follow a first order reaction. The proportion of vitamers changed markedly after thermal treatment, with a better retention of formyl derivatives. For spinach, folate losses were mainly due to diffusion while for green beans thermal degradation seemed to be preponderant. PMID:24679802

  19. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Choe, Yoong-Kee; Henson, Neil J.; Kim, Yu Seung

    2015-12-01

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.

  20. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    SciTech Connect

    Choe, Yoong-Kee; Henson, Neil J.; Kim, Yu Seung

    2015-12-31

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.

  1. Effects of Material Degradation on the Structural Integrity of Composite Materials: Experimental Investigation and Modeling of High Temperature Degradation Mechanisms

    NASA Technical Reports Server (NTRS)

    Cunningham, Ronan A.; McManus, Hugh L.

    1996-01-01

    It has previously been demonstrated that simple coupled reaction-diffusion models can approximate the aging behavior of PMR-15 resin subjected to different oxidative environments. Based on empirically observed phenomena, a model coupling chemical reactions, both thermal and oxidative, with diffusion of oxygen into the material bulk should allow simulation of the aging process. Through preliminary modeling techniques such as this it has become apparent that accurate analytical models cannot be created until the phenomena which cause the aging of these materials are quantified. An experimental program is currently underway to quantify all of the reaction/diffusion related mechanisms involved. The following contains a summary of the experimental data which has been collected through thermogravimetric analyses of neat PMR-15 resin, along with analytical predictions from models based on the empirical data. Thermogravimetric analyses were carried out in a number of different environments - nitrogen, air and oxygen. The nitrogen provides data for the purely thermal degradation mechanisms while those in air provide data for the coupled oxidative-thermal process. The intent here is to effectively subtract the nitrogen atmosphere data (assumed to represent only thermal reactions) from the air and oxygen atmosphere data to back-figure the purely oxidative reactions. Once purely oxidative (concentration dependent) reactions have been quantified it should then be possible to quantify the diffusion of oxygen into the material bulk.

  2. Degradation of Thiamethoxam in aqueous solution by ozonation: Influencing factors, intermediates, degradation mechanism and toxicity assessment.

    PubMed

    Zhao, Qinghua; Ge, Yanan; Zuo, Peng; Shi, Dong; Jia, Shouhua

    2016-03-01

    This paper focuses on the degradation of Thiamethoxam (THIA) in aqueous solution by ozonation. Four influencing factors: pH, THIA initial concentration, ozone concentration and temperature were investigated in order to optimize the conditions, and pH showed the greatest impact; the removal efficiency reached up to 71.19% under the condition of pH 5-11, THIA initial concentration 50-300 mg L(-1), the ozone concentration 10-22.5 mg L(-1) at 293-308 K after 90 min. Four main intermediates were separated and identified and the possible degradation mechanism was proposed. The luminous intensity of photobacteria and the chemical oxygen demand (COD) were measured to assess the changes of toxicity and mineralization in ozonation process, and results showed that the inhibition rate decreased by 60% and 76% of COD was removed after 180 min with the THIA initial concentration was 200 mg L(-1). Our study powerfully demonstrates that the degradation of THIA in aqueous solution by ozonation is a promising technology. PMID:26714292

  3. ArF pellicle degradation mechanism for resolving CD variation

    NASA Astrophysics Data System (ADS)

    Choi, Hyungseok; Ahn, Yohan; Ryu, Jua; Lee, Yangkoo; An, Bumhyun; Lee, Seokryeol

    2007-03-01

    With the introduction of ArF laser, a binary mask is preferred because a PSM mask is still weak to the crystal defect called as photomask haze although extensive studies trying to resolve the haze impact to a photomask have been performed by various researchers in company and school. However, a new problem was happened after a binary mask introduction that CD variation in an exposure shot is appeared and is gradually increased. And finally, CD variation considerably causes defects in wafer level. It was proven that CD variation is closely related to the change of the reticle transmittance by a lot of researches. In this study, the mechanism of ArF pellicle degradation is focused on because the pellicle degradation affects a reticle transmittance in direct. The components outgassed from a pellicle by the high photon energy of ArF laser, for example carbon or fluorine, are absorbed on the surface of the reticle, so that the transmittance of the reticle is decreased. The phenomena of the pellicle degradation have been studied by the various viewpoints, theoretical background, experiment and results tested in mass production line in this study. Therefore, this study has the important meaning by providing the substantial clues to resolve CD variation problem in a near future.

  4. Identification of age degradation in EPROM chips using infrared thermography

    NASA Astrophysics Data System (ADS)

    Allred, Lloyd G.

    1998-03-01

    In a recent upgrade of the digital flight control computer for the F-16, there was serious consternation expressed about the quality of the soldering repair process. Dozens of circuit cards failed to function after the upgrade, even though all of these cards operated correctly before the modifications. The shop called for the use of the IR camera to assist in diagnosing and repairing these cards. What the Neural Radiant Energy Detection found was faulty and marginal chips.Of particular interest was the presence of degraded EPROM chips on the Program Memory cards. While it is known that EPROMs have a limited life cycle, the failure has been further characterized. Thermography provides a quantification of the degradation in thermal performance as the EPROMs are reused. Pristine EPROM chips have a rise rate of about 0.008 degrees C/sec. When the heat rates exceed 0.021 degrees C/sec, the EPROM chips will not accept a program. Some of the chips exhibited heat rates exceeding 0.1 degrees C/sec. Some chips with degradation of 0.018 degrees C/sec would accept a program, but fail other functional tests. What is clear from these results is that IR thermography can be used to identify degrading EPROM chips for replacement before failures become immanent.

  5. Normal brain ageing: models and mechanisms

    PubMed Central

    Toescu, Emil C

    2005-01-01

    Normal ageing is associated with a degree of decline in a number of cognitive functions. Apart from the issues raised by the current attempts to expand the lifespan, understanding the mechanisms and the detailed metabolic interactions involved in the process of normal neuronal ageing continues to be a challenge. One model, supported by a significant amount of experimental evidence, views the cellular ageing as a metabolic state characterized by an altered function of the metabolic triad: mitochondria–reactive oxygen species (ROS)–intracellular Ca2+. The perturbation in the relationship between the members of this metabolic triad generate a state of decreased homeostatic reserve, in which the aged neurons could maintain adequate function during normal activity, as demonstrated by the fact that normal ageing is not associated with widespread neuronal loss, but become increasingly vulnerable to the effects of excessive metabolic loads, usually associated with trauma, ischaemia or neurodegenerative processes. This review will concentrate on some of the evidence showing altered mitochondrial function with ageing and also discuss some of the functional consequences that would result from such events, such as alterations in mitochondrial Ca2+ homeostasis, ATP production and generation of ROS. PMID:16321805

  6. Ages estimated from a diffusion equation model for scarp degradation

    USGS Publications Warehouse

    Colman, Steven M.; Watson, K.E.N.

    1983-01-01

    The diffusion equation derived from the continuity equation for hillslopes is applied to scarp erosion in unconsolidated materials. Solutions to this equation allow direct calculation of the product of the rate coefficient and the age of the scarp from measurements of scarp morphology. Where the rate coefficient can be estimated or can be derived from scarps of known age, this method allows direct calculation of unknown ages of scarps.

  7. Region-dependent aggrecan degradation patterns in the rat intervertebral disc are affected by mechanical loading in vivo

    PubMed Central

    Iatridis, James C.; Godburn, Karolyn; Wuertz, Karin; Alini, Mauro; Roughley, Peter J.

    2010-01-01

    Structured Abstract Study Design Immunoblotting study to evaluate aggrecan degradation patterns in rat intervertebral discs(IVDs) subjected to mechanical overload. Objective To evaluate the effects of in vivo dynamic compression overloading on aggrecan degradation products associated with matrix metalloproteinase(MMP) and aggrecanase activity in different regions of the IVD. Summary of Background Data Aggrecan cleavage at the MMP and aggrecanase sites are important events in human IVD aging, with distinct cleavage patterns in the annulus and nucleus regions. No such information is available on regional variations in rat IVDs, nor on how such cleavage is affected by mechanical loading. Methods Sprague-Dawley rats were instrumented with an Ilizarov-type device and subjected to dynamic compression (1 MPa and 1 Hz for 8 hours per day for 8 weeks). Control, sham, and overloaded IVDs were separated by disc region and analyzed for aggrecan degradation products using immunoblotting techniques with antibodies specific for the aggrecanase and MMP cleavage sites in the interglobular domain of aggrecan. Results Control IVDs exhibited strong regional variation in aggrecan degradation patterns with minimal degradation products being present in the nucleus pulposus(NP), degradation products associated with aggrecanase cleavage predominating in the inner annulus fibrosus(AF), and degradation products associated with MMP cleavage predominating in the outer annulus fibrosus. Dynamic compression overloading increased the amount of aggrecan degradation products associated with MMP cleavage particularly in the AF but also in the NP. Degradation profiles of sham IVDs were similar to control. Conclusions Aggrecan G1 regions resulting from proteolysis were found to have a strong regionally-specific pattern in the rat IVD, which was altered under excessive loading. The shift from aggrecanase to MMP-induced degradation products with dynamic compression overloading suggests that protein

  8. Impact of lipid-induced degradation on the mechanical properties of ultra-high molecular weight polyethylene for joint replacements.

    PubMed

    Sakoda, Hideyuki; Niimi, Shingo

    2016-01-01

    Gamma or electron beam irradiation of ultra-high molecular weight polyethylene (UHMWPE) used in artificial joints for sterilization and/or crosslinking purposes generates free radicals in the material, which causes long-term oxidative degradation of UHMWPE. Recently, another mechanism for the degradation of UHMWPE by the absorption of lipids during in vivo clinical use was proposed. However, knowledge on lipid-induced degradation is quite limited, compared with that on radical-induced degradation. In this study, lipid-induced degradation was simulated using squalene absorption and subsequent accelerated aging, and its impact on the mechanical properties of UHMWPE was evaluated. The simulated lipid-induced degradation caused an increased elastic modulus and decreased elongation with maximum degradation at the surfaces. These results imply that degradation of UHMWPE may occur during in vivo long-term use, even if free radicals are completely eliminated. Therefore, further investigation is required to clarify the impact of lipid-induced degradation on clinical outcomes, such as the wear and fatigue characteristics of UHMWPE components. PMID:26340645

  9. Degradation Mechanisms and Lifetime Prediction for Lithium-Ion Batteries -- A Control Perspective: Preprint

    SciTech Connect

    Smith, Kandler; Shi, Ying; Santhanagopalan, Shriram

    2015-07-29

    Predictive models of Li-ion battery lifetime must consider a multiplicity of electrochemical, thermal, and mechanical degradation modes experienced by batteries in application environments. To complicate matters, Li-ion batteries can experience different degradation trajectories that depend on storage and cycling history of the application environment. Rates of degradation are controlled by factors such as temperature history, electrochemical operating window, and charge/discharge rate. We present a generalized battery life prognostic model framework for battery systems design and control. The model framework consists of trial functions that are statistically regressed to Li-ion cell life datasets wherein the cells have been aged under different levels of stress. Degradation mechanisms and rate laws dependent on temperature, storage, and cycling condition are regressed to the data, with multiple model hypotheses evaluated and the best model down-selected based on statistics. The resulting life prognostic model, implemented in state variable form, is extensible to arbitrary real-world scenarios. The model is applicable in real-time control algorithms to maximize battery life and performance. We discuss efforts to reduce lifetime prediction error and accommodate its inevitable impact in controller design.

  10. Photolytic and photocatalytic degradation of tetracycline: Effect of humic acid on degradation kinetics and mechanisms.

    PubMed

    Li, Si; Hu, Jiangyong

    2016-11-15

    The widespread occurrence of tetracycline (TC) in the aquatic environment poses a potential risk to aquatic ecosystem and human health. In this study, elimination of TC by photolysis and TiO2 photocatalysis were investigated by using mercury-free UVA-LED as an alternative light source. Particular emphasis was given to the effect of humic acid (HA) on the reaction kinetics and mechanisms of TC removal. Photolytic degradation of TC was slightly enhanced by HA due to its photosensitization effect, as evidenced by the increased steady-state concentrations of OH. The most abundant transformation product of TC, which was formed by the attack of OH radical, was enhanced during photolytic degradation. During photocatalytic experiments, HA dramatically inhibited TC loss due to the surface deactivation of TiO2 and OH quenching. The steady-state concentration of OH was dramatically decreased in the presence of HA. Identification of transformation products showed that HA could inhibit the oxidation pathways initiated by OH during photocatalysis of TC. These findings provide further insights into the assessment of photolysis and photocatalysis for antibiotics elimination in natural waters where HA exists ubiquitously. PMID:27420385

  11. Nylon 6.6 accelerated aging studies : thermal-oxidative degradation and its interaction with hydrolysis.

    SciTech Connect

    Bernstein, Robert; Derzon, Dora Kay; Gillen, Kenneth T.

    2004-06-01

    Accelerated aging of Nylon 6.6 fibers used in parachutes has been conducted by following the tensile strength loss under both thermal-oxidative and 100% relative humidity conditions. Thermal-oxidative studies (air circulating ovens) were performed for time periods of weeks to years at temperatures ranging from 37 C to 138 C. Accelerated aging humidity experiments (100% RH) were performed under both an argon atmosphere to examine the 'pure' hydrolysis pathway, and under an oxygen atmosphere (oxygen partial pressure close to that occurring in air) to mimic true aging conditions. As expected the results indicated that degradation caused by humidity is much more important than thermal-oxidative degradation. Surprisingly when both oxygen and humidity were present the rate of degradation was dramatically enhanced relative to humidity aging in the absence of oxygen. This significant and previously unknown phenomena underscores the importance of careful accelerated aging that truly mimics real world storage conditions.

  12. Mechanisms of charcoal degradation during its initial stages of decomposition

    NASA Astrophysics Data System (ADS)

    Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W. I.

    2010-05-01

    Future climatic changes might result in an increased potential for wildfires, whereby incorporation of charred biomass into soil would increase. The incomplete combustion of biomass results in the production of a chemically heterogeneous class of highly condensed compounds known as pyrogenic C (PyC), which is generally considered resistant to microbial degradation. Recently, studies based on short-term laboratory incubations with soil have indicated that PyC can also eventually degrade (Baldock and Smernik, 2002; Hamer et al., 2004) and it is now widely accepted that a significant quantity of these resistant fraction of soil must have undergone degradation in terrestrial environments. Charcoal has been shown to decompose faster in the initial stages (first 2-3 months) and stabilize later (Kuzyakov et al., 2009). However, studies describing charcoal transformation processes remain scarce. The different potential degradation mechanisms have not yet been studied in combination, and therefore the relative importance for PyC degradation has not been evaluated. We are conducting an incubation experiment to study the biological, chemical and physical degradation/stabilization processes of PyC in soil under controlled conditions. We use Pinus ponderosa 13C/15N labeled (13C: 800 per mil, 15N: 4.2 atom %) wood and charcoal (pyrolysed at 450 °C under N2 atmosphere). We incubate soil from Lägeren forest (Wettingen, Switzerland) with three kind of organic inputs, labeled wood, char and no littler control. The decomposition rates would be estimated based on 13C of CO2 entrapped in NaOH. Time course destructive sampling would be done during the study. Lyophilized soil subsamples will be used for analysis of the amount of 13C incorporation in the microbial biomass using fumigation extraction method and phospholipids fatty acid analysis (PLFA). The remaining PyC in the soil would be characterized for the changes in its chemistry at the molecular level using Benzenepolycarboxlic

  13. Dihydrogen catalysis: a degradation mechanism for N2-fixation intermediates.

    PubMed

    Asatryan, Rubik; Bozzelli, Joseph W; Ruckenstein, Eli

    2012-11-29

    Molecular hydrogen plays multiple roles in activation of nitrogen. Among others, it inhibits the overall process of N(2)-reduction catalyzed by nitrogenase enzyme. The H(2)-assisted dehydrogenation and the H-atom transfer reactions (called dihydrogen catalysis, DHC) are suggested as possible mechanisms for the degradation and removal of potential intermediates formed during the reduction of nitrogen. Several iron-organic model reactions associated with the core stereospecific reaction (cis-N(2)H(2) + H(2) → N(2) + H(2) + H(2)) are examined using a comprehensive density functional theory and ab initio analysis of the corresponding potential energy surfaces. A variety of energetically feasible decomposition pathways are identified for the DHC-oxidation of iron-bound [N(x)H(y)]-species. A liberated diazene intermediate (HN═NH) is suggested to interact in situ with two proximal hydridic H-atoms of an activated (hydrided) Fe-catalyst to produce N(2) and H(2) with a low or even no activation barrier. The majority of identified pathways are shown to be highly sensitive to the electronic environment and spin configuration of metallocomplexes. The H(2)-assisted transport of a single H-atom from a bound [N(x)H(y)] moiety to either the proximal or distal (Fe, S or N) active centers of a catalyst provides an alternative degradation (interconversion) mechanism for the relevant intermediates. The two types of molecular hydrogen-assisted reactions highlighted above, namely, the H(2)-assisted dehydrogenation and the transport of H-atoms, suggest theoretical interpretations for the observed H(2)-inhibition of N(2) activation and HD formation (in the presence of D(2)). The DHC reactions of various [N(x)H(y)] moieties are expected to play significant roles in the industrial high-pressure hydrodenitrification and other catalytic processes involving the metabolism of molecular hydrogen. PMID:23095090

  14. Atomic vacancies significantly degrade the mechanical properties of phosphorene

    NASA Astrophysics Data System (ADS)

    Sha, Zhen-Dong; Pei, Qing-Xiang; Zhang, Ying-Yan; Zhang, Yong-Wei

    2016-08-01

    Due to low formation energies, it is very easy to create atomic defects in phosphorene during its fabrication process. How these atomic defects affect its mechanical behavior, however, remain unknown. Here, we report on a systematic study of the effect of atomic vacancies on the mechanical properties and failure behavior of phosphorene using molecular dynamics simulations. It is found that atomic vacancies induce local stress concentration and cause early bond-breaking, leading to a significant degradation of the mechanical properties of the material. More specifically, a 2% concentration of randomly distributed mono-vacancies is able to reduce the fracture strength by ∼40%. An increase in temperature from 10 to 400 K can further deteriorate the fracture strength by ∼60%. The fracture strength of defective phosphorene is also found to be affected by defect distribution. When the defects are patterned in a line, the reduction in fracture strength greatly depends on the tilt angle and the loading direction. Furthermore, we find that di-vacancies cause an even larger reduction in fracture strength than mono-vacancies when the loading is in an armchair direction. These findings provide important guidelines for the structural design of phosphorene in future applications.

  15. Atomic vacancies significantly degrade the mechanical properties of phosphorene.

    PubMed

    Sha, Zhen-Dong; Pei, Qing-Xiang; Zhang, Ying-Yan; Zhang, Yong-Wei

    2016-08-01

    Due to low formation energies, it is very easy to create atomic defects in phosphorene during its fabrication process. How these atomic defects affect its mechanical behavior, however, remain unknown. Here, we report on a systematic study of the effect of atomic vacancies on the mechanical properties and failure behavior of phosphorene using molecular dynamics simulations. It is found that atomic vacancies induce local stress concentration and cause early bond-breaking, leading to a significant degradation of the mechanical properties of the material. More specifically, a 2% concentration of randomly distributed mono-vacancies is able to reduce the fracture strength by ∼40%. An increase in temperature from 10 to 400 K can further deteriorate the fracture strength by ∼60%. The fracture strength of defective phosphorene is also found to be affected by defect distribution. When the defects are patterned in a line, the reduction in fracture strength greatly depends on the tilt angle and the loading direction. Furthermore, we find that di-vacancies cause an even larger reduction in fracture strength than mono-vacancies when the loading is in an armchair direction. These findings provide important guidelines for the structural design of phosphorene in future applications. PMID:27345189

  16. Identification of CSSC Caused by Aging and Degradation

    SciTech Connect

    Florescu, Gheorghe; Cojan, Mihail

    2006-07-01

    PSA studies, that were developed for some NPPs, permit the using of the created models to perform many research tests, in order to optimize the structures, systems and components (SSCs) operation or to identify the NPP or systems weaknesses, due to specific or special factors. SSCs that influence decisively the NPP reliability are considered as critical. Also, for the accident conditions, the SSC, which have a major influence to the system availability or operability, are considered as critical. Many worldwide NPPs reached the life time or are very close to do that. Several SSCs have shorter life times than NPP's life time. Ageing is one of the factors that decrease the SSC life time. Due to ageing, if are not replaced, some SSCs, or groups of redundant SSCs, become critical looking to safety. Some questions for what to do in the situation when a SSC must be replaced and the SSC specific manufacturer does not exist, could also be put. The paper tried to solve the problem of SSC modeling by introducing of an ageing factor in SSC model. Fault tree (F/T) modeling approach is assumed. There are two possibilities for modeling: failure rates that are changed or specific MCS. (authors)

  17. Peroxisome degradation in mammals: mechanisms of action, recent advances, and perspectives

    PubMed Central

    Nordgren, Marcus; Wang, Bo; Apanasets, Oksana; Fransen, Marc

    2013-01-01

    Peroxisomes are remarkably dynamic organelles that participate in a diverse array of cellular processes, including the metabolism of lipids and reactive oxygen species. In order to regulate peroxisome function in response to changing nutritional and environmental stimuli, new organelles need to be formed and superfluous and dysfunctional organelles have to be selectively removed. Disturbances in any of these processes have been associated with the etiology and progression of various congenital neurodegenerative and age-related human disorders. The aim of this review is to critically explore our current knowledge of how peroxisomes are degraded in mammalian cells and how defects in this process may contribute to human disease. Some of the key issues highlighted include the current concepts of peroxisome removal, the peroxisome quality control mechanisms, the initial triggers for peroxisome degradation, the factors for dysfunctional peroxisome recognition, and the regulation of peroxisome homeostasis. We also dissect the functional and mechanistic relationship between different forms of selective organelle degradation and consider how lysosomal dysfunction may lead to defects in peroxisome turnover. In addition, we draw lessons from studies on other organisms and extrapolate this knowledge to mammals. Finally, we discuss the potential pathological implications of dysfunctional peroxisome degradation for human health. PMID:23785334

  18. Aging mechanisms for concrete components of High-Level Waste storage tanks

    SciTech Connect

    Kassir, M.; Bandyopadhyay, K.; Bush, S.; Mather, B.; Shewmon, P.; Streicher, M.; Thompson, B.; van Rooyen, D.; Weeks, J.

    1995-05-01

    The age-related degradation mechanisms which affect the concrete and the reinforcing steel in the high-level waste (HLW) storage tanks art evaluated with respect to their potential significance to the continued performance of the concrete, and am classified into non-significant and potentially significant. The identified potentially significant degradation mechanisms include the effects of elevated temperature, freezing and thawing, leaching of calcium hydroxide, aggressive chemical attack, and corrosion of the reinforcing steel. To the extent that available knowledge permits, these mechanisms are generically evaluated and quantified so that site-specific plans may be developed to verify whether significant degradation has occurred in the concrete, and, if so, to formulate mitigating measures to avoid further deterioration and possibly repair the degradation or pursue other management options.

  19. Benzoxazinone-Mediated Triazine Degradation: A Proposed Reaction Mechanism.

    PubMed

    Willett, C D; Lerch, R N; Lin, C-H; Goyne, K W; Leigh, N D; Roberts, C A

    2016-06-22

    The role of benzoxazinones (Bx, 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one) in triazine resistance in plants has been studied for over half a century. In this research, fundamental parameters of the reaction between DIBOA-Glc (2-β-d-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one) and atrazine (ATR, 6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine) were examined. Through a series of experiments employing a variety of chromatographic and spectroscopic techniques, the DIBOA-Glc/ATR reaction was characterized in terms of reactant and product kinetics, stoichiometry, identification of a reaction intermediate, and reaction products formed. Results of these experiments demonstrated that the reaction mechanism proceeds via nucleophilic attack of the hydroxamic acid moiety of DIBOA-Glc at the C-2 position of the triazine ring to form hydroxyatrazine (HA, 2-hydroxy-4-ethylamino-6-isopropylamino-s-triazine), with associated degradation of DIBOA-Glc. Degradation of reactants followed first-order kinetics with a noncatalytic role of DIBOA-Glc. A reaction intermediate was identified as a DIBOA-Glc-HA conjugate, indicating a 1:1 DIBOA-Glc:ATR stoichiometry. Reaction products included HA and Cl(-), but definitive identification of DIBOA-Glc reaction product(s) was not attained. With these reaction parameters elucidated, DIBOA-Glc can be evaluated in terms of its potential for a myriad of applications, including its use to address the problem of widespread ATR contamination of soil and water resources. PMID:27215133

  20. Resorbable composites with bioresorbable glass fibers for load-bearing applications. In vitro degradation and degradation mechanism.

    PubMed

    Lehtonen, Timo J; Tuominen, Jukka U; Hiekkanen, Elina

    2013-01-01

    An in vitro degradation study of three bioresorbable glass fiber-reinforced poly(l-lactide-co-dl-lactide) (PLDLA) composites was carried out in simulated body fluid (SBF), to simulate body conditions, and deionized water, to evaluate the nature of the degradation products. The changes in mechanical and chemical properties were systematically characterized over 52 weeks dissolution time to determine the degradation mechanism and investigate strength retention by the bioresorbable glass fiber-reinforced PLDLA composite. The degradation mechanism was found to be a combination of surface and bulk erosion and does not follow the typical core-accelerated degradation mechanism of poly(α-hydroxyacids). Strength retention by bioresorbable glass fiber-reinforced PLDLA composites can be tailored by changing the oxide composition of the glass fibers, but the structure-property relationship of the glass fibers has to be understood and controlled so that the phenomenon of ion leaching can be utilized to control the degradation rate. Therefore, these high performance composites are likely to open up several new possibilities for utilizing resorbable materials in clinical applications which could not be realized in the past. PMID:22963847

  1. Microscopic degradation mechanism of polyimide film caused by surface discharge under bipolar continuous square impulse voltage

    NASA Astrophysics Data System (ADS)

    Luo, Yang; Wu, Guang-Ning; Liu, Ji-Wu; Peng, Jia; Gao, Guo-Qiang; Zhu, Guang-Ya; Wang, Peng; Cao, Kai-Jiang

    2014-02-01

    Polyimide (PI) film is an important type of insulating material used in inverter-fed motors. Partial discharge (PD) under a sequence of high-frequency square impulses is one of the key factors that lead to premature failures in insulation systems of inverter-fed motors. In order to explore the damage mechanism of PI film caused by discharge, an aging system of surface discharge under bipolar continuous square impulse voltage (BCSIV) is designed based on the ASTM 2275 01 standard and the electrical aging tests of PI film samples are performed above the partial discharge inception voltage (PDIV). The chemical bonds of PI polymer chains are analyzed through Fourier transform infrared spectroscopy (FTIR) and the dielectric properties of unaged and aged PI samples are investigated by LCR testers HIOKI 3532-50. Finally, the micro-morphology and micro-structure changes of PI film samples are observed through scanning electron microscopy (SEM). The results show that the physical and chemical effects of discharge cut off the chemical bonds of PI polymer chains. The fractures of ether bond (C—O—C) and imide ring (C—N—C) on the backbone of a PI polymer chain leads to the decrease of molecular weight, which results in the degradation of PI polymers and the generation of new chemical groups and materials, like carboxylic acid, ketone, aldehydes, etc. The variation of microscopic structure of PI polymers can change the orientation ability of polarizable units when the samples are under an AC electric field, which would cause the dielectric constant ɛ to increase and dielectric loss tan δ to decrease. The SEM images show that the degradation path of PI film is initiated from the surface and then gradually extends to the interior with continuous aging. The injection charge could result in the PI macromolecular chain degradation and increase the trap density in the PI polymer bulk.

  2. Semiempirical Predictions of Chemical Degradation Reaction Mechanisms of CL-20 as Related to Molecular Structure

    SciTech Connect

    Qasim, Mohammad M.; Furey, John; Fredrickson, Herbert L.; Szecsody, Jim E.; Mcgrath, Chris J.; Bajpai, Rakesh

    2004-10-01

    Quantum mechanical methods and force field molecular mechanics were used to characterize cage cyclic nitramines and to predict environmental degradation mechanisms. Due to structural similarities it is predicted that, under homologous circumstances, the major environmental RDX degradation pathways should also be effective for CL-20 and similar cyclic nitramines.

  3. Epigenetic Mechanisms of the Aging Human Retina

    PubMed Central

    Pennington, Katie L.; DeAngelis, Margaret M.

    2015-01-01

    Degenerative retinal diseases, such as glaucoma, age-related macular degeneration, and diabetic retinopathy, have complex etiologies with environmental, genetic, and epigenetic contributions to disease pathology. Much effort has gone into elucidating both the genetic and the environmental risk factors for these retinal diseases. However, little is known about how these genetic and environmental risk factors bring about molecular changes that lead to pathology. Epigenetic mechanisms have received extensive attention of late for their promise of bridging the gap between environmental exposures and disease development via their influence on gene expression. Recent studies have identified epigenetic changes that associate with the incidence and/or progression of each of these retinal diseases. Therefore, these epigenetic modifications may be involved in the underlying pathological mechanisms leading to blindness. Further genome-wide epigenetic studies that incorporate well-characterized tissue samples, consider challenges similar to those relevant to gene expression studies, and combine the genome-wide epigenetic data with genome-wide genetic and expression data to identify additional potentially causative agents of disease are needed. Such studies will allow researchers to create much-needed therapeutics to prevent and/or intervene in disease progression. Improved therapeutics will greatly enhance the quality of life and reduce the burden of disease management for millions of patients living with these potentially blinding conditions. PMID:26966390

  4. Thermal degradation reaction mechanism of xylose: A DFT study

    NASA Astrophysics Data System (ADS)

    Huang, Jinbao; He, Chao; Wu, Longqin; Tong, Hong

    2016-08-01

    The thermal degradation reaction mechanism of xylose as hemicellulose model compound was investigated by using density functional theory methods M062X with the 6-31++G(d,p) basis set. Eight possible pyrolytic reaction pathways were proposed and the standard kinetic and thermodynamic parameters in all reaction pathways were calculated at different temperatures. In reaction pathway (1), xylose is first transformed into acyclic containing-carbonyl isomer, and then the isomer further decomposes through four possible pyrolysis pathways (1-1)-(1-4). Pathways (2) and (3) depict an immediate ring-opening process through the simultaneous breaking of C-O and C-C bonds. Pathways (4)-(7) describe the pyrolysis processes of various anhydro-xyloses through a direct ring-opening process. Pathway (8) gives the evolutionary process of pyranones. The calculation results show that reaction pathways (1), (2) and (5) are the major reaction channels and reaction pathways (3), (4), and (6)-(8) are the competitive reaction channels in pyrolysis of xylose. The major products of xylose pyrolysis are low molecular products such as 2-furaldehyde, glycolaldehyde, acetaldehyde, methylglyoxal and acetone, and the main competitive products are formaldehyde, formic acid, acetic acid, CO2, CH4, acetol, pyranone, and so on.

  5. Lignocellulose degradation mechanisms across the Tree of Life.

    PubMed

    Cragg, Simon M; Beckham, Gregg T; Bruce, Neil C; Bugg, Timothy D H; Distel, Daniel L; Dupree, Paul; Etxabe, Amaia Green; Goodell, Barry S; Jellison, Jody; McGeehan, John E; McQueen-Mason, Simon J; Schnorr, Kirk; Walton, Paul H; Watts, Joy E M; Zimmer, Martin

    2015-12-01

    Organisms use diverse mechanisms involving multiple complementary enzymes, particularly glycoside hydrolases (GHs), to deconstruct lignocellulose. Lytic polysaccharide monooxygenases (LPMOs) produced by bacteria and fungi facilitate deconstruction as does the Fenton chemistry of brown-rot fungi. Lignin depolymerisation is achieved by white-rot fungi and certain bacteria, using peroxidases and laccases. Meta-omics is now revealing the complexity of prokaryotic degradative activity in lignocellulose-rich environments. Protists from termite guts and some oomycetes produce multiple lignocellulolytic enzymes. Lignocellulose-consuming animals secrete some GHs, but most harbour a diverse enzyme-secreting gut microflora in a mutualism that is particularly complex in termites. Shipworms however, house GH-secreting and LPMO-secreting bacteria separate from the site of digestion and the isopod Limnoria relies on endogenous enzymes alone. The omics revolution is identifying many novel enzymes and paradigms for biomass deconstruction, but more emphasis on function is required, particularly for enzyme cocktails, in which LPMOs may play an important role. PMID:26583519

  6. Relative humidity and temperature dependence of mechanical degradation of natural fiber composites

    NASA Astrophysics Data System (ADS)

    Pan, YiHui; Zhong, Zheng

    2016-06-01

    In this paper, the mechanical degradation of natural fiber composites is studied with the consideration of the relative humidity and the temperature. A nonlinear constitutive model is established, which employs an internal variable to describe the mechanical degradation related to the energy dissipation during moisture absorption. The existing experimental researches demonstrated that the mechanical degradation is an irreversible thermodynamic process induced by the degradation of fibers and the damages of interfaces between fiber and matrix, both of which depend on the variation of the relative humidity or the temperature. The evolution of the mechanical degradation is obtained through the determination of dissipation rates as a function of the relative humidity and the temperature. The theoretically predicted mechanical degradations are compared with experimental results of sisal fiber reinforced composites subject to different relative humidity and temperatures, and a good agreement is found.

  7. The mechanism of sulforaphene degradation to different water contents.

    PubMed

    Tian, Guifang; Li, Yuan; Cheng, Li; Yuan, Qipeng; Tang, Pingwah; Kuang, Pengqun; Hu, Jing

    2016-03-01

    Sulforaphene extracted from radish seeds was strongly associated with cancer prevention. However, sulforaphene was unstable in aqueous medium and at high temperature. This instability impairs many useful applications of sulforaphene. In this paper, the stability of sulforaphene (purity above 95%) during storage at -20°C, 4°C and 26°C was studied. The degradation product was purified by preparative HPLC and identified by ESI/MS, NMR ((1)H and (13)C NMR) and FTIR spectroscopy. The degradation pathway of sulforaphene was presented. Furthermore, we found that the degradation rate of sulforaphene was closely related to the water content of sulforaphene sample. The higher the water content was, the faster the sulforaphene sample degraded. A mathematical model was developed to predict the degradation constant at various water contents. It provided a guideline for industry to improve the stability of sulforaphene during preparation, application and storage. PMID:26471648

  8. Early Age-Related Macular Degeneration Impairs Tolerance To Stimulus Degradation

    PubMed Central

    Liu, Lei; White, Janis

    2010-01-01

    Purpose Pathologic changes of retinal photoreceptors associated with early age-related macular degeneration (AMD) have been well established, but the disease is usually asymptomatic at the early stage and traditional suprathreshold clinical tests often fail to reveal functional deficiencies. The aim of this study is to demonstrate subtle changes of one suprathreshold visual function in early AMD eyes. Methods The quality of pre-attentively discriminable texture stimuli was systematically degraded through random deletion of texture checks. The subjects’ task was to make a forced-choice decision on whether two equally degraded patches contained samples of the same or different types of textures. Tolerance to texture stimulus degradation was measured in young and elderly normal controls and in patients with early AMD. Results Subjects were trained to perform the texture discrimination task until they made few errors in discriminating intact textures. Texture discrimination deteriorated with increasing stimulus degradation in all subjects. There was no significant difference between performance of young and elderly normal controls. Early AMD eyes showed significantly less tolerance to stimulus degradation than age-similar normal controls at a range of degradation levels. After controlling for visual acuity, normal subjects still performed significantly better than early AMD eyes around 22% check deletion. There was no significant difference between better eyes of early AMD patients and fellow eyes of late AMD eyes. Performance on the degraded texture task was not correlated with visual acuity. A mild blur of the stimulus had little effect on discrimination of degraded textures. Conclusions Early AMD may not directly affect suprathreshold visual functions when the stimuli are intact and contain redundant information, but may manifest itself as a reduction of tolerance to stimulus degradation in the form of localized information loss. The performance of patients with

  9. Mechanism and kinetics of parathion degradation under ultrasonic irradiation.

    PubMed

    Yao, Juan-Juan; Gao, Nai-Yun; Li, Cong; Li, Lei; Xu, Bin

    2010-03-15

    The parathion degradation under ultrasonic irradiation in aqueous solution was investigated. The results indicate that at the conditions in question, degradation rate of parathion decreased with increasing initial concentration and decreasing power. The optimal frequency for parathion degradation was 600 kHz. The free radical reactions predominate in the sonochemical degradation of parathion and the reaction zones are predominately at the bubble interface and, to a much lesser extent, in bulk solution. The gas/liquid interfacial regions are the real effective reaction sites for sonochemical degradation of parathion. The reaction can be well described as a gas/liquid heterogeneous reaction which obeys a kinetic model based on Langmuir-Hinshelwood model. The main pathways of parathion degradation by ultrasonic irradiation were also proposed by qualitative and quantitative analysis of organic and inorganic byproducts. It is indicated that the N(2) in air takes part in the parathion degradation through the formation of NO(2) under ultrasonic irradiation. Parathion is decomposed into paraoxon and 4-nitrophenol in the first step via two different pathways, respectively, which is in agreement with the theoretical molecular orbital (MO) calculations. PMID:19854573

  10. The Intricate Interplay between Mechanisms Underlying Aging and Cancer

    PubMed Central

    Piano, Amanda; Titorenko, Vladimir I.

    2015-01-01

    Age is the major risk factor in the incidence of cancer, a hyperplastic disease associated with aging. Here, we discuss the complex interplay between mechanisms underlying aging and cancer as a reciprocal relationship. This relationship progresses with organismal age, follows the history of cell proliferation and senescence, is driven by common or antagonistic causes underlying aging and cancer in an age-dependent fashion, and is maintained via age-related convergent and divergent mechanisms. We summarize our knowledge of these mechanisms, outline the most important unanswered questions and suggest directions for future research. PMID:25657853

  11. Molecular mechanisms associated with xylan degradation by Xanthomonas plant pathogens.

    PubMed

    Santos, Camila Ramos; Hoffmam, Zaira Bruna; de Matos Martins, Vanesa Peixoto; Zanphorlin, Leticia Maria; de Paula Assis, Leandro Henrique; Honorato, Rodrigo Vargas; Lopes de Oliveira, Paulo Sérgio; Ruller, Roberto; Murakami, Mario Tyago

    2014-11-14

    Xanthomonas pathogens attack a variety of economically relevant plants, and their xylan CUT system (carbohydrate utilization with TonB-dependent outer membrane transporter system) contains two major xylanase-related genes, xynA and xynB, which influence biofilm formation and virulence by molecular mechanisms that are still elusive. Herein, we demonstrated that XynA is a rare reducing end xylose-releasing exo-oligoxylanase and not an endo-β-1,4-xylanase as predicted. Structural analysis revealed that an insertion in the β7-α7 loop induces dimerization and promotes a physical barrier at the +2 subsite conferring this unique mode of action within the GH10 family. A single mutation that impaired dimerization became XynA active against xylan, and high endolytic activity was achieved when this loop was tailored to match a canonical sequence of endo-β-1,4-xylanases, supporting our mechanistic model. On the other hand, the divergent XynB proved to be a classical endo-β-1,4-xylanase, despite the low sequence similarity to characterized GH10 xylanases. Interestingly, this enzyme contains a calcium ion bound nearby to the glycone-binding region, which is required for catalytic activity and structural stability. These results shed light on the molecular basis for xylan degradation by Xanthomonas and suggest how these enzymes synergistically assist infection and pathogenesis. Our findings indicate that XynB contributes to breach the plant cell wall barrier, providing nutrients and facilitating the translocation of effector molecules, whereas the exo-oligoxylanase XynA possibly participates in the suppression of oligosaccharide-induced immune responses. PMID:25266726

  12. Investigation of accelerated stress factors and failure/degradation mechanisms

    NASA Astrophysics Data System (ADS)

    Lathrop, J. W.

    1984-03-01

    Results of the performance tests on unencapsulated cells are described. Equivalent circuit parameters; characteristics of a degraded solar cell; and atomic and molecular species at the cell surface are detailed.

  13. The stability and degradation mechanism of sulforaphene in solvents.

    PubMed

    Tian, Guifang; Tang, Pingwah; Xie, Rui; Cheng, Li; Yuan, Qipeng; Hu, Jing

    2016-05-15

    Sulforaphene, a natural compound, has been investigated as a potential anticancer agent. However, the stability of sulforaphene, in various solvents, and its degradation pathway have not been appropriately reported. This instability impairs the preparation process, the biological evaluation experiments, and the applications of sulforaphene. In this study, the stability of sulforaphene stored at 26°C was investigated in each of the following six solvents: two kinds of protic solvents (methanol and ethanol) and four kinds of aprotic solvents (acetonitrile, dichloromethane, ethyl acetate and acetone). Sulforaphene was found to be stable in aprotic solvents and unstable in the protic solvents. The degradation products of sulforaphene in protic solvents (methanol and ethanol) were purified by the preparative HPLC and identified by ESI/MS and NMR ((1)H NMR). The degradation pathways of sulforaphene in methanol and ethanol were proposed. It was found that sulforaphene was degraded into two kinds of structural isomer in alcohols. PMID:26775975

  14. Aspartic Acid Racemization and Collagen Degradation Markers Reveal an Accumulation of Damage in Tendon Collagen That Is Enhanced with Aging*

    PubMed Central

    Thorpe, Chavaunne T.; Streeter, Ian; Pinchbeck, Gina L.; Goodship, Allen E.; Clegg, Peter D.; Birch, Helen L.

    2010-01-01

    Little is known about the rate at which protein turnover occurs in living tendon and whether the rate differs between tendons with different physiological roles. In this study, we have quantified the racemization of aspartic acid to calculate the age of the collagenous and non-collagenous components of the high strain injury-prone superficial digital flexor tendon (SDFT) and low strain rarely injured common digital extensor tendon (CDET) in a group of horses with a wide age range. In addition, the turnover of collagen was assessed indirectly by measuring the levels of collagen degradation markers (collagenase-generated neoepitope and cross-linked telopeptide of type I collagen). The fractional increase in d-Asp was similar (p = 0.7) in the SDFT (5.87 × 10−4/year) and CDET (5.82 × 10−4/year) tissue, and d/l-Asp ratios showed a good correlation with pentosidine levels. We calculated a mean (±S.E.) collagen half-life of 197.53 (±18.23) years for the SDFT, which increased significantly with horse age (p = 0.03) and was significantly (p < 0.001) higher than that for the CDET (34.03 (±3.39) years). Using similar calculations, the half-life of non-collagenous protein was 2.18 (±0.41) years in the SDFT and was significantly (p = 0.04) lower than the value of 3.51 (±0.51) years for the CDET. Collagen degradation markers were higher in the CDET and suggested an accumulation of partially degraded collagen within the matrix with aging in the SDFT. We propose that increased susceptibility to injury in older individuals results from an inability to remove partially degraded collagen from the matrix leading to reduced mechanical competence. PMID:20308077

  15. Perception of Acoustically Degraded Sentences in Bilingual Listeners Who Differ in Age of English Acquisition

    ERIC Educational Resources Information Center

    Shi, Lu-Feng

    2010-01-01

    Purpose: The effects of acoustic degradation and context use on sentence perception were evaluated in listeners differing in age of English acquisition. Method: Five groups of 8 listeners, native monolingual (NM), native bilingual (NB), and early, late, and very late non-native bilingual (NN-E, NN-L, and NN-VL, respectively), identified target…

  16. Effects of fatigue on the chemical and mechanical degradation of model stent sub-units.

    PubMed

    Dreher, Maureen L; Nagaraja, Srinidhi; Batchelor, Benjamin

    2016-06-01

    Understanding the fatigue and durability performance of implantable cardiovascular stents is critical for assessing their performance. When the stent is manufactured from an absorbable material, however, this durability assessment is complicated by the transient nature of the device. Methodologies for evaluating the fatigue performance of absorbable stents while accurately simulating the degradation are limited and little is known about the interaction between fatigue and degradation. In this study, we investigated the fatigue behavior and effect of fatigue on the degradation rate for a model absorbable cardiovascular stent. Custom v-shaped stent sub-units manufactured from poly(L-lactide), i.e., PLLA, were subjected to a simultaneous fatigue and degradation study with cycle counts representative of one year of expected in vivo use. Fatigue loading was carried out such that the polymer degraded at a rate that was aligned with a modest degree of fatigue acceleration. Control, un-loaded specimens were also degraded under static immersion conditions representative of simulated degradation without fatigue. The study identified that fatigue loading during degradation significantly increased specimen stiffness and lowered the force at break. Fatigue loading also significantly increased the degree of molecular weight decline highlighting an interaction between mechanical loading and chemical degradation. This study demonstrates that fatigue loading during degradation can affect both the mechanical properties and the chemical degradation rate. The results are important for defining appropriate in vitro degradation conditions for absorbable stent preclinical evaluation. PMID:26759973

  17. Micromechanical Modeling Study of Mechanical Inhibition of Enzymatic Degradation of Collagen Tissues.

    PubMed

    Tonge, Theresa K; Ruberti, Jeffrey W; Nguyen, Thao D

    2015-12-15

    This study investigates how the collagen fiber structure influences the enzymatic degradation of collagen tissues. We developed a micromechanical model of a fibrous collagen tissue undergoing enzymatic degradation based on two central hypotheses. The collagen fibers are crimped in the undeformed configuration. Enzymatic degradation is an energy activated process and the activation energy is increased by the axial strain energy density of the fiber. We determined the intrinsic degradation rate and characteristic energy for mechanical inhibition from fibril-level degradation experiments and applied the parameters to predict the effect of the crimped fiber structure and fiber properties on the degradation of bovine cornea and pericardium tissues under controlled tension. We then applied the model to examine the effect of the tissue stress state on the rate of tissue degradation and the anisotropic fiber structures that developed from enzymatic degradation. PMID:26682825

  18. A Review of Molecular-Level Mechanism of Membrane Degradation in the Polymer Electrolyte Fuel Cell

    PubMed Central

    Ishimoto, Takayoshi; Koyama, Michihisa

    2012-01-01

    Chemical degradation of perfluorosulfonic acid (PFSA) membrane is one of the most serious problems for stable and long-term operations of the polymer electrolyte fuel cell (PEFC). The chemical degradation is caused by the chemical reaction between the PFSA membrane and chemical species such as free radicals. Although chemical degradation of the PFSA membrane has been studied by various experimental techniques, the mechanism of chemical degradation relies much on speculations from ex-situ observations. Recent activities applying theoretical methods such as density functional theory, in situ experimental observation, and mechanistic study by using simplified model compound systems have led to gradual clarification of the atomistic details of the chemical degradation mechanism. In this review paper, we summarize recent reports on the chemical degradation mechanism of the PFSA membrane from an atomistic point of view. PMID:24958288

  19. Mechanisms and regulation of the degradation of cyclin B.

    PubMed Central

    Hershko, A

    1999-01-01

    The degradation of the cyclin B subunit of protein kinase Cdk1/cyclin B is required for inactivation of the kinase and exit from mitosis. Cyclin B is degraded by the ubiquitin pathway, a system involved in most selective protein degradation in eukaryotic cells. In this pathway, proteins are targeted for degradation by ligation to ubiquitin, a process carried out by the sequential action of three enzymes: the ubiquitin-activating enzyme E1, a ubiquitin-carrier protein E2 and a ubiquitin-protein ligase E3. In the system responsible for cyclin B degradation, the E3-like function is carried out by a large complex called cyclosome or anaphase-promoting complex (APC). In the early embryonic cell cycles, the cyclosome is inactive in the interphase, but becomes active at the end of mitosis. Activation requires phosphorylation of the cyclosome/APC by protein kinase Cdk1/cyclin B. The lag kinetics of cyclosome activation may be explained by Suc1-assisted multiple phosphorylations of partly phosphorylated complex. The presence of a Fizzy/Cdc20-like protein is necessary for maximal activity of the mitotic form of cyclosome/APC in cyclin-ubiquitin ligation. PMID:10582242

  20. Emerging programmed aging mechanisms and their medical implications.

    PubMed

    Goldsmith, Theodore C

    2016-01-01

    For many generations programmed aging in humans was considered theoretically impossible and medical attempts to treat or delay age-related diseases were based on non-programmed aging theories. However, there is now an extensive theoretical basis for programmed mammal aging and substantially funded medical research efforts based on programmed aging theories are underway. This article describes the very different disease mechanism concepts that logically result from the theories and the impacts emerging programmed aging mechanisms will have on funding and performing medical research on age-related conditions. PMID:26547271

  1. Depth profiling of mechanical degradation of PV backsheets after UV exposure

    NASA Astrophysics Data System (ADS)

    Gu, Xiaohong; Krommenhoek, Peter J.; Lin, Chiao-Chi; Yu, Li-Chieh; Nguyen, Tinh; Watson, Stephanie S.

    2015-09-01

    Polymeric multilayer backsheets protect the photovoltaic modules from damage of moisture and ultraviolet (UV) while providing electrical insulation. Due to the multilayer structures, the properties of the inner layers of the backsheets, including their interfaces, during weathering are not well known. In this study, a commercial type of PPE (polyethylene terephthalate (PET)/PET/ethylene vinyl acetate (EVA)) backsheet films was selected as a model system for a depth profiling study of mechanical properties of a backsheet film during UV exposure. The NIST SPHERE (Simulated Photodegradation via High Energy Radiant Exposure) was used for the accelerated laboratory exposure of the materials with UV at 85°C and two relative humidities (RH) of 5 % (dry) and 60 % (humid). Cryomicrotomy was used to obtain cross-sectional PPE samples. Mechanical depth profiling of the cross-sections of aged and unaged samples was conducted by nanoindentation, and a peak-force based quantitative nanomechanical atomic force microscopy (QNM-AFM) mapping techniquewas used to investigate the microstructure and adhesion properties of the adhesive tie layers. The nanoindentation results show the stiffening of the elastic modulus in the PET outer and pigmented EVA layers. From QNM-AFM, the microstructures and adhesion properties of the adhesive layers between PET outer and core layers and between PET core and EVA inner layers are revealed and found to degrade significantly after aging under humidity environment. The results from mechanical depth profiling of the PPE backsheet are further related to the previous chemical depth profiling of the same material, providing new insights into the effects of accelerated UV and humidity on the degradation of multilayer backsheet.

  2. Sonolytic and sonophotolytic degradation of Carbamazepine: Kinetic and mechanisms.

    PubMed

    Rao, Yongfang; Yang, Haisong; Xue, Dan; Guo, Yang; Qi, Fei; Ma, Jun

    2016-09-01

    An in-depth investigation on the ultrasonic decomposition of Carbamazepine (CBZ), one of the most regularly identified drugs in the environment, was conducted. The effects of diverse variables were evaluated, such as frequency, power, solution pH, initial CBZ concentration and varied inorganic anions. Reaction order was determined on the basis of analyzing reaction kinetics of CBZ degradation. The sonophotolysis and photolysis of CBZ was also examined in this contribution. The influence of water composition on the sonolytic and sonophotolytic elimination of CBZ was analyzed. Additionally, 21 intermediates were identified during sonolytic degradation of CBZ based on LC/ESI-MS/MS analysis, among which two escaped from the detection in previous studies. Possible decay pathways were proposed accordingly. The epoxidation, cleavage of double bond, hydration, hydroxylation, ring contraction and intramolecular cyclization were believed to be involved in sonochemical degradation of CBZ. PMID:27150783

  3. Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

    USGS Publications Warehouse

    Lerch, R.N.; Thurman, E.M.; Kruger, E.L.

    1997-01-01

    This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

  4. Benzoxazinone-mediated triazine degradation: A proposed reaction mechanism

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The role of benzoxazinones (Bx, 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one)) in triazine degradation and resistance has been studied for over half a century. In this research, the fundamental parameters of the reaction between DIBOA-Glc (2-ß-D-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one) and atrazin...

  5. Mechanical property degradation of graphite/polyimide composites after exposure to moisture or shuttle orbiter fluids

    NASA Technical Reports Server (NTRS)

    Lisagor, W. B.

    1979-01-01

    The effects of moisture exposure on the mechanical properties of graphite polyimide systems are presented. The mechanism of the degradation and the magnitude of the affect associated with specific mechanical properties is investigated. An experimental effort involving exposure to selected environmental variables and subsequent mechanical property testing and analysis is included.

  6. Methods And Systms For Analyzing The Degradation And Failure Of Mechanical Systems

    DOEpatents

    Jarrell, Donald B.; Sisk, Daniel R.; Hatley, Darrel D.; Kirihara, Leslie J.; Peters, Timothy J.

    2005-02-08

    Methods and systems for identifying, understanding, and predicting the degradation and failure of mechanical systems are disclosed. The methods include measuring and quantifying stressors that are responsible for the activation of degradation mechanisms in the machine component of interest. The intensity of the stressor may be correlated with the rate of physical degradation according to some determinable function such that a derivative relationship exists between the machine performance, degradation, and the underlying stressor. The derivative relationship may be used to make diagnostic and prognostic calculations concerning the performance and projected life of the machine. These calculations may be performed in real time to allow the machine operator to quickly adjust the operational parameters of the machinery in order to help minimize or eliminate the effects of the degradation mechanism, thereby prolonging the life of the machine. Various systems implementing the methods are also disclosed.

  7. Age Related Decline in Postural Control Mechanisms.

    ERIC Educational Resources Information Center

    Stelmach, George E.; And Others

    1989-01-01

    Studied voluntary and reflexive mechanisms of postural control of young (N=8) and elderly (N=8) adults through measurement of reflexive reactions to large-fast and small-slow ankle rotation postural disturbances. Found reflexive mechanisms relatively intact for both groups although elderly appeared more disadvantaged when posture was under the…

  8. Plumbrook Hypersonic Tunnel Facility Graphite Furnace Degradation Mechanisms

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.

    1999-01-01

    A recent rebuild revealed extensive degradation to the large graphite induction furnace in the Hypersonic Tunnel Facility (HTF). This damage to the graphite blocks and insulating felt is examined and modeled with thermochemical equilibrium codes. The primary reactions appear to be with water vapor and the nitrogen purge gas. Based on these conclusions, several changes are recommended. An inert purge gas (e.g. argon or helium) and controlling and monitoring water vapor to about 10 ppm should decrease the damage substantially.

  9. Degradation of TATP, TNT, and RDX using mechanically alloyed metals

    NASA Technical Reports Server (NTRS)

    Clausen, Christian (Inventor); Geiger, Cherie (Inventor); Sigman, Michael (Inventor); Fidler, Rebecca (Inventor)

    2012-01-01

    Bimetallic alloys prepared in a ball milling process, such as iron nickel (FeNi), iron palladium (FePd), and magnesium palladium (MgPd) provide in situ catalyst system for remediating and degrading nitro explosive compounds. Specifically, munitions, such as, 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), nitrocellulose and nitroglycerine that have become contaminants in groundwater, soil, and other structures are treated on site to remediate explosive contamination.

  10. Degradation mechanism for planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kouhei; Furumoto, Yoshikazu; Shahiduzzaman, M.; Kuwabara, Takayuki; Takahashi, Kohshin; Taima, Tetsuya

    2016-04-01

    Organic-inorganic hybrid perovskite materials have recently emerged as a promising cost- and energy-efficient light absorber material for photovoltaic applications. Unfortunately, perovskite solar cells have a problem with decreasing power conversion efficiency owing to their degradation in air. To clarify the cause of the degradation of perovskite solar cells, we exposed deposited CH3NH3PbI3 and HC(NH2)2PbI3 films to an O2 or (H2O+N2) atmosphere condition. Analysis of these films revealed that a large energy band gap was observed as a result of the influence of the H2O molecule in CH3NH3PbI3 and HC(NH2)2PbI3. Under the (H2O+N2) atmosphere condition, the existence of CH3NH3I and HC(NH2)2I molecules was found to affect the morphology and as well as the crystalline diffraction peak. The resultant perovskite crystalline structure was degraded by H2O molecules under the air exposure condition.

  11. Technical note: nitrogen fertilization effects on the degradation of aged diesel oil in composted drilling wastes.

    PubMed

    Choi, Woo-Jung; Chang, Scott X

    2009-07-01

    Hydrocarbon-contaminated wastes generated from oil and gas drilling activities may be used as a soil amendment once composted and further decomposition of residual hydrocarbons can be accomplished after the composts are applied to soils. To test if N fertilization may enhance hydrocarbon decomposition, we investigated the effects of N application on hydrocarbon degradation in different-aged composts (1-, 2-, 3-, and 4-year-old composts, coded as 1Y, 2Y, 3Y, and 4Y composts, respectively) through a pot experiment planted with white spruce (Picea glauca [Moench] Voss) seedlings. The percentage degradation of total petroleum hydrocarbon (TPH, C11 to C40) in the composts without N fertilization was correlated to initial NH4+ concentrations (R = 0.99, P < 0.001). The percentage degradation of TPH was highest in the 3Y compost (41.1%) that had an initial level of 325.3 mg NH4+ -N kg(-1) and the lowest in the IY compost (9.3%) that had an initial level of 8.3 mg NH4+ -N kg(-1). The degradation of TPH was enhanced by Nfertilization in the 1Y (from 9.3 to 15.3%) and 4Y composts (from 14.3 to 22.6%) that had low initial NH4+ concentrations. Our results show that application of NH4+ -based fertilizers may enhance the degradation of TPH when initial NH4+ concentrations in the compost are low. PMID:19810347

  12. Characterization of the Degradation Mechanisms of Lysine-derived Aliphatic Poly(ester urethane) Scaffolds

    PubMed Central

    Hafeman, Andrea E.; Zienkiewicz, Katarzyna J.; Zachman, Angela L.; Sung, Hak-Joon; Nanney, Lillian B.; Davidson, Jeffrey M.; Guelcher, Scott A.

    2010-01-01

    Characterization of the degradation mechanism of polymeric scaffolds and delivery systems for regenerative medicine is essential to assess their clinical applicability. Key performance criteria include induction of a minimal, transient inflammatory response and controlled degradation to soluble non-cytotoxic breakdown products that are cleared from the body by physiological processes. Scaffolds fabricated from biodegradable poly(ester urethane)s (PEURs) undergo controlled degradation to non-cytotoxic breakdown products and support the ingrowth of new tissue in preclinical models of tissue regeneration. While previous studies have shown that PEUR scaffolds prepared from lysine-derived polyisocyanates degrade faster under in vivo compared to in vitro conditions, the degradation mechanism is not well understood. In this study, we have shown that PEUR scaffolds prepared from lysine triisocyanate (LTI) or a trimer of hexamethylene diisocyanate (HDIt) undergo hydrolytic, esterolytic, and oxidative degradation. Hydrolysis of ester bonds to yield α-hydroxy acids is the dominant mechanism in buffer, and esterolytic media modestly increase the degradation rate. While HDIt scaffolds show a modest (<20%) increase in degradation rate in oxidative medium, LTI scaffolds degrade six times faster in oxidative medium. Furthermore, the in vitro rate of degradation of LTI scaffolds in oxidative medium approximates the in vivo rate in rat excisional wounds, and histological sections show macrophages expressing myeloperoxidase at the material surface. While recent preclinical studies have underscored the potential of injectable PEUR scaffolds and delivery systems for tissue regeneration, this promising class of biomaterials has a limited regulatory history. Elucidation of the macrophage-mediated oxidative mechanism by which LTI scaffolds degrade in vivo provides key insights into the ultimate fate of these materials when injected into the body. PMID:20864156

  13. Characterization of the degradation mechanisms of lysine-derived aliphatic poly(ester urethane) scaffolds.

    PubMed

    Hafeman, Andrea E; Zienkiewicz, Katarzyna J; Zachman, Angela L; Sung, Hak-Joon; Nanney, Lillian B; Davidson, Jeffrey M; Guelcher, Scott A

    2011-01-01

    Characterization of the degradation mechanism of polymeric scaffolds and delivery systems for regenerative medicine is essential to assess their clinical applicability. Key performance criteria include induction of a minimal, transient inflammatory response and controlled degradation to soluble non-cytotoxic breakdown products that are cleared from the body by physiological processes. Scaffolds fabricated from biodegradable poly(ester urethane)s (PEURs) undergo controlled degradation to non-cytotoxic breakdown products and support the ingrowth of new tissue in preclinical models of tissue regeneration. While previous studies have shown that PEUR scaffolds prepared from lysine-derived polyisocyanates degrade faster under in vivo compared to in vitro conditions, the degradation mechanism is not well understood. In this study, we have shown that PEUR scaffolds prepared from lysine triisocyanate (LTI) or a trimer of hexamethylene diisocyanate (HDIt) undergo hydrolytic, esterolytic, and oxidative degradation. Hydrolysis of ester bonds to yield α-hydroxy acids is the dominant mechanism in buffer, and esterolytic media modestly increase the degradation rate. While HDIt scaffolds show a modest (<20%) increase in degradation rate in oxidative medium, LTI scaffolds degrade six times faster in oxidative medium. Furthermore, the in vitro rate of degradation of LTI scaffolds in oxidative medium approximates the in vivo rate in rat excisional wounds, and histological sections show macrophages expressing myeloperoxidase at the material surface. While recent preclinical studies have underscored the potential of injectable PEUR scaffolds and delivery systems for tissue regeneration, this promising class of biomaterials has a limited regulatory history. Elucidation of the macrophage-mediated oxidative mechanism by which LTI scaffolds degrade in vivo provides key insights into the ultimate fate of these materials when injected into the body. PMID:20864156

  14. Bovine meniscal tissue exhibits age- and interleukin-1 dose-dependent degradation patterns and composition-function relationships.

    PubMed

    Ling, Carrie H-Y; Lai, Janice H; Wong, Ivan J; Levenston, Marc E

    2016-05-01

    Despite increasing evidence that meniscal degeneration is an early event in the development of knee osteoarthritis, relatively little is known regarding the sequence or functional implications of cytokine-induced meniscal degradation or how degradation varies with age. This study examined dose-dependent patterns of interleukin-1 (IL-1)-induced matrix degradation in explants from the radially middle regions of juvenile and adult bovine menisci. Tissue explants were cultured for 10 days in the presence of 0, 1.25, 5, or 20 ng/ml recombinant human IL-1α. Juvenile explants exhibited immediate and extensive sulfated glycosaminoglycan (sGAG) loss and subsequent collagen release beginning after 4-6 days, with relatively little IL-1 dose-dependence. Adult explants exhibited a more graded response to IL-1, with dose-dependent sGAG release and a lower fraction of sGAG released (but greater absolute release) than juvenile explants. In contrast to juvenile explants, adult explants exhibited minimal collagen release over the 10-day culture. Compressive and shear moduli reflected the changes in explant composition, with substantial decreases for both ages but a greater relative decrease in juvenile tissue. Dynamic moduli exhibited stronger dependence on explant sGAG content for juvenile tissue, likely reflecting concomitant changes to both proteoglycan and collagen tissue components. The patterns of tissue degradation suggest that, like in articular cartilage, meniscal proteoglycans may partially protect collagen from cell-mediated degeneration. A more detailed view of functional changes in meniscal tissue mechanics with degeneration will help to establish the relevance of in vitro culture models and will advance understanding of how meniscal degeneration contributes to overall joint changes in early stage osteoarthritis. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:801-811, 2016. PMID:26519862

  15. Degradation of enoxacin antibiotic by the electro-Fenton process: Optimization, biodegradability improvement and degradation mechanism.

    PubMed

    Annabi, Cyrine; Fourcade, Florence; Soutrel, Isabelle; Geneste, Florence; Floner, Didier; Bellakhal, Nizar; Amrane, Abdeltif

    2016-01-01

    This study aims to investigate the effectiveness of the electro-Fenton process on the removal of a second generation of fluoroquinolone, enoxacin. The electrochemical reactor involved a carbon-felt cathode and a platinum anode. The influence of some experimental parameters, namely the initial enoxacin concentration, the applied current intensity and the Fe(II) amount, was examined. The degradation of the target molecule was accompanied by an increase of the biodegradability, assessed from the BOD5 on COD ratio, which increased from 0 before treatment until 0.5 after 180 min of electrolysis at 50 mg L(-1) initial enoxacin concentration, 0.2 mmol L(-1) Fe(II) concentration and 300 mA applied current intensity. TOC and COD time-courses were also evaluated during electrolysis and reached maximum residual yields of 54% and 43% after 120 min of treatment, respectively. Moreover, a simultaneous generation of inorganic ions (fluorides, ammonium and nitrates) were observed and 3 short chain carboxylic acids (formic, acetic and oxalic acids) were identified and monitored during 180 min of electrolysis. By-products were identified according to UPLC-MS/MS results and a degradation pathway was proposed. PMID:26413803

  16. Ultrasound as a Complementary Tool to Internal Mixers for Investigation of Thermal Mechanical Degradation of PET

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Zhao, Lijuan; Tatibouët, Jacques; Jen, Cheng-kuei

    2008-07-01

    An ultrasonically instrumented internal mixer was used to study thermal mechanical degradation of PET samples with different levels of water content and under different processing temperatures and blade speeds. The strength of ultrasound signals reflected from a roller blade of an internal mixer appeared to be more sensitive to PET degradation than the torque measurement means available on the internal mixer, suggesting that ultrasound could provide additional information on material property changes. A main advantage of ultrasonic degradation monitoring over torque measurement is that it could be implemented at various locations of an extruder to obtain localized melt degradation information.

  17. Cathode diffusion and degradation mechanism of polymeric light emitting devices

    NASA Astrophysics Data System (ADS)

    Suh, Min Chul; Chung, Ho Kyoon; Kim, Sang-Yeol; Kwon, Jang Hyuk; Chin, Byung Doo

    2005-09-01

    Rutherford backscattering spectroscopy was applied to investigate the diffusion of metals into polymeric light emitting layer by a continuous device operation. The change of substrate (indium/tin) signal as well as calcium penetration after device operation was conspicuous using pristine light emitting polymer, whereas annealed device above polymer's glass transition temperature indicated almost no migration of calcium. This can be a direct evidence of the molecular conformation and rigidity change of light emitting polymer, which affects the degradation behavior by the metal diffusion into organic thin film.

  18. Age Differences in the Use of Coping Mechanisms.

    ERIC Educational Resources Information Center

    McCrae, Robert R.

    1982-01-01

    Reports two cross-sectional studies assessing the influence of age on the use of 28 coping mechanisms. Results showed older people coped similiarly to younger people, and where they employed different mechanisms it was because of different types of stress. Middle-aged and older people used less hostile and escapist reactions. (Author/RC)

  19. Mechanism-based Representative Volume Elements (RVEs) for Predicting Property Degradations in Multiphase Materials

    SciTech Connect

    Xu, Wei; Sun, Xin; Li, Dongsheng; Ryu, Seun; Khaleel, Mohammad A.

    2013-02-01

    Quantitative understanding of the evolving thermal-mechanical properties of a multi-phase material hinges upon the availability of quantitative statistically representative microstructure descriptions. Questions then arise as to whether a two-dimensional (2D) or a three-dimensional (3D) representative volume element (RVE) should be considered as the statistically representative microstructure. Although 3D models are more representative than 2D models in general, they are usually computationally expensive and difficult to be reconstructed. In this paper, we evaluate the accuracy of a 2D RVE in predicting the property degradations induced by different degradation mechanisms with the multiphase solid oxide fuel cell (SOFC) anode material as an example. Both 2D and 3D microstructure RVEs of the anodes are adopted to quantify the effects of two different degradation mechanisms: humidity-induced electrochemical degradation and phosphorus poisoning induced structural degradation. The predictions of the 2D model are then compared with the available experimental measurements and the results from the 3D model. It is found that the 2D model, limited by its inability of reproducing the realistic electrical percolation, is unable to accurately predict the degradation of thermo-electrical properties. On the other hand, for the phosphorus poisoning induced structural degradation, both 2D and 3D microstructures yield similar results, indicating that the 2D model is capable of providing computationally efficient yet accurate results for studying the structural degradation within the anodes.

  20. Mechanisms of Enzymatic Degradation of Amyloid Beta Microfibrils Generating Nanofilaments and Nanospheres Related to Cytotoxicity†

    PubMed Central

    Numata, Keiji; Kaplan, David L.

    2010-01-01

    Amyloid beta (Aβ) fibrils are found in brain tissue of persons with Alzheimer’s disease (AD), where they accumulate as plaques. One way to reduce Aβ accumulation in the brain and potentially treat AD is with Aβ-degrading enzymes such as Neprilysin (NEP) and Insulin-Degrading Enzyme (IDE). However, enzymatic responses and degradation mechanisms of Aβ fibrils (crystalline-state Aβ) have not been investigated, particularly with respect to how to avoid cytotoxicity of the degradation products to neuronal cells. Thus, insight into mechanisms of enzymatic degradation of Aβ fibrils would be instructive as a route to elucidating different structural features related to degradation and to cytotoxicity. We report mechanisms of enzymatic degradation of Aβ with cross-beta structures and show the series of steps involved in the digestion Aβ microfibrils to nanospheres or nanofilaments by protease XIV or alpha-chymotrypsin, respectively. These degradation products, which contained almost the same secondary structures, showed different cytotoxicities, indicating that relationships between nano-assembled structures and cytotoxicity of Aβ peptides are more significant rather than the beta-sheet content. In addition, the enzymatic digestion at the Lys28 loop region linking the two beta sheets in Aβ fibrils is suggested as a key target related to cytotoxicity, a feature that can be selectively targeted based on the choice of protease. PMID:20196618

  1. A molecular simulation study of chemical degradation and mechanical deformation of hydrated Nafion membranes

    NASA Astrophysics Data System (ADS)

    Xie, Jing; Ban, Shuai; Liu, Bei; Zhou, Hongjun

    2016-01-01

    A combined modeling approach using kinetic Monte Carlo and molecular dynamics simulations is applied to investigate both chemical and mechanical degradation of Nafion membranes on the molecular level. In different hydration conditions, two major degradation reactions are identified to be the main chain unzipping and the side chain scission. The dissolution process of Nafion is evaluated in terms of weight loss, production emission rate and evolution of functional groups. Further, the complicated structural deformation is preliminarily investigated by imposing linear strain on degraded Nafion membrane. Different craze patterns are compared before and after chemical degradation, and the mechanism of crack propagation is proposed. Finally, prospective applications of our modeling approach are addressed for future studies of membrane degradation phenomena under fuel cell operation conditions.

  2. An Update on Inflamm-Aging: Mechanisms, Prevention, and Treatment

    PubMed Central

    Wu, Junzhen

    2016-01-01

    Inflamm-aging is a challenging and promising new branch of aging-related research fields that includes areas such as immunosenescence. Increasing evidence indicates that inflamm-aging is intensively associated with many aging diseases, such as Alzheimer's disease, atherosclerosis, heart disease, type II diabetes, and cancer. Mounting studies have focused on the role of inflamm-aging in disease progression and many advances have been made in the last decade. However, the underlying mechanisms by which inflamm-aging affects pathological changes and disease development are still unclear. Here, we review studies of inflamm-aging that explore the concept, pathological features, mechanisms, intervention, and the therapeutic strategies of inflamm-aging in disease progression. PMID:27493973

  3. A current genetic and epigenetic view on human aging mechanisms.

    PubMed

    Ostojić, Sala; Pereza, Nina; Kapović, Miljenko

    2009-06-01

    The process of aging is one of the most complex and intriguing biological phenomenons. Aging is a genetically regulated process in which the organism's maximum lifespan potential is pre-determined, while the rate of aging is influenced by environmental factors and lifestyle. Considering the complexity of mechanisms involved in the regulation of aging process, up to this date there isn't a major, unifying theory which could explain them. As genetic/epigenetic and environmental factors both inevitably influence the aging process, here we present a review on the genetic and epigenetic regulation of the most important molecular and cellular mechanisms involved in the process of aging. Based on the studies on oxidative stress, metabolism, genome stability, epigenetic modifications and cellular senescence in animal models and humans, we give an overview of key genetic and molecular pathways related to aging. As most of genetic manipulations which influence the aging process also affect reproduction, we discuss aging in humans as a post-reproductive genetically determined process. After the age of reproductive success, aging continously progresses which clinically coincides with the onset of most chronic diseases, cancers and dementions. As evolution shapes the genomes for reproductive success and not for post-reproductive survival, aging could be defined as a protective mechanism which ensures the preservation and progress of species through the modification, trasmission and improvement of genetic material. PMID:19662799

  4. Oxidative degradation of triclosan by potassium permanganate: Kinetics, degradation products, reaction mechanism, and toxicity evaluation.

    PubMed

    Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

    2016-10-15

    In this study, we systematically investigated the potential applicability of potassium permanganate for removal of triclosan (TCS) in water treatment. A series of kinetic experiments were carried out to study the influence of various factors, including the pH, oxidant doses, temperature, and presence of typical anions (Cl(-), SO4(2-), NO3(-)), humic acid (HA), and fulvic acid (FA) on triclosan removal. The optimal reaction conditions were: pH = 8.0, [TCS]0:[KMnO4]0 = 1:2.5, and T = 25 °C, where 20 mg/L of TCS could be completely degraded in 120 s. However, the rate of TCS (20 μg/L) oxidation by KMnO4 ([TCS]0:[KMnO4]0 = 1:2.5) was 1.64 × 10(-3) mg L(-1)·h(-1), lower than that at an initial concentration of 20 mg/L (2.24 × 10(3) mg L(-1)·h(-1)). A total of eleven products were detected by liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) analysis, including phenol and its derivatives, benzoquinone, an organic acid, and aldehyde. Two main reaction pathways involving CO bond cleavage (-C(8)O(7)-) and benzene ring opening (in the less chlorinated benzene ring) were proposed, and were further confirmed based on frontier electron density calculations and point charges. Furthermore, the changes in the toxicity of the reaction solution during TCS oxidation by KMnO4 were evaluated by using both the luminescent bacteria Photobacterium phosphoreum and the water flea Daphnia magna. The toxicity of 20 mg/L triclosan to D. magna and P. phosphoreum after 60 min was reduced by 95.2% and 43.0%, respectively. Phenol and 1,4-benzoquinone, the two representative degradation products formed during permanganate oxidation, would yield low concentrations of DBPs (STHMFP, 20.99-278.97 μg/mg; SHAAFP, 7.86 × 10(-4)-45.77 μg/mg) after chlorination and chloramination. Overall, KMnO4 can be used as an effective oxidizing agent for TCS removal in water and wastewater treatment. PMID:27459151

  5. Environment assisted degradation mechanisms in advanced light metals

    NASA Technical Reports Server (NTRS)

    Gangloff, R. P.; Stoner, G. E.; Swanson, R. E.

    1989-01-01

    A multifaceted research program on the performance of advanced light metallic alloys in aggressive aerospace environments, and associated environmental failure mechanisms was initiated. The general goal is to characterize alloy behavior quantitatively and to develop predictive mechanisms for environmental failure modes. Successes in this regard will provide the basis for metallurgical optimization of alloy performance, for chemical control of aggressive environments, and for engineering life prediction with damage tolerance and long term reliability.

  6. Electro-peroxone degradation of diethyl phthalate: Cathode selection, operational parameters, and degradation mechanisms.

    PubMed

    Hou, Meifang; Chu, Yaofei; Li, Xiang; Wang, Huijiao; Yao, Weikun; Yu, Gang; Murayama, Seiichi; Wang, Yujue

    2016-12-01

    This study compares the degradation of diethyl phthalate (DEP) by the electro-peroxone (E-peroxone) process with three different carbon-based cathodes, namely, carbon-polytetrafluorethylene (carbon-PTFE), carbon felt, and reticulated vitreous carbon (RVC). Results show that the three cathodes had different electrocatalytic activity for converting sparged O2 to H2O2, which increased in order of carbon felt, RVC, and carbon-PTFE. The in-situ generated H2O2 then reacts with sparged O3 to yield OH, which can in turn oxidize ozone-refractory DEP toward complete mineralization. In general, satisfactory total organic carbon removal yields (76.4-91.8%) could be obtained after 60min of the E-peroxone treatment with the three carbon-based cathodes, and the highest yield was obtained with the carbon-PTFE cathode due to its highest activity for H2O2 generation. In addition, the carbon-PTFE and carbon felt cathodes exhibited excellent stability over six cycles of the E-peroxone treatment of DEP solutions. Based on the intermediates (e.g., monoethyl phthalate, phthalic acid, phenolics, and carboxylic acids) identified by HPLC-UV, plausible reaction pathways were proposed for DEP mineralization by the E-peroxone process. The results of this study indicate that carbon-based cathodes generally have good electrocatalytic activity and stability for application in extended E-peroxone operations to effectively remove phthalates from water. PMID:26777107

  7. Molecular mechanisms and in vivo mouse models of skin aging associated with dermal matrix alterations.

    PubMed

    Hwang, Kyung-A; Yi, Bo-Rim; Choi, Kyung-Chul

    2011-03-01

    Skin is the most superficial body organ and plays an important role in protecting the body from environmental damage and in forming social relations. With the increase of the aging population in our society, dermatological and cosmetic concerns of skin aging are rapidly increasing. Skin aging is a complex process combined with intrinsic and extrinsic factors. Intrinsic or chronological skin aging results from the passage of time and is influenced by genetic factors. Extrinsic skin aging is mainly determined by UV irradiation, also called photoaging. These two types of aging processes are superimposed on sun-exposed skin, and have a common feature of causing dermal matrix alterations that mostly contribute to the formation of wrinkles, laxity, and fragility of aged skin. The dermal matrix contains extracellular matrix proteins such as collagen, elastin, and proteoglycans that confer the strength and resiliency of skin. Skin aging associated with dermal matrix alterations and atrophy can be caused by cellular senescence of dermal cells like fibroblasts, and decreased synthesis and accelerated degradation of dermal matrix components, especially collagen fibers. Both intrinsic aging and photoaging exert influence during each step of dermal matrix alteration via different mechanisms. Mouse models of skin aging have been extensively developed to elucidate intrinsic aging and photoaging processes, to validate in vitro biochemical data, and to test the effects of pharmacological tools for retarding skin aging because they have the advantages of being genetically similar to humans and are easily available. PMID:21826153

  8. Micro-mechanical model for the tension-stabilized enzymatic degradation of collagen tissues

    NASA Astrophysics Data System (ADS)

    Nguyen, Thao; Ruberti, Jeffery

    We present a study of how the collagen fiber structure influences the enzymatic degradation of collagen tissues. Experiments of collagen fibrils and tissues show that mechanical tension can slow and halt enzymatic degradation. Tissue-level experiments also show that degradation rate is minimum at a stretch level coincident with the onset of strain-stiffening in the stress response. To understand these phenomena, we developed a micro-mechanical model of a fibrous collagen tissue undergoing enzymatic degradation. Collagen fibers are described as sinusoidal elastica beams, and the tissue is described as a distribution of fibers. We assumed that the degradation reaction is inhibited by the axial strain energy of the crimped collagen fibers. The degradation rate law was calibrated to experiments on isolated single fibrils from bovine sclera. The fiber crimp and properties were fit to uniaxial tension tests of tissue strips. The fibril-level kinetic and tissue-level structural parameters were used to predict tissue-level degradation-induced creep rate under a constant applied force. We showed that we could accurately predict the degradation-induce creep rate of the pericardium and cornea once we accounted for differences in the fiber crimp structure and properties.

  9. Enantioselective Degradation Mechanism of Beta-Cypermethrin in Soil From the Perspective of Functional Genes.

    PubMed

    Yang, Zhong-Hua; Ji, Guo-Dong

    2015-12-01

    The behavior and mechanisms of the enantioselective degradation of beta-cypermethrin were studied in soil. The four isomers were degraded at different rates, and the enantiomer fractions of alpha-cypermethrin and theta-cypermethrin exceeded 0.5. Moreover, 3-phenoxybenzoic acid, phenol, and protocatechuic acid were detected; based on the presence of these metabolites, we predicted the degradation pathway and identified the functional genes that are related to this degradation process. We established quantitative relationships between the data on degradation kinetics and functional genes; we found that the quantitative relationships between different enantiomers differed even under the same conditions, and the genes pobA and pytH played key roles in limiting the degradation rate. Data obtained using path analysis revealed that the same gene had different direct and indirect effects on the degradation of different isomers. A mechanism was successfully proposed to explain the selective degradation of chiral compounds based on the perspective of functional genes. PMID:26403376

  10. Biodegradable Poly(Ethylene Glycol) Hydrogels Based on a Self-Elimination Degradation Mechanism

    PubMed Central

    Deshmukh, Manjeet; Singh, Yashveer; Gunaseelan, Simi; Gao, Dayuan; Stein, Stanley; Sinko, Patrick J.

    2010-01-01

    Two vinyl sulfone functionalized crosslinkers were developed for the purpose of preparing degradable poly(ethylene glycol) (PEG) hydrogels (EMXL and GABA-EMXL hydrogels). A self-elimination degradation mechanism in which an N-terminal residue of a glutamine is converted to pyroglutamic acid with subsequent release of diamino PEG (DAP) is proposed. The hydrogels were formed via Michael addition by mixing degradable or nondegradable crosslinkers and copolymer {4% w/v; poly[PEG-alt-poly(mercapto-succinic acid)]} at room temperature in phosphate buffer (PB, pH=7.4). Hydrogel degradation was characterized by assessing diamino PEG release and examining morphological changes as well as the swelling and weight loss ratio under physiological conditions (37 °C). Degradation of EMXL and GABA-EMXL hydrogels occurred by surface erosion (confirmed by SEM). GABA-EMXL degradation was significantly faster (~3-fold) than EMXL; however, the degradation of both hydrogels in mouse plasma was 12-times slower than in PBS. The slower degradation rate in plasma as compared to buffer is consistent with the presence of γ-glutamyltransferase, γ-glutamylcyclotransferase and/or glutaminyl cyclase (QC), which have been shown to suppress pyroglutamic acid formation. The current studies suggest that EMXL and GABA-EMXL hydrogels may have biomedical applications where 1 to 2 week degradation timeframes are optimal. PMID:20561680

  11. Theoretical analysis of degradation mechanisms in the formation of morphogen gradients

    NASA Astrophysics Data System (ADS)

    Bozorgui, Behnaz; Teimouri, Hamid; Kolomeisky, Anatoly B.

    2015-07-01

    Fundamental biological processes of development of tissues and organs in multicellular organisms are governed by various signaling molecules, which are called morphogens. It is known that spatial and temporal variations in the concentration profiles of signaling molecules, which are frequently referred as morphogen gradients, lead to a cell differentiation via activating specific genes in a concentration-dependent manner. It is widely accepted that the establishment of the morphogen gradients involves multiple biochemical reactions and diffusion processes. One of the critical elements in the formation of morphogen gradients is a degradation of signaling molecules. We develop a new theoretical approach that provides a comprehensive description of the degradation mechanisms. It is based on the idea that the degradation works as an effective potential that drives the signaling molecules away from the source region. Utilizing the method of first-passage processes, the dynamics of the formation of morphogen gradients for various degradation mechanisms is explicitly evaluated. It is found that linear degradation processes lead to a dynamic behavior specified by times to form the morphogen gradients that depend linearly on the distance from the source. This is because the effective potential due to the degradation is quite strong. At the same time, nonlinear degradation mechanisms yield a quadratic scaling in the morphogen gradients formation times since the effective potentials are much weaker. Physical-chemical explanations of these phenomena are presented.

  12. Environment assisted degradation mechanisms in advanced light metals

    NASA Technical Reports Server (NTRS)

    Gangloff, Richard P.; Stoner, Glenn E.; Swanson, Robert E.

    1988-01-01

    The general goals of the research program are to characterize alloy behavior quantitatively and to develop predictive mechanisms for environmental failure modes. Successes in this regard will provide the basis for metallurgical optimization of alloy performance, for chemical control of aggressive environments, and for engineering life prediction with damage tolerance and long term reliability.

  13. Chemical and Mechanical Degradation of Sulfonated Poly(sulfone) Membranes in Vanadium Redox Flow Batteries

    SciTech Connect

    Kim, Soowhan; Tighe, Timothy B.; Schwenzer, Birgit; Yan, Jingling; Zhang, Jianlu; Liu, Jun; Yang, Zhenguo; Hickner, Michael A.

    2011-10-01

    A sulfonated poly(sulfone) (S-Radel{reg_sign}) membrane with high proton conductivity and low vanadium ion diffusion showed high initial performance in a vanadium redox flow battery (VRFB) but suffered damage during charge/discharge cycling. The S-Radel membrane had different degradation behaviors in flow cell cycling and ex-situ vanadium ion immersion tests. The S-Radel membrane immersed in V5+ solution cracked into small pieces, but in the VRFB cell, the membrane underwent internal delamination preferentially on the side of the membrane that faced the positive electrode. A vanadium-rich interface was observed near the membrane surface that experienced delamination and Raman spectroscopic analysis of the surfaces of the membrane indicated a slightly depressed 1026 cm-1 band corresponding to the sulfonate SO2 stretch for the degraded surface. Even though the S-Radel membrane underwent severe mechanical damage during the flow cell cycling, significant chemical degradation was not obvious from the spectroscopic analyses. For the VRFB containing an S-Radel membrane, an increase in membrane resistance caused an abnormal voltage depression during the discharge cycle. The reversible increase in membrane resistance and severe mechanical degradation of the membrane during cycling may be attributed repeated formation and dissolution of particles inside the membrane. The mechanical stresses imposed by the particles coupled with a small amount of chemical degradation of the polymer by V5+, are likely degradation mechanisms of the S-Radel membrane in VRFBs under high state-of-charge conditions.

  14. New amines for CO{sub 2} capture. II. oxidative degradation mechanisms

    SciTech Connect

    Lepaumier, H.; Picq, D.; Carrette, P.L.

    2009-10-15

    This study examines oxidative degradation of 12 ethanolamines and ethylenediamines. They were chosen to establish structure-property relationships: the role of replacement of the alcohol function by one second amine function, amine nature, steric hindrance, and cyclic structure were studied. Degradation of aqueous amine solutions was evaluated at 140{sup o}C under air pressure (2 MPa) in stainless steel reactors for 15 days. At the end of the run, most degradation products were identified by gas chromatography (GC)/mass spectrometry (MS); amounts of remaining amine and its degradation products were determined with the quantitative GC method. Main degradation mechanisms are proposed, and some relationships between structure and chemical stability are given.

  15. Age-related changes in collagen synthesis and degradation in rat tissues. Importance of degradation of newly synthesized collagen in regulating collagen production.

    PubMed

    Mays, P K; McAnulty, R J; Campa, J S; Laurent, G J

    1991-06-01

    During developmental growth, collagens are believed to be continuously deposited into an extracellular matrix which is increasingly stabilized by the formation of covalent cross-links throughout life. However, the age-related changes in rates of synthetic and degradative processes are less well understood. In the present study we measured rates of collagen synthesis in vivo using a flooding dose of unlabelled proline given with [14C]proline and determining production of hydroxy[14C]proline. Degradation of newly synthesized collagen was estimated from the amount of free hydroxy [14C]proline in tissues 30 min after injection. Collagen fractional synthesis rates ranged from about 5%/day in skeletal muscle to 20%/day in hearts of rats aged 1 month. At 15 months of age, collagen fractional synthesis rates had decreased markedly in lung and skin, but in skeletal muscle and heart, rates were unchanged. At 24 months of age, synthesis rates had decreased by at least 10-fold in all tissues, compared with rates at 1 month. The proportion of newly synthesized collagen degraded ranged from 6.4 +/- 0.4% in skin to 61.6 +/- 5.0% in heart at 1 month of age. During aging the proportion degraded increased in all tissues to maximal values at 15 months, ranging from 56 +/- 7% in skin to 96 +/- 1% in heart. These data suggest that there are marked age-related changes in rates of collagen metabolism. They also indicate that synthesis is active even in old animals, where the bulk of collagens produced are destined to be degraded. PMID:2049064

  16. New insights on molecular mechanisms of renal aging.

    PubMed

    Schmitt, R; Melk, A

    2012-11-01

    Long-term transplant outcome is importantly influenced by the age of the organ donor. The mechanisms how age carries out its pathophysiological impact on graft survival are still not understood. One major contributing factor for the observed poor performance of old donor kidneys seems in particular the age-related loss in renal regenerative capacity. In this review, we will summarize recent findings about the molecular basis of renal aging with specific focus on the potential role of somatic cellular senescence and mitochondrial aging in renal transplant outcome. PMID:22882799

  17. Correlation of Chemical and Mechanical Property Changes During Oxidative Degradation of Neoprene

    SciTech Connect

    Celina, M.; Wise, J.; Ottesen, D.K.; Gillen, K.T.; Clough, R.L.

    1999-07-01

    The thermal degradation of a commercial, stabilized, unfilled neoprene (chloroprene) rubber was investigated at temperatures up to 140 C. The degradation of this material is dominated by oxidation rather than dehydrochlorination. Important heterogeneous oxidation effects were observed at the various temperatures investigated using infrared micro-spectroscopy and modulus profiling. Intensive degradation-related spectral changes in the IR occurred in the conjugated carbonyl and hydroxyl regions. Quantitative analysis revealed some differences in the development of the IR oxidation profiles, particularly towards the sample surface. These chemical degradation profiles were compared with modulus profiles (mechanical properties). It is concluded that the profile development is fundamentally described by a diffusion-limited autoxidation mechanism. Oxygen consumption measurements showed that the oxidation rates display non-Arrhenius behavior (curvature) at low temperatures. The current results, when compared to those of a previously studied, clay-filled commercial neoprene formulation, indicate that the clay filler acts as an antioxidant, but only at low temperatures.

  18. Critical analysis on degradation mechanism of dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Mohamad Shahimin, Mukhzeer; Suhaimi, Suriati; Abd Wahid, Mohd Halim; Retnasamy, Vithyacharan; Ahmad Hambali, Nor Azura Malini; Reshak, Ali Hussain

    2015-09-01

    This paper reports on a précis of degradation mechanism for dye-sensitized solar cell (DSSCs). The review indicates progress in the understanding of degradation mechanism, in particular, the large improvement in the analysis of the materials used in DSSCs. The paper discussed on the stability issues of the dye, advancement of the photoelectrode film lifetime, changes in the electrolyte components and degradation analysis of the counter electrode. The photoelectrochemical parameters were evaluated in view of the possible degradation routes via open circuit voltage (Voc), short circuit current (Isc), fill factor (FF) and overall conversion efficiency (η) from the current-voltage curve. This analysis covers several types of materials that have paved the way for better-performing solar cells and directly influenced the stability and reliability of DSSCs. The new research trend together with the previous research has been highlighted to examine the key challenges faced in developing the ultimate DSSCs.

  19. Low-Temperature Aging Mechanisms in U-6wt% Nb

    SciTech Connect

    Hsiung, L L

    2004-12-07

    Phase stability and aging mechanisms in a water-quenched (WQ) U-6wt% Nb (U-14at% Nb) alloy artificially aged at 200 C and naturally aged at ambient temperature for 15 years have been investigated and studied using Vickers-hardness measurement, X-ray diffraction (XRD) analysis, and transmission electron microscopy (TEM) techniques. Age hardening/softening phenomenon is recorded from the artificially aged samples based upon the microhardness measurement. The age hardening can be readily rationalized by the occurrence of fine-scaled Nb segregation, or spinodal decomposition, within the {alpha}'' domains, which results in the formation of a modulated structure containing nano-scaled Nb-rich and Nb-lean domains. Prolonged aging leads to age softening of the alloy by coarsening of the modulated structure. Chemical ordering, or disorder-order phase transformation, is found within the naturally aged alloy according to TEM observations of antiphase domain boundaries (APBs) and superlattice diffraction patterns. A possible superlattice structure for the ordered {alpha}'' phase observed in the naturally aged sample and underlying low-temperature aging mechanisms are proposed.

  20. On the Degradation Mechanism of Low-Voltage Underground Cable with Poly(Vinyl Chloride) Insulation

    NASA Astrophysics Data System (ADS)

    Tawancy, H. M.; Hassan, M.

    2016-06-01

    A study has been undertaken to determine the degradation mechanism leading to localized short-circuit failures of an underground low-voltage cable with PVC insulation. It is shown that that the insulation of outer sheath and conductor cores has been cracked by thermal degradation involving dehydrochlorination, oxidation, and loss of plasticizers leading to current leakage between the cores. Most evidence points out that overheating due to poor connection of copper wires as well as a chemically active soil has caused the observed degradation.

  1. Microscopic Degradation Mechanisms in Silicon Photovoltaic Module under Long-Term Environmental Exposure

    NASA Astrophysics Data System (ADS)

    Matsuda, Keiko; Watanabe, Takeshi; Sakaguchi, Koichi; Yoshikawa, Masanobu; Doi, Takuya; Masuda, Atsushi

    2012-10-01

    We used several analytical methods to identify the mechanism underlying the performance degradation in a photovoltaic (PV) module subjected to long-term (10 years) field exposure. Cloudy visual defects in this module were caused by delamination between the poly(ethylene vinyl acetate) (EVA) and antireflection coating films on the Si substrate. The delamination was considered to be caused by the formation of a segregation layer and oxidative degradation of EVA. Furthermore, it was found that sodium ions diffused from the superstrate glass into the EVA film and Si cell. We confirm that diffusion of sodium ions caused the degradation of Si cells and the superstrate glass of this module.

  2. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    PubMed

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC. PMID:26452660

  3. Reaction and degradation mechanism in all-solid-state lithium-air batteries.

    PubMed

    Kitaura, Hirokazu; Zhou, Haoshen

    2015-12-25

    The reaction and degradation mechanism in all-solid-state Li-air batteries was investigated to improve the cycling performance. It is suggested that Li2O2 is first produced by the H2O-mediated electrochemical reactions during discharging and Li2CO3 is produced by the following chemical reactions. Disruption of the CNTs and residual discharge products, which cause the capacity degradation during cycling, were observed. PMID:26478218

  4. Distinct Mechanisms of Impairment in Cognitive Ageing and Alzheimer's Disease

    ERIC Educational Resources Information Center

    Mapstone, Mark; Dickerson, Kathryn; Duffy, Charles J.

    2008-01-01

    Similar manifestations of functional decline in ageing and Alzheimer's disease obscure differences in the underlying cognitive mechanisms of impairment. We sought to examine the contributions of top-down attentional and bottom-up perceptual factors to visual self-movement processing in ageing and Alzheimer's disease. We administered a novel…

  5. Understanding Irreversible Degradation of Nb3Sn Wires with Fundamental Fracture Mechanics

    SciTech Connect

    Zhai, Yuhu; Calzolaio, Ciro; Senatore, Carmine

    2014-08-01

    Irreversible performance degradation of advanced Nb3Sn superconducting wires subjected to transverse or axial mechanical loading is a critical issue for the design of large-scale fusion and accelerator magnets such as ITER and LHC. Recent SULTAN tests indicate that most cable-in-conduit conductors for ITER coils made of Nb3Sn wires processed by various fabrication techniques show similar performance degradation under cyclic loading. The irreversible degradation due to filament fracture and local strain accumulation in Nb3Sn wires cannot be described by the existing strand scaling law. Fracture mechanic modeling combined with X-ray diffraction imaging of filament micro-crack formation inside the wires under mechanical loading may reveal exciting insights to the wire degradation mechanisms. We apply fundamental fracture mechanics with a singularity approach to study influence of wire filament microstructure of initial void size and distribution to local stress concentration and potential crack propagation. We report impact of the scale and density of the void structure on stress concentration in the composite wire materials for crack initiation. These initial defects result in an irreversible degradation of the critical current beyond certain applied stress. We also discuss options to minimize stress concentration in the design of the material microstructure for enhanced wire performance for future applications.

  6. Molecular mechanisms of biological aging in intervertebral discs.

    PubMed

    Vo, Nam V; Hartman, Robert A; Patil, Prashanti R; Risbud, Makarand V; Kletsas, Dimitris; Iatridis, James C; Hoyland, Judith A; Le Maitre, Christine L; Sowa, Gwendolyn A; Kang, James D

    2016-08-01

    Advanced age is the greatest risk factor for the majority of human ailments, including spine-related chronic disability and back pain, which stem from age-associated intervertebral disc degeneration (IDD). Given the rapid global rise in the aging population, understanding the biology of intervertebral disc aging in order to develop effective therapeutic interventions to combat the adverse effects of aging on disc health is now imperative. Fortunately, recent advances in aging research have begun to shed light on the basic biological process of aging. Here we review some of these insights and organize the complex process of disc aging into three different phases to guide research efforts to understand the biology of disc aging. The objective of this review is to provide an overview of the current knowledge and the recent progress made to elucidate specific molecular mechanisms underlying disc aging. In particular, studies over the last few years have uncovered cellular senescence and genomic instability as important drivers of disc aging. Supporting evidence comes from DNA repair-deficient animal models that show increased disc cellular senescence and accelerated disc aging. Additionally, stress-induced senescent cells have now been well documented to secrete catabolic factors, which can negatively impact the physiology of neighboring cells and ECM. These along with other molecular drivers of aging are reviewed in depth to shed crucial insights into the underlying mechanisms of age-related disc degeneration. We also highlight molecular targets for novel therapies and emerging candidate therapeutics that may mitigate age-associated IDD. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:1289-1306, 2016. PMID:26890203

  7. Molecular Mechanisms of Biological Aging in Intervertebral Discs

    PubMed Central

    Vo, Nam V.; Hartman, Robert A.; Patil, Prashanti R.; Risbud, Makarand V.; Kletsas, Dimitris; Iatridis, James C.; Hoyland, Judith A.; Le Maitre, Christine L.; Sowa, Gwendolyn A.; Kang, James D.

    2016-01-01

    Advanced age is the greatest risk factor for the majority of human ailments, including spine-related chronic disability and back pain, which stem from age-associated intervertebral disc degeneration (IDD). Given the rapid global rise in the aging population, understanding the biology of intervertebral disc aging in order to develop effective therapeutic interventions to combat the adverse effects of aging on disc health is now imperative. Fortunately, recent advances in aging research have begun to shed light on the basic biological process of aging. Here we review some of these insights and organize the complex process of disc aging into three different phases to guide research efforts to understand the biology of disc aging. The objective of this review is to provide an overview of the current knowledge and the recent progress made to elucidate specific molecular mechanisms underlying disc aging. In particular, studies over the last few years have uncovered cellular senescence and genomic instability as important drivers of disc aging. Supporting evidence comes from DNA repair-deficient animal models that show increased disc cellular senescence and accelerated disc aging. Additionally, stress-induced senescent cells have now been well documented to secrete catabolic factors, which can negatively impact the physiology of neighboring cells and ECM. These along with other molecular drivers of aging are reviewed in depth to shed crucial insights into the underlying mechanisms of age-related disc degeneration. We also highlight molecular targets for novel therapies and emerging candidate therapeutics that may mitigate age-associated IDD. PMID:26890203

  8. Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

    PubMed

    Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

    2012-10-15

    This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism. PMID:22939355

  9. Aging and emotional memory: cognitive mechanisms underlying the positivity effect.

    PubMed

    Spaniol, Julia; Voss, Andreas; Grady, Cheryl L

    2008-12-01

    Younger adults tend to remember negative information better than positive or neutral information (negativity bias). The negativity bias is reduced in aging, with older adults occasionally exhibiting superior memory for positive, as opposed to negative or neutral, information (positivity bias). Two experiments with younger (N=24 in Experiment 1, N=25 in Experiment 2; age range: 18-35 years) and older adults (N=24 in both experiments; age range: 60-85 years) investigated the cognitive mechanisms responsible for age-related differences in recognition memory for emotional information. Results from diffusion model analyses (R. Ratcliff, 1978) indicated that the effects of valence on response bias were similar in both age groups but that Age x Valence interactions emerged in memory retrieval. Specifically, older adults experienced greater overall familiarity for positive items than younger adults. We interpret this finding in terms of an age-related increase in the accessibility of positive information in long-term memory. PMID:19140656

  10. Studies of the degradation mechanisms in high-power diode lasers using multi-channel micro-thermography

    NASA Astrophysics Data System (ADS)

    Kozłowska, Anna; Tomm, Jens W.; Wawrzyniak, Piotr; Maląg, Andrzej; Weik, Fritz; Latoszek, Mateusz

    2005-09-01

    We demonstrate the applicability of imaging thermography for investigations of mechanisms associated with gradual degradation in diode lasers. The introduction of two spectral channels provides the means for separate observation of deep level luminescence and thermal radiation emitted according to Planck's law. In the near IR region we found the signal detected by the camera to be mainly affected by mid-gap deep-level luminescence. An intensity increase of the luminescence signal for an aged diode laser compared to an unaged device is noticed. It can be explained by an increase of deep level defect concentration during the aging. In the mid IR, we mainly encounter thermal radiation, which can be used for the analysis of the thermal properties of devices. In present work the thermal behavior of the device subjected to an aging of 3000 hours is analyzed. A significant increase of device temperature is noticed.

  11. Mechanism of anaerobic degradation of triethanolamine by a homoacetogenic bacterium

    SciTech Connect

    Speranza, Giovanna . E-mail: giovanna.speranza@unimi.it; Morelli, Carlo F.; Cairoli, Paola; Mueller, Britta; Schink, Bernhard

    2006-10-20

    Triethanolamine (TEA) is converted into acetate and ammonia by a strictly anaerobic, gram-positive Acetobacterium strain LuTria3. Fermentation experiments with resting cell suspensions and specifically deuterated substrates indicate that in the acetate molecule the carboxylate and the methyl groups correspond to the alcoholic function and to its adjacent methylene group, respectively, of the 2-hydroxyethyl unit of TEA. A 1,2 shift of a hydrogen (deuterium) atom from -CH{sub 2} -O- to =N-CH{sub 2} - without exchange with the medium was observed. This fact gives evidence that a radical mechanism occurs involving the enzyme and/or coenzyme molecule as a hydrogen carrier. Such a biodegradation appears analogous to the conversion of 2-phenoxyethanol into acetate mediated by another strain of the anaerobic homoacetogenic bacterium Acetobacterium.

  12. Translation by Ribosomes with mRNA Degradation: Exclusion Processes on Aging Tracks

    NASA Astrophysics Data System (ADS)

    Nagar, Apoorva; Valleriani, Angelo; Lipowsky, Reinhard

    2011-12-01

    We investigate the role of degradation of mRNA on protein synthesis using the totally asymmetric simple exclusion process (TASEP) as the underlying model for ribosome dynamics. mRNA degradation has a strong effect on the lifetime distribution of the mRNA, which in turn affects polysome statistics such as the number of ribosomes present on an mRNA strand of a given size. An average over mRNA of all ages is equivalent to an average over possible configurations of the corresponding TASEP—both before steady state and in steady state. To evaluate the relevant quantities for the translation problem, we first study the approach towards steady state of the TASEP, starting with an empty lattice representing an unloaded mRNA. When approaching the high density phase, the system shows two distinct phases with the entry and exit boundaries taking control of the density at their respective ends in the second phase. The approach towards the maximal current phase exhibits the surprising property that the ribosome entry flux can exceed the maximum possible steady state value. In all phases, the averaging over the mRNA age distribution shows a decrease in the average ribosome density profile as a function of distance from the entry boundary. For entry/exit parameters corresponding to the high density phase of TASEP, the average ribosome density profile also has a maximum near the exit end.

  13. Relationship of Bacterial Richness to Organic Degradation Rate and Sediment Age in Subseafloor Sediment

    PubMed Central

    Walsh, Emily A.; Kirkpatrick, John B.; Pockalny, Robert; Sauvage, Justine; Spivack, Arthur J.; Murray, Richard W.; Sogin, Mitchell L.

    2016-01-01

    ABSTRACT Subseafloor sediment hosts a large, taxonomically rich, and metabolically diverse microbial ecosystem. However, the factors that control microbial diversity in subseafloor sediment have rarely been explored. Here, we show that bacterial richness varies with organic degradation rate and sediment age. At three open-ocean sites (in the Bering Sea and equatorial Pacific) and one continental margin site (Indian Ocean), richness decreases exponentially with increasing sediment depth. The rate of decrease in richness with increasing depth varies from site to site. The vertical succession of predominant terminal electron acceptors correlates with abundance-weighted community composition but does not drive the vertical decrease in richness. Vertical patterns of richness at the open-ocean sites closely match organic degradation rates; both properties are highest near the seafloor and decline together as sediment depth increases. This relationship suggests that (i) total catabolic activity and/or electron donor diversity exerts a primary influence on bacterial richness in marine sediment and (ii) many bacterial taxa that are poorly adapted for subseafloor sedimentary conditions are degraded in the geologically young sediment, where respiration rates are high. Richness consistently takes a few hundred thousand years to decline from near-seafloor values to much lower values in deep anoxic subseafloor sediment, regardless of sedimentation rate, predominant terminal electron acceptor, or oceanographic context. IMPORTANCE Subseafloor sediment provides a wonderful opportunity to investigate the drivers of microbial diversity in communities that may have been isolated for millions of years. Our paper shows the impact of in situ conditions on bacterial community structure in subseafloor sediment. Specifically, it shows that bacterial richness in subseafloor sediment declines exponentially with sediment age, and in parallel with organic-fueled oxidation rate. This result

  14. Quantitative evaluation of material degradation of thermally aged duplex stainless steels using chemical immersion test

    NASA Astrophysics Data System (ADS)

    Yi, Y. S.; Shoji, T.

    1996-12-01

    In order to develop a non-destructive evaluation technique for detection of thermal aging embrittlement of duplex stainless steels, corrosion tests on unaged and aged specimens of cast duplex stainless steels were performed in 5 wt% HCl solution. After the immersion test, the dissolution rate of specimens was obtained by a dissolved depth measurement with an AFM. In the measurements of dissolved depths, a replica technique was used for easier handling and also for a possible field application of the AFM analysis method. Changes in corrosion properties by aging measured in terms of the dissolved depth after the immersion were compared with the changes in mechanical properties by aging embrittlement. The changes in corrosion properties of unaged and aged specimen were analyzed in relation to the microstructural change by thermal aging. Based upon insights on the immersion test results and the comparison of the changes in corrosion properties and mechanical properties, a possible non-destructive detection and evaluation technique for thermal aging embrittlement by spinodal decomposition is proposed.

  15. Mechanisms of the anorexia of aging-a review.

    PubMed

    Wysokiński, Adam; Sobów, Tomasz; Kłoszewska, Iwona; Kostka, Tomasz

    2015-08-01

    Many, even healthy, older people fail to adequately regulate food intake and experience loss of weight. Aging-associated changes in the regulation of appetite and the lack of hunger have been termed as the anorexia of aging. The etiology of the anorexia of aging is multi-factorial and includes a combination of physiological changes associated with aging (decline in smell and taste, reduced central and peripheral drive to eat, delayed gastric emptying), pathological conditions (depression, dementia, somatic diseases, medications and iatrogenic interventions, oral-health status), and social factors (poverty, loneliness). However, exact mechanisms of the anorexia of aging remain to be elucidated. Many neurobiological mechanisms may be secondary to age-related changes in body composition and not associated with anorexia per se. Therefore, further studies on pathophysiological mechanisms of the anorexia of aging should employ accurate measurement of body fat and lean mass. The anorexia of aging is associated with protein-energy malnutrition, sarcopenia, frailty, functional deterioration, morbidity, and mortality. Since this symptom can lead to dramatic consequences, early identification and effective interventions are needed. One of the most important goals in the geriatric care is to optimize nutritional status of the elderly. PMID:26232135

  16. Mechanical degradation of fuel cell membranes under fatigue fracture tests

    NASA Astrophysics Data System (ADS)

    Khorasany, Ramin M. H.; Sadeghi Alavijeh, Alireza; Kjeang, Erik; Wang, G. G.; Rajapakse, R. K. N. D.

    2015-01-01

    The effects of cyclic stresses on the fatigue and mechanical stability of perfluorosulfonic acid (PFSA) membranes are experimentally investigated under standard fuel cell conditions. The experiments are conducted ex-situ by subjecting membrane specimens to cyclic uniaxial tension at controlled temperature and relative humidity. The fatigue lifetime is measured in terms of the number of cycles until ultimate fracture. The results indicate that the membrane fatigue lifetime is a strong function of the applied stress, temperature, and relative humidity. The fatigue life increases exponentially with reduced stresses in all cases. The effect of temperature is found to be more significant than that of humidity, with reduced fatigue life at high temperatures. The maximum membrane strain at fracture is determined to decrease exponentially with increasing membrane lifetime. At a given fatigue life, a membrane exposed to fuel cell conditions is shown to accommodate more plastic strain before fracture than one exposed to room conditions. Overall, the proposed ex-situ membrane fatigue experiment can be utilized to benchmark the fatigue lifetime of new materials in a fraction of the time and cost associated with conventional in-situ accelerated stress testing methods.

  17. Mechanical Impact Induces Cartilage Degradation via Mitogen Activated Protein Kinases

    PubMed Central

    Ding, Lei; Heying, Emily; Nicholson, Nathan; Stroud, Nicolas J.; Homandberg, Gene A.; Guo, Danping; Buckwalter, Joseph A.; Martin, James A.

    2010-01-01

    Objective To determine the activation of MAP kinases in and around cartilage subjected to mechanical damage and to determine the effects of their inhibitors on impaction induced chondrocyte death and cartilage degeneration. Design The phosphorylation of MAP kinases was examined with confocal microscopy and immunoblotting. The effects of MAP kinase inhibitors on impaction-induced chondrocyte death and proteoglycan loss were determined with fluorescent microscopy and DMMB assay. The expression of catabolic genes at mRNA levels was examined with quantitative real time PCR. Results Early p38 activation was detected at 20 min and 1 hr post-impaction. At 24 hr, enhanced phosphorylation of p38 and ERK1/2 was visualized in chondrocytes from in and around impact sites. The phosphorylation of p38 was increased by 3.0-fold in impact sites and 3.3-fold in adjacent cartilage. The phosphorylation of ERK-1 was increased by 5.8-fold in impact zone and 5.4-fold in adjacent cartilage; the phosphorylation of ERK-2 increased by 4.0-fold in impacted zone and 3.6-fold in adjacent cartilage. Furthermore, the blocking of p38 pathway did not inhibit impaction-induced ERK activation. The inhibition of p38 or ERK pathway significantly reduced injury-related chondrocyte death and proteoglycan losses. Quantative Real-time PCR analysis revealed that blunt impaction significantly up-regulated MMP-13, TNF-α, and ADAMTS-5 expression. Conclusion These findings implicate p38 and ERK MAPKs in the post injury spread of cartilage degeneration and suggest that the risk of PTOA following joint trauma could be decreased by blocking their activities, which might be involved in up-regulating expressions of MMP-13, ADAMTS-5, and TNF-α. PMID:20813194

  18. Comparison of mice with accelerated aging caused by distinct mechanisms.

    PubMed

    Gurkar, Aditi U; Niedernhofer, Laura J

    2015-08-01

    Aging is the primary risk factor for numerous chronic, debilitating diseases. These diseases impact quality of life of the elderly and consume a large portion of health care costs. The cost of age-related diseases will only increase as the world's population continues to live longer. Thus it would be advantageous to consider aging itself as a therapeutic target, potentially stemming multiple age-related diseases simultaneously. While logical, this is extremely challenging as the molecular mechanisms that drive aging are still unknown. Furthermore, clinical trials to treat aging are impractical. Even in preclinical models, testing interventions to extend healthspan in old age are lengthy and therefore costly. One approach to expedite aging studies is to take advantage of mouse strains that are engineered to age rapidly. These strains are genetically and phenotypically quite diverse. This review aims to offer a comparison of several of these strains to highlight their relative strengths and weaknesses as models of mammalian and more specifically human aging. Additionally, careful identification of commonalities among the strains may lead to the identification of fundamental pathways of aging. PMID:25617508

  19. Performance degradation mechanisms and modes in terrestrial photovoltaic arrays and technology for their diagnosis

    NASA Technical Reports Server (NTRS)

    Noel, G. T.; Sliemers, F. A.; Derringer, G. C.; Wood, V. E.; Wilkes, K. E.; Gaines, G. B.; Carmichael, D. C.

    1978-01-01

    Accelerated life-prediction test methodologies have been developed for the validation of a 20-year service life for low-cost photovoltaic arrays. Array failure modes, relevant materials property changes, and primary degradation mechanisms are discussed as a prerequisite to identifying suitable measurement techniques and instruments. Measurements must provide sufficient confidence to permit selection among alternative designs and materials and to stimulate widespread deployment of such arrays. Furthermore, the diversity of candidate materials and designs, and the variety of potential environmental stress combinations, degradation mechanisms and failure modes require that combinations of measurement techniques be identified which are suitable for the characterization of various encapsulation system-cell structure-environment combinations.

  20. Primary study on the contact degradation mechanism of CdZnTe detectors

    NASA Astrophysics Data System (ADS)

    Sang, Wenbin; Wei, Jin; Qi, Zhang; Wanwan, Li; Jiahua, Min; Jianyong, Teng; Yongbiao, Qian

    2004-07-01

    The metal-CdZnTe (CZT) interface plays a vital role in determining the contact characteristics, which is often the dominant factor influencing detector performance. The effects of the degradation of the interfacial layer between the metal contact layer and CZT surface on the mechanical and electrical properties have been investigated in this paper. The interfacial thermal stresses were simulated using 3-D finite element method (FEM). The results indicate that the maximum thermal stress is concentrated on the midst of the electrode and the magnitude of the stress produced by the different electrode materials in order is Al>Au>Pt>In. The adhesion forces between the metal contact layer and CZT surface were measured by using a Dage PC2400 Micro tester with the shear-off-method. The inter-diffusion between the metal contact layer and CZT was identified using the Anger depth profiles. The experimental results indicate that the electroless Au electrode on p-type high resistivity CZT is of smaller interfacial adhesion strength, but of better ohmicity than the sputtered Au. In addition, the aging effects on the contact characteristics of the detector were also examined.

  1. Light-Induced Ambient Degradation of Few-Layer Black Phosphorus: Mechanism and Protection.

    PubMed

    Zhou, Qionghua; Chen, Qian; Tong, Yilong; Wang, Jinlan

    2016-09-12

    The environmental instability of single- or few-layer black phosphorus (BP) has become a major hurdle for BP-based devices. The degradation mechanism remains unclear and finding ways to protect BP from degradation is still highly challenging. Based on ab initio electronic structure calculations and molecular dynamics simulations, a three-step picture on the ambient degradation of BP is provided: generation of superoxide under light, dissociation of the superoxide, and eventual breakdown under the action of water. The well-matched band gap and band-edge positions for the redox potential accelerates the degradation of thinner BP. Furthermore, it was found that the formation of P-O-P bonds can greatly stabilize the BP framework. A possible protection strategy using a fully oxidized BP layer as the native capping is thus proposed. Such a fully oxidization layer can resist corrosion from water and leave the BP underneath intact with simultaneous high hole mobility. PMID:27529543

  2. Mechanical Properties and Corrosion Characteristics of Thermally Aged Alloy 22

    SciTech Connect

    Rebak, R B; Crook, P

    2002-05-30

    Alloy 22 (UNS N06022) is a candidate material for the external wall of the high level nuclear waste containers for the potential repository site at Yucca Mountain. In the mill-annealed (MA) condition, Alloy 22 is a single face centered cubic phase. When exposed to temperatures on the order of 600 C and above for times higher than 1 h, this alloy may develop secondary phases that reduce its mechanical toughness and corrosion resistance. The objective of this work was to age Alloy 22 at temperatures between 482 C and 760 C for times between 0.25 h and 6,000 h and to study the mechanical and corrosion performance of the resulting material. Aging was carried out using wrought specimens as well as gas tungsten arc welded (GTAW) specimens. Mechanical and corrosion testing was carried out using ASTM standards. Results show-that the higher the aging temperature and the longer the aging time, the lower the impact toughness of the aged material and the lower its corrosion resistance. However, extrapolating both mechanical and corrosion laboratory data predicts that Alloy 22 will remain corrosion resistant and mechanically robust for the projected lifetime of the waste container.

  3. Diagnostic examination of Generation 2 lithium-ion cells and assessment ofperformance degradation mechanisms.

    SciTech Connect

    Abraham, D. P.; Dees, D. W.; Knuth, J.; Reynolds, E.; Gerald, R.; Hyung,Y.-E.; Belharouak, I.; Stoll, M.; Sammann, E.; MacLaren, S.; Haasch, R.; Twesten,R.; Sardela, M.; Battaglia, V.; Cairns, E.; Kerr, J.; Kerlau, M.; Kostecki, R.; Lei,J.; McCarthy, K.; McLarnon, F.; Reimer, J.; Richardson, T.; Ross, P.; Sloop,S.; Song, X.; Zhuang, V.; Balasubramanian, M.; McBreen, J.; Chung, K.-Y.; Yang, X.Q.; Yoon, W.-S.; Norin, L.

    2005-07-15

    The Advanced Technology Development (ATD) Program is a multilaboratory effort to assist industrial developers of high-power lithium-ion batteries overcome the barriers of cost, calendar life, abuse tolerance, and low-temperature performance so that this technology may be rendered practical for use in hybrid electric vehicles (HEVs). Included in the ATD Program is a comprehensive diagnostics effort conducted by researchers at Argonne National Laboratory (ANL), Brookhaven National Laboratory (BNL), and Lawrence Berkeley National Laboratory (LBNL). The goals of this effort are to identify and characterize processes that limit lithium-ion battery performance and calendar life, and ultimately to describe the specific mechanisms that cause performance degradation. This report is a compilation of the diagnostics effort conducted since spring 2001 to characterize Generation 2 ATD cells and cell components. The report is divided into a main body and appendices. Information on the diagnostic approach, details from individual diagnostic techniques, and details on the phenomenological model used to link the diagnostic data to the loss of 18650-cell electrochemical performance are included in the appendices. The main body of the report includes an overview of the 18650-cell test data, summarizes diagnostic data and modeling information contained in the appendices, and provides an assessment of the various mechanisms that have been postulated to explain performance degradation of the 18650 cells during accelerated aging. This report is intended to serve as a ready reference on ATD Generation 2 18650-cell performance and provide information on the tools for diagnostic examination and relevance of the acquired data. A comprehensive account of our experimental procedures and resulting data may be obtained by consulting the various references listed in the text. We hope that this report will serve as a roadmap for the diagnostic analyses of other lithium-ion technologies being

  4. Metolachlor Sorption and Degradation in Soil Amended with Fresh and Aged Biochars.

    PubMed

    Trigo, Carmen; Spokas, Kurt A; Hall, Kathleen E; Cox, Lucia; Koskinen, William C

    2016-04-27

    Addition of organic amendments such as biochar to soils can influence pesticide sorption-desorption processes and, in turn, the amount of pesticide readily availability for transport and biodegradation. Sorption-desorption processes are affected by both the physical and chemical properties of soils and pesticides, as well as soil-pesticide contact time, or aging. Changes in sorption-desorption of metolachlor with aging in soil amended with three macadamia nut shell biochars aged 0 (BCmac-fr), 1 year (BCmac-1yr), and 2 years (BCmac-2yr) and two wood biochars aged 0 (BCwood-fr) and 5 years (BCwood-5yr) were determined. Apparent sorption coefficient (Kd-app) values increased with incubation time to a greater extent in amended soil as compared to unamended soils; Kd-app increased by 1.2-fold for the unamended soil, 2.0-fold for BCwood-fr, 1.4-fold for BCwood-5yr, 2.4-fold for BCmac-fr, 2.5-fold for BCmac-1yr, and 1.9-fold for BCmac-4yr. The increase in calculated Kd-app value was the result of a 15% decrease in the metolachlor solution concentration extractable with CaCl2 solution with incubation time in soil as compared to a 50% decrease in amended soil with very little change in the sorbed concentration. Differences could possibly be due to diffusion to less accessible or stronger binding sites with time, a faster rate of degradation (in solution and on labile sites) than desorption, or a combination of the two in the amended soils. These data show that transport models would overpredict the depth of movement of metolachlor in soil if effects of aging or biochar amendments are not considered. PMID:27050383

  5. Mechanism of Polysulfone-Based Anion Exchange Membranes Degradation in Vanadium Flow Battery.

    PubMed

    Yuan, Zhizhang; Li, Xianfeng; Zhao, Yuyue; Zhang, Huamin

    2015-09-01

    The stability of hydrocarbon ion exchange membranes is one of the critical issues for a flow battery. However, the degradation mechanism of ion exchange membranes has been rarely investigated especially for anion exchange membranes. Here, the degradation mechanism of polysulfone based anion exchange membranes, carrying pyridine ion exchange groups, under vanadium flow battery (VFB) medium was investigated in detail. We find that sp(2) hybrid orbital interactions between pyridinic-nitrogen in 4,4'-bipyridine and benzylic carbon disrupt the charge state balance of pristine chloromethylated polysulfone. This difference in electronegativity inversely induces an electrophilic carbon center in the benzene ring, which can be attacked by the lone pair electron on the vanadium(V) oxygen species, further leading to the degradation of polymer backbone, while leaving the 4,4'-bipyridine ion exchange groups stable. This work represents a step toward design and construction of alternative type of chemically stable hydrocarbon ion exchange membranes for VFB. PMID:26284752

  6. Diversity, Structures, and Collagen-Degrading Mechanisms of Bacterial Collagenolytic Proteases

    PubMed Central

    Zhang, Yu-Zhong; Ran, Li-Yuan; Li, Chun-Yang

    2015-01-01

    Bacterial collagenolytic proteases are important because of their essential role in global collagen degradation and because of their virulence in some human bacterial infections. Bacterial collagenolytic proteases include some metalloproteases of the M9 family from Clostridium or Vibrio strains, some serine proteases distributed in the S1, S8, and S53 families, and members of the U32 family. In recent years, there has been remarkable progress in discovering new bacterial collagenolytic proteases and in investigating the collagen-degrading mechanisms of bacterial collagenolytic proteases. This review provides comprehensive insight into bacterial collagenolytic proteases, especially focusing on the structures and collagen-degrading mechanisms of representative bacterial collagenolytic proteases in each family. The roles of bacterial collagenolytic proteases in human diseases and global nitrogen cycling, together with the biotechnological and medical applications for these proteases, are also briefly discussed. PMID:26150451

  7. Effectiveness of storage practices in mitigating aging degradation during reactor layup

    SciTech Connect

    Enderlin, W.I.

    1995-09-01

    One of the issues identified in the US Nuclear Regulatory Commission`s Nuclear Plant Aging Research program plan is the need to understand the state of ``mothballed`` or other out-of-service equipment to ensure subsequent safe operation. Programs for proper storage and preservation of materials and components are required by NRC regulations (10 CFR 50, Appendix B). However, materials and components have been seriously degraded due to improper storage, protection, or layup, at facilities under construction as well as those with operating licenses. Pacific Northwest Laboratory has evaluated management of aging for unstarted or mothballed nuclear power plants. The investigations revealed that no uniform guidance in the industry addresses reactor layup. In each case investigated, layup was not initiated in a timely manner, primarily because of schedule uncertainty. Hence, it is reasonable to assume that this delay resulted in accelerated aging of some safety-significant structures, systems, and components (SSCs). The applicable layup process is site-specific. The reactor type, climatic setting, operational status, and materials of construction are factors that strongly dictate the layup method to be used. The adequacy of current layup practices, and hence their impact on safety-significant SSCS, is not fully understood.

  8. Degradation diagnosis of aged Li4Ti5O12/LiFePO4 batteries

    NASA Astrophysics Data System (ADS)

    Castaing, Rémi; Reynier, Yvan; Dupré, Nicolas; Schleich, Donald; Jouanneau Si Larbi, Séverine; Guyomard, Dominique; Moreau, Philippe

    2014-12-01

    Li4Ti5O12/LiFePO4 cells are cycled under 4 different conditions of discharge profile (galvanostatic or driving-based) and cycling rates (C/8 or 1C) during 4-5 months. All the cells exhibit capacity fade whose extent is not correlated with the aging condition. In order to understand aging phenomena, cells are disassembled at the end of cycle life and the recovered electrodes are analyzed using electrochemistry, electron microscopy, XRD and MAS-NMR. Positive and negative electrodes show no loss in active material and no change in electrochemical activity, active material structure and composite electrode structure. This rules out any irreversible electrode degradation. Lithium stoichiometry estimated by both XRD and electrochemistry is unexpectedly low in the positive electrode when the aging is stopped at full discharge. That indicates a loss of cyclable lithium or electrons leading to cell balancing evolution. That loss may have been caused by parasitic reactions occurring at both electrodes, in accordance with their rich surface chemistry as evidenced by MAS-NMR.

  9. Age-related changes in lung collagen metabolism. A role for degradation in regulating lung collagen production.

    PubMed

    Mays, P K; McAnulty, R J; Laurent, G J

    1989-08-01

    Lung collagen levels are determined by a balance between synthesis and degradation, processes known to have rapid rates in young animals. Here, we report age-related changes in lung collagen synthesis and degradation in rats at five ages from 1 month to 2 yr. Synthesis rates were determined after injection of [14C]proline with a flooding dose of unlabeled proline, and its appearance as hydroxy-[14C]proline in protein. To determine degradation of newly synthesized collagen, the appearance of hydroxy-[14C]proline, either free or in low-molecular-weight peptides, was compared with hydroxy-[14C]proline in protein. Fractional collagen synthesis rates decreased from 13.51 +/- 0.54%/day at 1 month to 0.97 +/- 0.14%/day at 2 yr of age (p less than 0.05). Total lung collagen production also fell, but only after 15 months, when it decreased from 2.01 +/- 0.16 mg/day at 15 months to 0.54 +/- 0.10 mg/day at 2 yr of age (p less than 0.05). Fractional rates of total collagen degradation, calculated from the difference between rates of synthesis and rates of collagen deposition, decreased 20-fold from 1 month to 2 yr of age. The proportion of newly synthesized collagen degraded increased from 27.6 +/- 3.2% at 1 month to a maximum of 82.3 +/- 1.1% at 15 months. These results suggest that lung collagen synthesis and degradation occur throughout life, and that degradative pathways may play important roles in regulating collagen production during growth and ageing. PMID:2788379

  10. Mechanisms Involved in the Aging-Induced Vascular Dysfunction

    PubMed Central

    El Assar, Mariam; Angulo, Javier; Vallejo, Susana; Peiró, Concepción; Sánchez-Ferrer, Carlos F.; Rodríguez-Mañas, Leocadio

    2012-01-01

    Vascular aging is a key process determining health status of aged population. Aging is an independent cardiovascular risk factor associated to an impairment of endothelial function, which is a very early and important event leading to cardiovascular disease. Vascular aging, formerly being considered an immutable and inexorable risk factor, is now viewed as a target process for intervention in order to achieve a healthier old age. A further knowledge of the mechanisms underlying the age-related vascular dysfunction is required to design an adequate therapeutic strategy to prevent or restore this impairment of vascular functionality. Among the proposed mechanisms that contribute to age-dependent endothelial dysfunction, this review is focused on the following aspects occurring into the vascular wall: (1) the reduction of nitric oxide (NO) bioavailability, caused by diminished NO synthesis and/or by augmented NO scavenging due to oxidative stress, leading to peroxynitrite formation (ONOO−); (2) the possible sources involved in the enhancement of oxidative stress; (3) the increased activity of vasoconstrictor factors; and (4) the development of a low-grade pro-inflammatory environment. Synergisms and interactions between all these pathways are also analyzed. Finally, a brief summary of some cellular mechanisms related to endothelial cell senescence (including telomere and telomerase, stress-induced senescence, as well as sirtuins) are implemented, as they are likely involved in the age-dependent endothelial dysfunction, as well as in the lower vascular repairing capacity observed in the elderly. Prevention or reversion of those mechanisms leading to endothelial dysfunction through life style modifications or pharmacological interventions could markedly improve cardiovascular health in older people. PMID:22783194

  11. A method to define degradation mechanisms and failure rates for piping

    SciTech Connect

    Gamble, R.M.; Gosselin, S.R.

    1996-12-01

    This paper describes a process currently being employed to develop an easy to use procedure for identifying degradation mechanisms and computing failure rates for piping. The procedure includes guidelines to identify degradation mechanisms that may be present in piping systems. The identified mechanisms along with other system or segment specific features of the piping determine the piping failure rate. Implementation of this procedure requires a data or knowledge base that reflects the service and operational conditions that affect piping reliability and availability. This procedure is being developed for use by plant engineers, and will not require expertise in probability, stress, or fracture mechanics analyses. The method can be used to provide input for performing plant safety assessments and defining risk based inspection programs.

  12. MECHANISMS OF THERMOPHILIC SURVIVAL, DEGRADATION BY THERMOPHILICS AND OPTIMIZATION OF THERMOPHILIC BACTERIA FOR BIODEGRADATION

    EPA Science Inventory

    We have developed a consortium of thermophilic methanotrophic bacteria from Yellowstone National Park that degrades TCE by the use of methyl monooxygenase. We are going to isolate the thermophiles in patent 5,858,763,determine their mechanisms of surviving extreme temperatures, d...

  13. ADIPIC ACID DEGRADATION MECHANISM IN AQUEOUS FGD (FLUE GAS DESULFURIZATION) SYSTEMS

    EPA Science Inventory

    The report gives results of a field and laboratory study of the adipic acid degradation mechanism in aqueous flue gas desulfurization (FGD) systems. (Adding adipic acid to limestone-based, SO2 wet scrubbers increases SO2 removal and limestone utilization. However, as much as 80% ...

  14. Aging and mechanical properties of NR/BR blends

    NASA Astrophysics Data System (ADS)

    Chiu, Hsien-Tang; Tsai, Peir-An

    2006-02-01

    The mechanical properties and post-thermal aging properties of natural rubber (NR) and polybutadiene rubber (BR) blends at different blending ratios are investigated herein. The experimental results show that both tensile and tear strengths of NR/BR blends increase with increasing NR content. BR has a higher compression stiffness than NR. The deformation of BR is less than that of NR under the same load conditions. With regard to aging properties, both tensile stress and strain of NR/BR blends decrease after prolonged aging. In addition, the stress loss of BR is lower than that of NR, meaning that the aging resistance property of BR is superior to that of NR. Furthermore, accumulated thermal history has shifted the glass transition temperature (T g) of NR/BR blends toward lower temperatures while the loss tangent (tan δ) value increases with prolonged thermal aging.

  15. Mechanisms of Methylene Blue Degradation in Three-dimensionally Integrated Micro-solution Plasma

    NASA Astrophysics Data System (ADS)

    Nomura, Ayano; Hayashi, Yui; Tanaka, Kenji; Shirafuji, Tatsuru; Goto, Motonobu

    2015-09-01

    Plasma in aqueous solution has attracted much attention because they are expected to have possibilities to solve water-related environmental issues. In such application-oriented researches, degradation of methylene blue (MB) or other organic dyes has been widely used for investigating the effects of the plasma treatment on the water with organic contaminants. However, there are few reports on the detailed analysis of the products after the plasma treatment of MB aqueous solution for understanding mechanisms of the degradation processes. We have hence analyzed our degradation products using matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. We have performed the MB degradation in three-dimensionally integrated micro-solution plasma, which has shown 16-fold higher performance in MB degradation than conventional solution plasma. The results of MALDI-TOF mass spectrometry have indicated the formation of sulfoxides in the first stage of the degradation. Then, the methyl groups on the sulfoxides are partially oxidized. The sulfoxides are separated to form two benzene derivatives after that. Finally, weak functional groups are removed from the benzene derivatives.

  16. Ubiquitin-proteasome-mediated degradation of keratin intermediate filaments in mechanically stimulated A549 cells.

    PubMed

    Jaitovich, Ariel; Mehta, Semil; Na, Ni; Ciechanover, Aaron; Goldman, Robert D; Ridge, Karen M

    2008-09-12

    We previously reported that shear stress induces phosphorylation and disassembly of keratin intermediate filaments (IFs). Shear stress also induces a time- and strain-dependent degradation of keratin IFs, and the current study examines the mechanisms involved in degradation of keratin proteins in human A549 cells exposed to 0-24 h of shear stress (7.5-30 dynes/cm(2)). Ubiquitin was found to be covalently associated with keratin proteins immunoprecipitated from shear-stressed cells, and pretreatment with the proteasomal inhibitor MG132 prevented the degradation of the keratin IF network. Importantly, phosphorylation of K8 Ser-73 is required for the shear stress-mediated ubiquitination, disassembly, and degradation of the keratin IF network. Immunofluorescence microscopy revealed that shear stress caused the thin array of keratin fibrils observed in control cells to be reorganized into a perinuclear aggregate, known as an aggresome, and that ubiquitin was also associated with this structure. Finally, the E2 enzymes, UbcH5b, -c, and Ubc3, but not E2-25K are required for the shear stress-mediated ubiquitin-proteasomal degradation of keratin proteins. These data suggest that shear stress promotes the disassembly and degradation of the keratin IF network via phosphorylation and the ubiquitin-proteasome pathway. PMID:18617517

  17. Latent Fingermark Aging Patterns (Part II): Color Contrast Between Ridges and Furrows as One Indicator of Degradation.

    PubMed

    De Alcaraz-Fossoul, Josep; Barrot Feixat, Carme; Tasker, Jack; McGarr, Luke; Stow, Karen; Carreras-Marin, Clara; Turbany Oset, Jaume; Gené Badia, Manel

    2016-07-01

    Currently, no established methodology exists to determine degradation patterns of latent fingermarks by visual means. This article is the second in a series of reports exploring quantifiable degradation-related parameters, which focuses on color contrast changes between fingermark ridges and furrows over time. Experiment variables included type of secretion (eccrine and sebaceous), substrate (glass and plastic), and exposure to natural light (dark, shade, and direct light). Fingermarks were sequentially visualized with titanium dioxide powder and photographed. Image histogram profiles were evaluated and combined with statistical analysis of color data values. Results indicate that sebaceous depositions on glass were generally less degraded by the effect of environmental conditions compared with those on plastic. In addition, aging in darkness was not always the best condition for preservation, and direct exposure to light seemed to inhibit visual degradation under certain conditions. Overall, the technique provided sufficient sensitivity to discern degradation patterns of fingermarks. PMID:27364272

  18. Chemical Degradation of Siloxane Stress Cushions (M97 and S5370) by Thermal, Mechanical and Spectroscopic Investigations

    SciTech Connect

    Maxwell, R S; Gee, R; Balazs, B; Cohenour, R; Sung, B

    2002-04-19

    We are currently investigating the long term aging of weapon organics in an effort to develop predictive capabilities for functional service life. As part of this effort, we have been studying multimechanism aging of M97 and 53370 stress cushions. Ionizing radiation, thermal degradation, and desiccation all affect the crosslink density and motional dynamics and thus the engineering performance of these materials. Our approach has been to develop molecular level understanding of the effects of such aging mechanisms on polymer properties by a combined approach utilizing solvent swelling, thermal, DMA, molecular modeling, and solid state NMR. This presentation will offer a survey of our current work, concentrating on the application of solid state NMR for correlating structure and polymer dynamics. An overview of the relationships between crosslink density, NMR relaxation times, polymer chain dynamics, and storage modulus measurements will be presented and the advantages of NMR will be discussed. It will be shown that silicone based polymers tend to crosslink upon exposure to {gamma}-radiation, undergo chain scission upon thermal degradation, and stiffen upon desiccation.

  19. Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

    PubMed

    Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

    2016-06-01

    The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability. PMID:27187246

  20. The effect of nucleus pulposus crosslinking and glycosaminoglycan degradation on disc mechanical function.

    PubMed

    Yerramalli, C S; Chou, A I; Miller, G J; Nicoll, S B; Chin, K R; Elliott, D M

    2007-01-01

    Altered mechanical loading, secondary to biochemical changes in the nucleus pulposus, is a potential mechanism in disc degeneration. An understanding of the role of this altered mechanical loading is only possible by separating the mechanical and biological effects of early nucleus pulposus changes. The objective of this study was to quantify the mechanical effect of decreased glycosaminoglycans (GAG) and increased crosslinking in the nucleus pulposus using in vitro rat lumbar discs. Following initial mechanical testing the discs were injected according to the four treatment groups: PBS control, chondroitinase-ABC (ChABC) for GAG degradation, genipin (Gen) for crosslinking, or a combination of chondroitinase and genipin (ChABC+Gen). After treatment the discs were again mechanically tested, followed by histology or biochemistry. Neutral zone mechanical properties were changed by approximately 20% for PBS, ChABC, and ChABC+Gen treatments (significant only for PBS in a paired comparison). These trends were reversed with genipin crosslinking alone. With ChABC treatment the effective compressive modulus increased and the GAG content decreased; with the combination of ChABC+Gen the mechanics and GAG content were unchanged. Degradation of nucleus pulposus GAG alters disc axial mechanics, potentially contributing to the degenerative cascade. Crosslinking is unlikely to contribute to degeneration, but may be a potential avenue of treatment. PMID:16715318

  1. Glycation-altered proteolysis as a pathobiologic mechanism that links dietary glycemic index, aging, and age-related disease (in nondiabetics).

    PubMed

    Uchiki, Tomoaki; Weikel, Karen A; Jiao, Wangwang; Shang, Fu; Caceres, Andrea; Pawlak, Dorota; Handa, James T; Brownlee, Michael; Nagaraj, Ram; Taylor, Allen

    2012-02-01

    Epidemiologic studies indicate that the risks for major age-related debilities including coronary heart disease, diabetes, and age-related macular degeneration (AMD) are diminished in people who consume lower glycemic index (GI) diets, but lack of a unifying physiobiochemical mechanism that explains the salutary effect is a barrier to implementing dietary practices that capture the benefits of consuming lower GI diets. We established a simple murine model of age-related retinal lesions that precede AMD (hereafter called AMD-like lesions). We found that consuming a higher GI diet promotes these AMD-like lesions. However, mice that consumed the lower vs. higher GI diet had significantly reduced frequency (P < 0.02) and severity (P < 0.05) of hallmark age-related retinal lesions such as basal deposits. Consuming higher GI diets was associated with > 3 fold higher accumulation of advanced glycation end products (AGEs) in retina, lens, liver, and brain in the age-matched mice, suggesting that higher GI diets induce systemic glycative stress that is etiologic for lesions. Data from live cell and cell-free systems show that the ubiquitin-proteasome system (UPS) and lysosome/autophagy pathway [lysosomal proteolytic system (LPS)] are involved in the degradation of AGEs. Glycatively modified substrates were degraded significantly slower than unmodified substrates by the UPS. Compounding the detriments of glycative stress, AGE modification of ubiquitin and ubiquitin-conjugating enzymes impaired UPS activities. Furthermore, ubiquitin conjugates and AGEs accumulate and are found in lysosomes when cells are glycatively stressed or the UPS or LPS/autophagy are inhibited, indicating that the UPS and LPS interact with one another to degrade AGEs. Together, these data explain why AGEs accumulate as glycative stress increases. PMID:21967227

  2. Modeling Aging and Mechanical Rejuvenation of Amorphous Solids

    NASA Astrophysics Data System (ADS)

    Semkiv, Mykhailo; Hütter, Markus

    2016-04-01

    The elasto-viscoplasticity of amorphous solids is modeled, with a focus on the effects of physical aging and mechanical rejuvenation. Using nonequilibrium thermodynamics, the concept of kinetic and configurational subsystems has been employed. The Hamiltonian structure of reversible dynamics is exploited to derive a constitutive relation for the stress tensor. Furthermore, it is demonstrated that accounting for mechanical rejuvenation results in a modification of the driving force for viscoplastic flow.

  3. Prediction of troponin-T degradation using color image texture features in 10d aged beef longissimus steaks.

    PubMed

    Sun, X; Chen, K J; Berg, E P; Newman, D J; Schwartz, C A; Keller, W L; Maddock Carlin, K R

    2014-02-01

    The objective was to use digital color image texture features to predict troponin-T degradation in beef. Image texture features, including 88 gray level co-occurrence texture features, 81 two-dimension fast Fourier transformation texture features, and 48 Gabor wavelet filter texture features, were extracted from color images of beef strip steaks (longissimus dorsi, n = 102) aged for 10d obtained using a digital camera and additional lighting. Steaks were designated degraded or not-degraded based on troponin-T degradation determined on d 3 and d 10 postmortem by immunoblotting. Statistical analysis (STEPWISE regression model) and artificial neural network (support vector machine model, SVM) methods were designed to classify protein degradation. The d 3 and d 10 STEPWISE models were 94% and 86% accurate, respectively, while the d 3 and d 10 SVM models were 63% and 71%, respectively, in predicting protein degradation in aged meat. STEPWISE and SVM models based on image texture features show potential to predict troponin-T degradation in meat. PMID:24200578

  4. On BaMgAl{sub 10}O{sub 17}:Eu{sup 2+} phosphor degradation mechanism by vacuum-ultraviolet excitation

    SciTech Connect

    Bizarri, G.; Moine, B.

    2005-12-01

    Additional to a correct color and a high efficiency, phosphors for plasma display panels must maintain their light output for thousands of hours. Often the degradation is the restricting factor in using phosphors. In this article, the mechanism of luminance decrease in blue-emitting BaMgAl{sub 10}O{sub 17}:Eu{sup 2+} phosphor during the operation of the PDPs has been studied. It is shown experimentally that the aging process is mainly due to the vacuum-ultraviolet excitation (VUV). It is demonstrated that the degradation mechanism can be accelerated by using a 193 nm laser excitation. Based on excitation, reflectance, thermoluminescence spectra, and aging or annealing processes by laser excitation, the main causes of the degradation are demonstrated. The aging process can be separated in two different processes according to the temperature: a first one, at low temperature, corresponding to the autoionization of luminescent centers (Eu{sup 2+}{yields}Eu{sup 3+}); and a second one, at high temperature, linked to the formation of traps in the phosphor. These traps induce a perturbation of the energy migration in the phosphor. In addition, the relevant parameters of trap formation are highlighted: density of the VUV excitation, temperature, and atmosphere/pressure surrounding the phosphor. A model of BaMgAl{sub 10}O{sub 17}:Eu{sup 2+} phosphor degradation mechanism is proposed.

  5. A fine balance: regulation of hippocampal Arc/Arg3.1 transcription, translation and degradation in a rat model of normal cognitive aging

    PubMed Central

    Fletcher, Bonnie R.; Hill, Gordon S.; Long, Jeffrey M.; Gallagher, Michela; Shapiro, Matthew L.; Rapp, Peter R.

    2014-01-01

    Memory decline is a common feature of aging. Expression of the immediate-early gene Arc is necessary for normal long-term memory, and although experience dependent Arc transcription is reportedly reduced in the aged rat hippocampus, it has not been clear whether this effect is an invariant consequence of growing older, or a finding linked specifically to age-related memory impairment. Here we show that experience dependent Arc mRNA expression in the hippocampus fails selectively among aged rats with spatial memory deficits. While these findings are consistent with the possibility that blunted Arc transcription contributes to cognitive aging, we also found increased basal ARC protein levels in the CA1 field of the hippocampus in aged rats with memory impairment, together with a loss of the experience dependent increase observed in young and unimpaired aged rats. Follow-up analysis revealed that increased basal translation and blunted ubiquitin mediated degradation may contribute to increased basal ARC protein levels noted in memory impaired aged rats. These findings indicate that Arc expression is regulated at multiple levels, and that several of these mechanisms are altered in cognitively impaired aged rats. Defining the influence of these alterations on the spatial and temporal fidelity of synapse specific, memory-related plasticity in the aged hippocampus is an important challenge. PMID:25151943

  6. Thermal degradation of new and aged urethane foam and epon 826 epoxy.

    SciTech Connect

    Kruizenga, Alan Michael; Mills, Bernice E.

    2013-08-01

    Thermal desorption spectroscopy was used to monitor the decomposition as a function of temperature for the foam and epoxy as a function of temperature in the range of 60C to 170C. Samples were studied with one day holds at each of the studied temperatures. Both new (FoamN and EpoxyN) and aged (FoamP and EpoxyP) samples were studied. During these ~10 day experiments, the foam samples lost 11 to 13% of their weight and the EpoxyN lost 10% of its weight. The amount of weight lost was difficult to quantify for EpoxyP because of its inert filler. The onset of the appearance of organic degradation products from FoamP began at 110C. Similar products did not appear until 120C for FoamN, suggesting some effect of the previous decades of storage for FoamP. In the case of the epoxies, the corresponding temperatures were 120C for EpoxyP and 110C for EpoxyN. Suggestions for why the aged epoxy seems more stable than newer sample include the possibility of incomplete curing or differences in composition. Recommendation to limit use temperature to 90-100C for both epoxy and foam.

  7. Evaluation of the effect of organic pro-degradant concentration in polypropylene exposed to the natural ageing

    SciTech Connect

    Montagna, L. S. E-mail: andrecatto@terra.com.br E-mail: mmcforte@hotmail.com Catto, A. L. E-mail: andrecatto@terra.com.br E-mail: mmcforte@hotmail.com Rossini, K. E-mail: andrecatto@terra.com.br E-mail: mmcforte@hotmail.com Forte, M. M. C. E-mail: andrecatto@terra.com.br E-mail: mmcforte@hotmail.com Santana, R. M. C. E-mail: andrecatto@terra.com.br E-mail: mmcforte@hotmail.com

    2014-05-15

    The production and consumption of plastics in the last decade has recorded a remarkable increase in the scientific and industrial interest in environmentally degradable polymer (EDPs). Polymers wastes are deposited improperly, such as dumps, landfills, rivers and seas, causing a serious problem by the accumulation in the environment. The abiotic processes, like the photodegradation, are the most efficient occurring in the open environmental, where the polymers undergo degradation from the action of sunlight that result from direct exposure to solar radiation, however depend of the type of chemical ageing, which is the principal component of climatic ageing. The subject of this work is to study the influence of concentration of organic pro-degradant (1, 2 and 3 % w/w) in the polypropylene (PP) exposed in natural ageing. PP samples with and without the additive were processed in plates square form, obtained by thermal compression molding (TCM) using a press at 200°C under 2 tons for 5 min, and then were exposed at natural ageing during 120 days. The presence of organic additive influenced on PP degradability, this fact was assessed by changes in the thermal and morphology properties of the samples after 120 days of natural ageing. Scanning Electronic Microscopy (SEM) results of the morphological surface of the modified PP samples showed greater degradation photochemical oxidative when compared to neat PP, due to increase of rugosity and formation of microvoids. PP samples with different pro-degradant concentration under natural ageing presented a degree of crystallinity, obtained by Differential Scanning Calorimeter (DSC) increases in comparing the neat PP.

  8. Evaluation of the effect of organic pro-degradant concentration in polypropylene exposed to the natural ageing

    NASA Astrophysics Data System (ADS)

    Montagna, L. S.; Catto, A. L.; Rossini, K.; Forte, M. M. C.; Santana, R. M. C.

    2014-05-01

    The production and consumption of plastics in the last decade has recorded a remarkable increase in the scientific and industrial interest in environmentally degradable polymer (EDPs). Polymers wastes are deposited improperly, such as dumps, landfills, rivers and seas, causing a serious problem by the accumulation in the environment. The abiotic processes, like the photodegradation, are the most efficient occurring in the open environmental, where the polymers undergo degradation from the action of sunlight that result from direct exposure to solar radiation, however depend of the type of chemical ageing, which is the principal component of climatic ageing. The subject of this work is to study the influence of concentration of organic pro-degradant (1, 2 and 3 % w/w) in the polypropylene (PP) exposed in natural ageing. PP samples with and without the additive were processed in plates square form, obtained by thermal compression molding (TCM) using a press at 200°C under 2 tons for 5 min, and then were exposed at natural ageing during 120 days. The presence of organic additive influenced on PP degradability, this fact was assessed by changes in the thermal and morphology properties of the samples after 120 days of natural ageing. Scanning Electronic Microscopy (SEM) results of the morphological surface of the modified PP samples showed greater degradation photochemical oxidative when compared to neat PP, due to increase of rugosity and formation of microvoids. PP samples with different pro-degradant concentration under natural ageing presented a degree of crystallinity, obtained by Differential Scanning Calorimeter (DSC) increases in comparing the neat PP.

  9. ROS, Cell Senescence, and Novel Molecular Mechanisms in Aging and Age-Related Diseases

    PubMed Central

    Davalli, Pierpaola; Mitic, Tijana; Caporali, Andrea; Lauriola, Angela; D'Arca, Domenico

    2016-01-01

    The aging process worsens the human body functions at multiple levels, thus causing its gradual decrease to resist stress, damage, and disease. Besides changes in gene expression and metabolic control, the aging rate has been associated with the production of high levels of Reactive Oxygen Species (ROS) and/or Reactive Nitrosative Species (RNS). Specific increases of ROS level have been demonstrated as potentially critical for induction and maintenance of cell senescence process. Causal connection between ROS, aging, age-related pathologies, and cell senescence is studied intensely. Senescent cells have been proposed as a target for interventions to delay the aging and its related diseases or to improve the diseases treatment. Therapeutic interventions towards senescent cells might allow restoring the health and curing the diseases that share basal processes, rather than curing each disease in separate and symptomatic way. Here, we review observations on ROS ability of inducing cell senescence through novel mechanisms that underpin aging processes. Particular emphasis is addressed to the novel mechanisms of ROS involvement in epigenetic regulation of cell senescence and aging, with the aim to individuate specific pathways, which might promote healthy lifespan and improve aging. PMID:27247702

  10. Thermal ageing mechanisms of VVER-1000 reactor pressure vessel steels

    NASA Astrophysics Data System (ADS)

    Shtrombakh, Yaroslav I.; Gurovich, Boris A.; Kuleshova, Evgenia A.; Maltsev, Dmitry A.; Fedotova, Svetlana V.; Chernobaeva, Anna A.

    2014-09-01

    In this paper a complex of microstructural studies (TEM and SEM) and a comparative analysis of the results of these studies with the data of mechanical tests of temperature sets of VVER-1000 RPV surveillance specimens with exposure times up to ∼200,000 h were conducted. Special annealing of control and temperature sets of SS which provides the dissolution of grain boundary segregation was performed to clarify the mechanisms of thermal ageing. It was demonstrated that during long-term exposures up to 200,000 h at the operating temperature of about 310-320 °C thermal ageing effects reveal themselves only for the weld metal (Ni content ⩾ 1.35%) and are the result of grain boundary segregation accumulation (development of reversible temper brittleness). The obtained results improve the accuracy of prediction of the thermal ageing rate of VVER-1000 materials in case of RPV service life extension up to 60 years.

  11. Effect of Hygrothermal Aging on the Mechanical Properties of Fluorinated and Nonfluorinated Clay-Epoxy Nanocomposites

    PubMed Central

    Hamim, Salah U.; Singh, Raman P.

    2014-01-01

    Hydrophilic nature of epoxy polymers can lead to both reversible and irreversible/permanent changes in epoxy upon moisture absorption. The permanent changes leading to the degradation of mechanical properties due to combined effect of moisture and elevated temperature on EPON 862, Nanomer I.28E, and Somasif MAE clay-epoxy nanocomposites are investigated in this study. The extent of permanent degradation on fracture and flexural properties due to the hygrothermal aging is determined by drying the epoxy and their clay-epoxy nanocomposites after moisture absorption. Significant permanent damage is observed for fracture toughness and flexural modulus, while the extent of permanent damage is less significant for flexural strength. It is also observed that permanent degradation in Somasif MAE clay-epoxy nanocomposites is higher compared to Nanomer I.28E clay-epoxy nanocomposites. Fourier transform infrared (FTIR) spectroscopy revealed that both clays retained their original chemical structure after the absorption-desorption cycle without undergoing significant changes. Scanning electron microscopy (SEM) images of the fracture surfaces provide evidence that Somasif MAE clay particles offered very little resistance to crack propagation in case of redried specimens when compared to Nanomer I.28E counterpart. The reason for the observed higher extent of permanent degradation in Somasif MAE clay-epoxy system has been attributed to the weakening of the filler-matrix interface. PMID:27379285

  12. Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

    DOE PAGESBeta

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; Kim, Gi -Heon; Mukherjee, Partha P.

    2015-06-17

    In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constantmore » voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.« less

  13. Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

    SciTech Connect

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; Kim, Gi -Heon; Mukherjee, Partha P.

    2015-06-17

    In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constant voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.

  14. Semi-Degradable Poly(β-amino ester) Networks with Temporally-Controlled Enhancement of Mechanical Properties

    PubMed Central

    Safranski, David L.; Weiss, Daiana; Clark, J. Brian; Taylor, W.R.; Gall, Ken

    2014-01-01

    Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss in mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. PMID:24769113

  15. Identification and Assessment of Material Models for Age-Related Degradation of Structures and Passive Components in Nuclear Power Plants

    SciTech Connect

    Nie,J.; Braverman, J.; Hofmayer, C.; Kim, M. K.; Choi, I-K.

    2009-04-27

    When performing seismic safety assessments of nuclear power plants (NPPs), the potential effects of age-related degradation on structures, systems, and components (SSCs) should be considered. To address the issue of aging degradation, the Korea Atomic Energy Research Institute (KAERI) has embarked on a five-year research project to develop a realistic seismic risk evaluation system which will include the consideration of aging of structures and components in NPPs. Three specific areas that are included in the KAERI research project, related to seismic probabilistic risk assessment (PRA), are probabilistic seismic hazard analysis, seismic fragility analysis including the effects of aging, and a plant seismic risk analysis. To support the development of seismic capability evaluation technology for degraded structures and components, KAERI entered into a collaboration agreement with Brookhaven National Laboratory (BNL) in 2007. The collaborative research effort is intended to continue over a five year period with the goal of developing seismic fragility analysis methods that consider the potential effects of age-related degradation of SSCs, and using these results as input to seismic PRAs. In the Year 1 scope of work BNL collected and reviewed degradation occurrences in US NPPs and identified important aging characteristics needed for the seismic capability evaluations that will be performed in the subsequent evaluations in the years that follow. This information is presented in the Annual Report for the Year 1 Task, identified as BNL Report-81741-2008 and also designated as KAERI/RR-2931/2008. The report presents results of the statistical and trending analysis of this data and compares the results to prior aging studies. In addition, the report provides a description of U.S. current regulatory requirements, regulatory guidance documents, generic communications, industry standards and guidance, and past research related to aging degradation of SSCs. This report

  16. Acid-catalyzed hydrolysis of BMS-582664: degradation product identification and mechanism elucidation.

    PubMed

    Zhao, Fang; Derbin, George; Miller, Scott; Badawy, Sherif; Hussain, Munir

    2012-09-01

    BMS-582664 is an investigational drug intended for cancer treatment through oral administration. The preformulation studies revealed two unexpected degradation products under acidic conditions by reversed-phase high-performance liquid chromatography with ultraviolet detection. Additional liquid chromatography-mass spectrometry results suggested that these were cleavage (hydrolysis) products of a diaryl ether. To further understand the degradation mechanism, the reaction was carried out in (18) O-labeled water. The (18) O was found to be incorporated in only one of the two hydrolysis products. The results suggest that the corresponding α carbon in the heterocycle was unusually eletrophilic in acidic conditions probably because of the protonation of the neighboring nitrogen. This led to the selective attack by water and the consequent hydrolysis products. The study provides a new example of hydrolytic degradation of pharmaceutical compounds, and the reaction center is an aromatic heterocyclic carbon with an aryloxy substitution. PMID:22189636

  17. Detection and location of mechanical system degradation by using detector signal noise data

    SciTech Connect

    Damiano, B.; Blakeman, E.D.; Phillips, L.D.

    1994-06-01

    This report describes the investigation of a diagnostic method for detecting and locating the source of structural degradation in mechanical systems. The goal of this investigation was to determine whether the diagnostic method would be practically and successfully applied to detect and locate structural changes in a mechanical system. The diagnostic method uses a mathematical model of the mechanical system to define relationships between system parameters, such as spring rates and damping rates, and measurable spectral features, such as natural frequencies and mode shapes. These model-defined relationships are incorporated into a neural network, which is used to relate measured spectral features to system parameters. The diagnosis of the system`s condition is performed by presenting the neural network with measured spectral features and comparing the system parameters estimated by the neural network to previously estimated values. Changes in the estimated system parameters indicate the location and severity of degradation in the mechanical system. The investigation involved applying the method by using computer-simulated data and data collected from a bench-top mechanical system. The effects of neural network training set size and composition on the accuracy of the model parameter estimates were investigated by using computer-simulated data. The measured data were used to demonstrate that the method can be applied to estimate the parameters of a {open_quotes}real{close_quotes} mechanical system. The results show that this diagnostic method can be applied to successfully locate and estimate the magnitude of structural changes in a mechanical system. The average error in the estimated spring rate values of the bench-top mechanical system was approximately 5 to 10%. This degree of accuracy is sufficient to permit the use of this method for detecting and locating structural degradation in mechanical systems.

  18. Deciphering Transcriptional Regulatory Mechanisms Associated with Hemicellulose Degradation in Neurospora crassa

    PubMed Central

    Sun, Jianping; Tian, Chaoguang; Diamond, Spencer

    2012-01-01

    Hemicellulose, the second most abundant plant biomass fraction after cellulose, is widely viewed as a potential substrate for the production of liquid fuels and other value-added materials. Degradation of hemicellulose by filamentous fungi requires production of many different enzymes, which are induced by biopolymers or its derivatives and regulated mainly at the transcriptional level through transcription factors (TFs). Neurospora crassa, a model filamentous fungus, expresses and secretes enzymes required for plant cell wall deconstruction. To better understand genes specifically associated with degradation of hemicellulose, we applied secretome and transcriptome analysis to N. crassa grown on beechwood xylan. We identified 34 secreted proteins and 353 genes with elevated transcription on xylan. The xylanolytic phenotype of strains with deletions in genes identified from the secretome and transcriptome analysis of the wild type was assessed, revealing functions for known and unknown proteins associated with hemicellulose degradation. By evaluating phenotypes of strains containing deletions of predicted TF genes in N. crassa, we identified a TF (XLR-1; xylan degradation regulator 1) essential for hemicellulose degradation that is an ortholog to XlnR/XYR1 in Aspergillus and Trichoderma species, respectively, a major transcriptional regulator of genes encoding both cellulases and hemicellulases. Deletion of xlr-1 in N. crassa abolished growth on xylan and xylose, but growth on cellulose and cellulolytic activity were only slightly affected. To determine the regulatory mechanisms for hemicellulose degradation, we explored the transcriptional regulon of XLR-1 under xylose, xylanolytic, and cellulolytic conditions. XLR-1 regulated only some predicted hemicellulase genes in N. crassa and was required for a full induction of several cellulase genes. Hemicellulase gene expression was induced by a combination of release from carbon catabolite repression (CCR) and induction

  19. A highly efficient degradation mechanism of methyl orange using Fe-based metallic glass powders.

    PubMed

    Xie, Shenghui; Huang, Ping; Kruzic, Jamie J; Zeng, Xierong; Qian, Haixia

    2016-01-01

    A new Fe-based metallic glass with composition Fe76B12Si9Y3 (at. %) is found to have extraordinary degradation efficiency towards methyl orange (MO, C14H14N3SO3) in strong acidic and near neutral environments compared to crystalline zero-valent iron (ZVI) powders and other Fe-based metallic glasses. The influence of temperature (294-328 K) on the degradation reaction rate was measured using ball-milled metallic glass powders revealing a low thermal activation energy barrier of 22.6 kJ/mol. The excellent properties are mainly attributed to the heterogeneous structure consisting of local Fe-rich and Fe-poor atomic clusters, rather than the large specific surface and strong residual stress in the powders. The metallic glass powders can sustain almost unchanged degradation efficiency after 13 cycles at room temperature, while a drop in degradation efficiency with further cycles is attributed to visible surface oxidation. Triple quadrupole mass spectrometry analysis conducted during the reaction was used to elucidate the underlying degradation mechanism. The present findings may provide a new, highly efficient and low cost commercial method for azo dye wastewater treatment. PMID:26902824

  20. Chemical stability and degradation mechanisms of triangular Ag, Ag@Au, and Au nanoprisms.

    PubMed

    Lee, Kee Eun; Hesketh, Amelia V; Kelly, Timothy L

    2014-06-28

    Anisotropic metal nanoparticles have found use in a variety of plasmonic applications because of the large near-field enhancements associated with them; however, the very features that give rise to these enhancements (e.g., sharply curved edges and tips) often have high surface energies and are easily degraded. This paper describes the stability and degradation mechanisms of triangular silver, gold-coated silver, and gold nanoprisms upon exposure to a wide variety of adverse conditions, including halide ions, thiols, amines and elevated temperatures. The silver nanoprisms were immediately and irreversibly degraded under all of the conditions studied. In contrast, the core-shell Ag@Au nanoprisms were less susceptible to etching by chlorides and bromides, but were rapidly degraded by iodides, amines and thiols by a different degradation pathway. Only the pure gold nanoprisms were stable to all of the conditions tested. These results have important implications for the suitability of triangular nanoprisms in many applications; this is particularly true in biological or environmental fields, where the nanoparticles would inevitably be exposed to a wide variety of chemical stimuli. PMID:24827005

  1. A highly efficient degradation mechanism of methyl orange using Fe-based metallic glass powders

    NASA Astrophysics Data System (ADS)

    Xie, Shenghui; Huang, Ping; Kruzic, Jamie J.; Zeng, Xierong; Qian, Haixia

    2016-02-01

    A new Fe-based metallic glass with composition Fe76B12Si9Y3 (at. %) is found to have extraordinary degradation efficiency towards methyl orange (MO, C14H14N3SO3) in strong acidic and near neutral environments compared to crystalline zero-valent iron (ZVI) powders and other Fe-based metallic glasses. The influence of temperature (294-328 K) on the degradation reaction rate was measured using ball-milled metallic glass powders revealing a low thermal activation energy barrier of 22.6 kJ/mol. The excellent properties are mainly attributed to the heterogeneous structure consisting of local Fe-rich and Fe-poor atomic clusters, rather than the large specific surface and strong residual stress in the powders. The metallic glass powders can sustain almost unchanged degradation efficiency after 13 cycles at room temperature, while a drop in degradation efficiency with further cycles is attributed to visible surface oxidation. Triple quadrupole mass spectrometry analysis conducted during the reaction was used to elucidate the underlying degradation mechanism. The present findings may provide a new, highly efficient and low cost commercial method for azo dye wastewater treatment.

  2. A highly efficient degradation mechanism of methyl orange using Fe-based metallic glass powders

    PubMed Central

    Xie, Shenghui; Huang, Ping; Kruzic, Jamie J.; Zeng, Xierong; Qian, Haixia

    2016-01-01

    A new Fe-based metallic glass with composition Fe76B12Si9Y3 (at. %) is found to have extraordinary degradation efficiency towards methyl orange (MO, C14H14N3SO3) in strong acidic and near neutral environments compared to crystalline zero-valent iron (ZVI) powders and other Fe-based metallic glasses. The influence of temperature (294–328 K) on the degradation reaction rate was measured using ball-milled metallic glass powders revealing a low thermal activation energy barrier of 22.6 kJ/mol. The excellent properties are mainly attributed to the heterogeneous structure consisting of local Fe-rich and Fe-poor atomic clusters, rather than the large specific surface and strong residual stress in the powders. The metallic glass powders can sustain almost unchanged degradation efficiency after 13 cycles at room temperature, while a drop in degradation efficiency with further cycles is attributed to visible surface oxidation. Triple quadrupole mass spectrometry analysis conducted during the reaction was used to elucidate the underlying degradation mechanism. The present findings may provide a new, highly efficient and low cost commercial method for azo dye wastewater treatment. PMID:26902824

  3. The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes.

    PubMed

    Bensalah, Nasr; Dbira, Sondos; Bedoui, Ahmed

    2016-07-01

    In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond (BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in NaCl; however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and NaClO4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine (Cl2, HClO, ClO(-)) electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density (≤10mA/cm(2)) and neutral medium (pH in the range 6-9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate. PMID:27372125

  4. Low temperature aging mechanism identification and lithium deposition in a large format lithium iron phosphate battery for different charge profiles

    NASA Astrophysics Data System (ADS)

    Ouyang, Minggao; Chu, Zhengyu; Lu, Languang; Li, Jianqiu; Han, Xuebing; Feng, Xuning; Liu, Guangming

    2015-07-01

    Charging procedures at low temperatures severely shorten the cycle life of lithium ion batteries due to lithium deposition on the negative electrode. In this paper, cycle life tests are conducted to reveal the influence of the charging current rate and the cut-off voltage limit on the aging mechanisms of a large format LiFePO4 battery at a low temperature (-10 °C). The capacity degradation rates accelerate rapidly after the charging current reaches 0.25 C or the cut-off voltage reaches 3.55 V. Therefore the scheduled current and voltage during low-temperature charging should be reconsidered to avoid capacity degradation. Lithium deposition contributes to low-temperature aging mechanisms, as something needle-like which might be deposited lithium is observed on the surface of the negative electrode after disassembling the aged battery cell. To confirm our explanation, incremental capacity analysis (ICA) is performed to identify the characteristics of the lithium deposition induced battery aging mechanisms. Furthermore, the aging mechanism is quantified using a mechanistic model, whose parameters are estimated with the particle swarm optimization algorithm (PSO). The loss of reversible lithium originating from secondary SEI formation and dead lithium is confirmed as the cause of the aging.

  5. The influence of silanisation on the mechanical and degradation behaviour of PLGA/HA composites.

    PubMed

    Naik, Ashutosh; Best, Serena M; Cameron, Ruth E

    2015-03-01

    This study investigates the influence of silanisation on the mechanical and degradation behaviour of PLGA/HA composites. Three different silanes (mercaptopropyl trimethoxy silane (MPTMS), aminopropyl trimethoxy silane (APTMS) and aminopropyltriethoxy silane (APTES)) were applied to HA substrates in order to study the effect of head group (which binds to the polymer) and tail group (which binds to the surface hydroxyl groups in HA). A composite of hydroxyapatite (HA) and poly(d,l lactide-co-glycolide (50:50)) (PLGA) was investigated. The influence of concentration, the reaction time, drying temperature and substrate surface on silanisation was examined. TGA was used to detect the degree of silanisation. HA with MPTMS (1wt.% MPTMS with reaction time of 1h) was used as filler in PLGA-30wt.% HA composites for an in-vitro degradation study carried out in PBS. In addition, the mechanical properties of the composites were studied. Silanisation affects the properties of the composite by improving the bonding at the interface and hence it was found to influence the plastic mechanical properties rather than the elastic mechanical properties or the degradation profile of the composite. PMID:25579967

  6. Mechanical behaviour of degradable phosphate glass fibres and composites-a review.

    PubMed

    Colquhoun, R; Tanner, K E

    2016-02-01

    Biodegradable materials are potentially an advantageous alternative to the traditional metallic fracture fixation devices used in the reconstruction of bone tissue defects. This is due to the occurrence of stress shielding in the surrounding bone tissue that arises from the absence of mechanical stimulus to the regenerating bone due to the mismatch between the elastic modulus of bone and the metal implant. However although degradable polymers may alleviate such issues, these inert materials possess insufficient mechanical properties to be considered as a suitable alternative to current metallic devices at sites of sufficient mechanical loading. Phosphate based glasses are an advantageous group of materials for tissue regenerative applications due to their ability to completely degrade in vivo at highly controllable rates based on the specific glass composition. Furthermore the release of the glass's constituent ions can evoke a therapeutic stimulus in vivo (i.e. osteoinduction) whilst also generating a bioactive response. The processing of these materials into fibres subsequently allows them to act as reinforcing agents in degradable polymers to simultaneously increase its mechanical properties and enhance its in vivo response. However despite the various review articles relating to the compositional influences of different phosphate glass systems, there has been limited work summarising the mechanical properties of different phosphate based glass fibres and their subsequent incorporation as a reinforcing agent in degradable composite materials. As a result, this review article examines the compositional influences behind the development of different phosphate based glass fibre compositions intended as composite reinforcing agents along with an analysis of different potential composite configurations. This includes variations in the fibre content, matrix material and fibre architecture as well as other novel composites designs. PMID:26694533

  7. Mechanical Regulation of Cardiac Aging in Model Systems.

    PubMed

    Sessions, Ayla O; Engler, Adam J

    2016-05-13

    Unlike diet and exercise, which individuals can modulate according to their lifestyle, aging is unavoidable. With normal or healthy aging, the heart undergoes extensive vascular, cellular, and interstitial molecular changes that result in stiffer less compliant hearts that experience a general decline in organ function. Although these molecular changes deemed cardiac remodeling were once thought to be concomitant with advanced cardiovascular disease, they can be found in patients without manifestation of clinical disease. It is now mostly acknowledged that these age-related mechanical changes confer vulnerability of the heart to cardiovascular stresses associated with disease, such as hypertension and atherosclerosis. However, recent studies have aimed at differentiating the initial compensatory changes that occur within the heart with age to maintain contractile function from the maladaptive responses associated with disease. This work has identified new targets to improve cardiac function during aging. Spanning invertebrate to vertebrate models, we use this review to delineate some hallmarks of physiological versus pathological remodeling that occur in the cardiomyocyte and its microenvironment, focusing especially on the mechanical changes that occur within the sarcomere, intercalated disc, costamere, and extracellular matrix. PMID:27174949

  8. Cost comparison of mechanically ventilated patients across the age span

    PubMed Central

    Hayman, William R.; Leuthner, Steven R.; Laventhal, Naomi T.; Brousseau, David; Lagatta, Joanne M.

    2016-01-01

    Objective to compare use of mechanical ventilation and hospital costs across ventilated patients of all ages, preterm through adults, in a nationally-representative sample. Study Design secondary analysis of the 2009 Agency for Healthcare Research and Quality National Inpatient Sample. Results 1,107,563 (2.8%) patients received mechanical ventilation. For surviving ventilated patients, median costs for infants ≤32 weeks’ gestation were $51,000–$209,000, whereas median costs for older patients were lower, from $17,000–$25,000. For non-surviving ventilated patients, median costs were $27,000–$39,000 except at the extremes of age; the median cost was $10,000 for <24 week newborns, and $14,000 for 91+ year adults. Newborns of all gestational ages had a disproportionate share of hospital costs relative to their total volume. Conclusions Most ICU resources at the extremes of age are not directed toward non-surviving patients. From a perinatal perspective, attention should be directed toward improving outcomes and reducing costs for all infants, not just at the earliest gestational ages. PMID:26468935

  9. System Voltage Potential-Induced Degradation Mechanisms in PV Modules and Methods for Test: Preprint

    SciTech Connect

    Hacke, P.; Terwilliger, K.; Smith, R.; Glick, S.; Pankow, J.; Kempe, M.; Kurtz, S.; Bennett, I.; Kloos, M.

    2011-07-01

    Over the past decade, degradation and power loss have been observed in PV modules resulting from the stress exerted by system voltage bias. This is due in part to qualification tests and standards that do not adequately evaluate for the durability of modules to the long-term effects of high voltage bias experienced in fielded arrays. High voltage can lead to module degradation by multiple mechanisms. The extent of the voltage bias degradation is linked to the leakage current or coulombs passed from the silicon active layer through the encapsulant and glass to the grounded module frame, which can be experimentally determined; however, competing processes make the effect non-linear and history-dependent. Appropriate testing methods and stress levels are described that demonstrate module durability to system voltage potential-induced degradation (PID) mechanisms. This information, along with outdoor testing that is in progress, is used to estimate the acceleration factors needed to evaluate the durability of modules to system voltage stress. Na-rich precipitates are observed on the cell surface after stressing the module to induce PID in damp heat with negative bias applied to the active layer.

  10. System Voltage Potential-Induced Degradation Mechanisms in PV Modules and Methods for Test

    SciTech Connect

    Hacke, P.; Terwilliger, K.; Smith, R.; Glick, S.; Pankow, J.; Kempe, M.; Kurtz, S.; Bennett, I.; Kloos, M.

    2011-01-01

    Over the past decade, degradation and power loss have been observed in PV modules resulting from the stress exerted by system voltage bias. This is due in part to qualification tests and standards that do not adequately evaluate for the durability of modules to the long-term effects of high voltage bias experienced in fielded arrays. High voltage can lead to module degradation by multiple mechanisms. The extent of the voltage bias degradation is linked to the leakage current or culombs passed from the silicon active layer through the encapsulant and glass to the grounded module frame, which can be experimentally determined; however, competing processes make the effect non-linear and history-dependent. Appropriate testing methods and stress levels are described that demonstrate module durability to system voltage potential-induced degradation (PID) mechanisms. This information, along with outdoor testing that is in progress, is used to estimate the acceleration factors needed to evaluate the durability of modules to system voltage stress. Na-rich precipitates are observed on the cell surface after stressing the module to induce PID in damp heat with negative bias applied to the active layer.

  11. An efficient and environment-friendly method of removing graphene oxide in wastewater and its degradation mechanisms.

    PubMed

    Zhang, Chao-Zhi; Li, Ting; Yuan, Yang; Xu, Jianqiang

    2016-06-01

    Graphene and graphene oxide (GO) have already existed in air, water and soil due to their popular application in functional materials. However, degradation of graphene and GO in wastewater has not been reported. Degradation of GO plays a key role in the elimination of graphene and GO in wastewater due to graphene being easily oxidized to GO. In this paper, GO was completely degraded to give CO2 by Photo-Fenton. The degradation intermediates were determined by UV-vis absorption spectra, elemental analysis (EA), fourier transform infrared (FT-IR) and liquid chromatography-mass spectrometry (LC-MS). Experimental results showed that graphene oxide was completely degraded to give CO2 after 28 days. Based on UV, FT-IR, LC-MS spectra and EA data of these degradation intermediates, the degradation mechanisms of GO were supposed. This paper suggests an efficient and environment-friendly method to degrade GO and graphene. PMID:27042978

  12. Theoretical predictions of chemical degradation reaction mechanisms of RDX and other cyclic nitramines derived from their molecular structures.

    PubMed

    Qasim, M; Fredrickson, H; McGrath, C; Furey, J; Bajpai, R

    2005-06-01

    Analysis of environmental degradation pathways of contaminants is aided by predictions of likely reaction mechanisms and intermediate products derived from computational models of molecular structure. Quantum mechanical methods and force-field molecular mechanics were used to characterize cyclic nitramines. Likely degradation mechanisms for hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) include hydroxylation utilizing addition of hydroxide ions to initiate proton abstraction via 2nd order rate elimination (E2) or via nucleophilic substitution of nitro groups, reductive chemical and biochemical degradation, and free radical oxidation. Due to structural similarities, it is predicted that, under homologous circumstances, certain RDX environmental degradation pathways should also be effective for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and similar cyclic nitramines. Computational models provided a theoretical framework whereby likely transformation mechanisms and transformation products of cyclic nitramines were predicted and used to elucidate in situ degradation pathways. PMID:15804809

  13. Material Aging and Degradation Detection and Remaining Life Assessment for Plant Life Management

    SciTech Connect

    Ramuhalli, Pradeep; Henager, Charles H.; Griffin, Jeffrey W.; Meyer, Ryan M.; Coble, Jamie B.; Pitman, Stan G.; Bond, Leonard J.

    2012-12-31

    One of the major factors that may impact long term operations is structural material degradation, Detecting materials degradation, estimating the remaining useful life (RUL) of the component, and determining approaches to mitigating the degradation are important from the perspective of long term operations. In this study, multiple nondestructive measurement and monitoring methods were evaluated for their ability to assess the material degradation state. Metrics quantifying the level of damage from these measurements were defined, and evaluated for their ability to provide estimates of remaining life of the component. An example of estimating the RUL from nondestructive measurements of material degradation condition is provided.

  14. Stability and degradation of organic photovoltaics fabricated, aged, and characterized by the ISOS 3 inter-laboratory collaboration

    NASA Astrophysics Data System (ADS)

    Tanenbaum, David M.; Hermenau, Martin; Voroshazi, Eszter; Lloyd, Matthew T.; Galagan, Yulia; Zimmermann, Birger; Hösel, Markus; Dam, Henrik F.; Jørgensen, Mikkel; Gevorgyan, Suren; Kudret, Suleyman; Maes, Wouter; Lutsen, Laurence; Vanderzande, Dirk; Würfel, Uli; Andriessen, Ronn; Rösch, Roland; Hoppe, Harald; Lira-Cantu, Monica; Teran-Escobar, Gerardo; Dupuis, Aurélie; Bussière, Pierre-Olivier; Rivaton, Agnès.; Uzunoglu, Gülsah Y.; Germack, David; Andreasen, Birgitta; Madsen, Morten V.; Norrman, Kion; Bundgaard, Eva; Krebs, Frederik C.

    2012-09-01

    Seven distinct sets (n >= 12) of state of the art organic photovoltaic devices were prepared by leading research laboratories in a collaboration planned at the Third International Summit on Organic Photovoltaic Stability (ISOS-3). All devices were shipped to DTU and characterized simultaneously up to 1830 h in accordance with established ISOS-3 protocols under three distinct illumination conditions: accelerated full sun simulation; low level indoor fluorescent lighting; and dark storage with daily measurement under full sun simulation. Three nominally identical devices were used in each experiment both to provide an assessment of the homogeneity of the samples and to distribute samples for a variety of post soaking analytical measurements at six distinct laboratories enabling comparison at various stages in the degradation of the devices. Characterization includes current-voltage curves, light beam induced current (LBIC) imaging, dark lock-in thermography (DLIT), photoluminescence (PL), electroluminescence (EL), in situ incident photon-to-electron conversion efficiency (IPCE), time of flight secondary ion mass spectrometry (TOF-SIMS), cross sectional electron microscopy (SEM), UV visible spectroscopy, fluorescence microscopy, and atomic force microscopy (AFM). Over 100 devices with more than 300 cells were used in the study. We present here design of the device sets, results both on individual devices and uniformity of device sets from the wide range of characterization methods applied at different stages of aging under the three illumination conditions. We will discuss how these data can help elucidate the degradation mechanisms as well as the benefits and challenges associated with the unprecedented size of the collaboration.

  15. Mechanisms of soil degradation and consequences for carbon stocks on Tibetan grasslands

    NASA Astrophysics Data System (ADS)

    Kuzyakov, Yakov; Schleuss, Per-Marten; Miehe, Georg; Heitkamp, Felix; Sebeer, Elke; Spielvogel, Sandra; Xu, Xingliang; Guggenberger, Georg

    2016-04-01

    Tibetan grasslands provide tremendous sinks for carbon (C) and represent important grazing ground. Strong degradation - the destroying the upper root-mat/soil horizon of Kobresia pastures, has dramatic consequences for soil organic carbon (SOC) and nutrient storage. To demonstrate specific degradation patterns and elucidate mechanisms, as well as to assess consequences for SOC storage, we investigated a sequence of six degradation stages common over the whole Kobresia ecosystem. The soil degradation sequence consists of following mechanisms: Overgrazing and trampling by livestock provide the prerequisite for grassland degradation as both (a) cause plant dying, (b) reduce grassland recovery and (c) destroy protective Kobresia root-mats. These anthropogenic induced processes are amplified by naturally occurring degradation in harsh climate. The frequently repeated soil moisture and temperature fluctuations induce volume changes and tensions leading to polygonal cracking of the root mats. Then the plants die and erosion gradually extend the surface cracks. Soil erosion cause a high SOC loss from the upper horizons (0-10 cm: ~5.1 kg C m-2), whereas SOC loss beneath the surface cracks is caused by both, decreasing root C-input and SOC mineralization (SOC losses by mineralization: ~2.5 kg C m-2). Root biomass decreases with degradation and indicated lower C input. The negative δ13C shift of SOC reflects intensive decomposition and corresponds to a relative enrichment of 13C depleted lignin components. We conclude that the combined effects of overgrazing and harsh climate reduce root C input, increase SOC decomposition and initiate erosion leading to SOC loss up to 70% of intact soil (0-30 cm: ~7.6 kg C m-2). Consequently, a high amount of C is released back to the atmosphere as CO2, or is deposited in depressions and river beds creating a potential source of N2O and CH4. Concluding, anthropogenically induced overgrazing makes the Kobresia root-mat sensitive to natural

  16. Degradation of trichloroethene by siderite-catalyzed hydrogen peroxide and persulfate: Investigation of reaction mechanisms and degradation products

    PubMed Central

    Yan, Ni; Liu, Fei; Xue, Qiang; Brusseau, Mark L.; Liu, Yali; Wang, Junjie

    2015-01-01

    A binary catalytic system, siderite-catalyzed hydrogen peroxide (H2O2) coupled with persulfate (S2O82−), was investigated for the remediation of trichloroethene (TCE) contamination. Batch experiments were conducted to investigate reaction mechanisms, oxidant decomposition rates, and degradation products. By using high performance liquid chromatography (HPLC) coupled with electron paramagnetic resonance (EPR), we identified four radicals (hydroxyl (HO·), sulfate (SO4−·), hydroperoxyl (HO2·), and superoxide (O2−·)) in the siderite-catalyzed H2O2-S2O82− system. In the absence of S2O82− (i.e., siderite-catalyzed H2O2), a majority of H2O2 was decomposed in the first hour of the experiment, resulting in the waste of HO·. The addition of S2O82− moderated the H2O2 decomposition rate, producing a more sustainable release of hydroxyl radicals that improved the treatment efficiency. Furthermore, the heat released by H2O2 decomposition accelerated the activation of S2O82−, and the resultant SO4−· was the primary oxidative agent during the first two hours of the reaction. Dichloroacetic acid was firstly detected by ion chromatography (IC). The results of this study indicate a new insight to the reaction mechanism for the catalytic binary H2O2-S2O82− oxidant system, and the delineation of radicals and the discovery of the chlorinated byproduct provide useful information for efficient treatment of chlorinated-solvent contamination in groundwater. PMID:26236152

  17. Degradation Kinetics and Mechanism of a β-Lactam Antibiotic Intermediate, 6-Aminopenicillanic Acid, in a New Integrated Production Process.

    PubMed

    Su, Min; Sun, Hua; Zhao, Yingying; Lu, Aidang; Cao, Xiaohui; Wang, Jingkang

    2016-01-01

    In an effort to promote sustainability and to reduce manufacturing costs, the traditional production process for 6-aminopenicillanic acid (6-APA) has been modified to include less processing units. The objectives of this study are to investigate the degradation kinetics of 6-APA, to propose a reasonable degradation mechanism, and to optimize the manufacturing conditions within this new process. A series of degradation kinetic studies were conducted in the presence of impurities, as well as at various chemical and physical conditions. The concentrations of 6-APA were determined by high-performance liquid chromatography. An Arrhenius-type kinetic model was established to give a more accurate prediction on the degradation rates of 6-APA. A hydrolysis degradation mechanism is shown to be the major pathway for 6-APA. The degradation mechanisms and the kinetic models for 6-APA in the new system enable the design of a good manufacturing process with optimized parameters. PMID:26852849

  18. Polymer Aging Techniques Applied to Degradation of a Polyurethane Propellant Binder

    SciTech Connect

    Assink, R.A.; Celina, M.; Graham, A.C.; Minier, L.M.

    1999-07-27

    The oxidative thermal aging of a crosslinked hydroxy-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) polyurethane rubber, commonly used as the polymeric binder matrix in solid rocket propellants, was studied at temperatures of RT to 125 C. We investigate changes in tensile elongation, mechanical hardening, polymer network properties, density, O{sub 2} permeation and molecular chain dynamics using a range of techniques including solvent swelling, detailed modulus profiling and NMR relaxation measurements. Using extensive data superposition and highly sensitive oxygen consumption measurements, we critically evaluate the Arrhenius methodology, which normally assumes a linear extrapolation of high temperature aging data. Significant curvature in the Arrhenius diagram of these oxidation rates was observed similar to previous results found for other rubber materials. Preliminary gel/network properties suggest that crosslinking is the dominant process at higher temperatures. We also assess the importance of other constituents such as ammonium perchlorate or aluminum powder in the propellant formulation.

  19. Poly(ethylene glycol) Hydrogels with Adaptable Mechanical and Degradation Properties for Use in Biomedical Applicationsa

    PubMed Central

    Parlato, Matthew; Reichert, Sarah; Barney, Neal

    2014-01-01

    Requirements of hydrogels for drug delivery, wound dressings, and surgical implantation can be extensive, including suitable mechanical properties and tailorable degradation time frames. Herein, an adaptable PEG-based hydrogel, whose mechanical properties and degradation rate can be systematically adjusted to meet these criteria by altering simple variables such as the PEG molecular weight, is described. The performance of these hydrogels in three physical manipulations (pushing, pulling, and folding), representative of manipulations that they may undergo during typical biomedical use, is also assessed. While not all of these formulations can withstand these manipulations, a subset did, and it is intended to further optimize these formulations for specific clinical applications. Additionally, the outcomes of the physical manipulation tests indicate that simply having a high modulus does not correlate with biomedical applicability. PMID:24949497

  20. Mechanical and microstructural/chemical degradation of coating and substrate in gas turbine blade

    SciTech Connect

    Sugita, Y.; Ito, M.; Sakurai, S.; Gold, C.R.; Bloomer, T.E.; Kameda, J.

    1995-12-31

    The mechanical property degradation (295--1223 K) and microstructural/chemical evolution of CoNiCrAlY coatings and superalloy (Rene 80) substrates in gas turbine blades operated in- service have been studied using a small punch (SP) testing technique and scanning Auger microprobe. In SP tests, coating cracks continuously and discretely propagated at 295 K and higher temperatures, respectively. The ductile-brittle transition temperature of the coatings was increased during long time exposure of gas turbine blades to oxidizing environments while that of the substrate did not change. The low cycle fatigue life of the coatings at 295 K was also reduced in-service. Oxidation and sulfur segregation near the coating surface were found to be major causes of the mechanical degradation of the coatings.

  1. Mechanism of hydroxyl radical generation from biochar suspensions: Implications to diethyl phthalate degradation.

    PubMed

    Fang, Guodong; Zhu, Changyin; Dionysiou, Dionysios D; Gao, Juan; Zhou, Dongmei

    2015-01-01

    This paper investigated hydroxyl radical (OH) generation from biochar suspensions for diethyl phthalate (DEP) degradation in the presence of oxygen. Electron paramagnetic resonance (EPR) coupled with a salicylic acid trapping method were used to detect free radicals in biochar and verify OH generation from biochar suspensions. Free radicals (FRs) in biochar could induce OH generation, and ≈12 spins of FRs were consumed to produce one trapped [OH] molecule. The proposed mechanism of OH generation was that FRs in biochar transferred electrons to O2 to produce the superoxide radical anion and hydrogen peroxide, which reacted further with FRs to produce OH. Free radical-quenching studies utilizing superoxide dismutase, catalase, and deferoxamine as scavengers were used to testify this mechanism. Furthermore, OH generated from biochar suspensions could degrade DEP efficiently. These findings of this study provide new insights into the physicochemical properties and environmental implications of biochar. PMID:25461005

  2. Kinetics and mechanisms of degradation of chloroacetonitriles by the UV/H2O2 process.

    PubMed

    Ling, Li; Sun, Jianliang; Fang, Jingyun; Shang, Chii

    2016-08-01

    Haloacetonitriles (HANs) are emerging disinfection by-products (DBPs) that are more toxic than the regulated DBPs and widely found in the chlorinated/chloraminated water. This paper studied kinetics and mechanisms of the degradation of chloroacetonitriles (CANs) by the UV/H2O2 process at pH 6 and 7.5 and H2O2 concentrations of 1 × 10(-3) M, 5 × 10(-3) M and 1 × 10(-2) M. The degradation followed pseudo first-order degradation kinetics. The degradation rate of monochloroacetonitrile (MCAN) remained similar, while those of dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN) increased with increasing pH and H2O2 concentrations. The different trends were attributed to the changing contributions of the two major mechanisms: the nucleophilic attack by hydroperoxide ions ( [Formula: see text] ) and the hydroxyl radical (•OH) oxidation. The second-order rate constants of [Formula: see text] towards MCAN, DCAN and TCAN were determined to be 11.8 (±0.62), 4.83 (±0.01) × 10(3), and 2.54 (±0.23) × 10(5) M(-1) s(-1), respectively, while that of •OH were 8.7 × 10(6), 4.4 × 10(6), and < 10(6) M(-1) s(-1), respectively. The degradation of TCAN was mainly attributed to the [Formula: see text] nucleophilic attack, while that of MCAN was dominated by the •OH oxidation. DCAN was degraded by both mechanisms. The nucleophilic attack increased linearly with increasing [Formula: see text] concentration as a result of increasing H2O2 concentration and/or pH, while the •OH oxidation was less dependent on H2O2 concentrations and/or pH. The nucleophilic attack mainly transformed HANs to haloacetamides, while the •OH oxidation dechlorinated HANs. This paper firstly illustrated the importance of the [Formula: see text] nucleophilic attack, in addition to the •OH oxidation, on the CAN degradation in the UV/H2O2 process. PMID:27161887

  3. Degradation mechanisms and stability forecasting and adhesion contacts of metal films with binary dielectric substrates

    SciTech Connect

    Stolyarova, S.; Nemirovsky, Y.; Simanovskis, A.

    1996-12-31

    In this paper the authors present their conception of degradation and stability on the adhesion contacts of metal films with binary nonmetallic crystals. There are numerous works devoted to the atomic scale determination of adhesion forces and development of adhesion interaction laws. But in the real life the kinetic processes, taking place on the adhesion contact, can lead to such dramatic changes in adhesion strength values that the initial adhesion characteristics do not worth much for practice. Sometimes, adhesion contact with a metal which supposed to be highly adhesive failes in a short period of aging time. What the authors have learned from their studies of the contact processes is that in many cases the aging could not be separately addressed to the individual properties of film metal or to those of the substrate material. It depends mainly on the relationships between the parameters of interacting pair. The question is: what parameters should be taken into account to explain degradation phenomena and to predict them? The purpose of the present work is to show how the relative chemical activity of film metal and substrate cation affects the contact degradation in a vacuum and in different environmental conditions.

  4. Lifestyles and Ageing: Targeting Key Mechanisms to Shift the Balance from Unhealthy to Healthy Ageing.

    PubMed

    Grassi, Claudio; Landi, Francesco; Delogu, Giovanni

    2014-01-01

    The increase in life expectancy has dramatically enhanced the prevalence of age-related chronic diseases resulting in growing costs for both society and individuals. Identification of strategies contributing to healthy ageing is thus one of the major challenges of the coming years. Lifestyle has a primary role among non-genetic factors affecting health and lifespan. In particular, nutrition, mental and physical activity impact the molecular and functional mechanisms whose alterations cause the major age-related diseases. A better understanding of mechanisms underlying the beneficial action of correct lifestyles is useful to develop interventions aimed at preventing and/or delaying the onset of chronic degenerative diseases, to identify high-risk populations who could be targeted in intervention trials as well as to identify novel biomarkers of healthy ageing. A multidisciplinary team of basic scientists and clinicians operating at the Catholic University Medical School in Rome is actively working on this topic to determine the ability of healthy lifestyles to promote active ageing and counteract the major age-related diseases affecting brain health, musculoskeletal function and gut microenvironment. This chapter summarizes our strategic approaches, the major results we obtained so far and the main experimental and translational perspectives. PMID:26630517

  5. Age of sex-determining mechanisms in vertebrates.

    PubMed

    WITSCHI, E

    1959-08-14

    Certain characteristic patterns of physiologic sex determination are not causally linked with types of genic and chromosomal constitution (XX-XY or ZW-ZZ). The observed widespread but not universal parallelism in the distribution of genetic and physiologic patterns among vertebrate groups expresses genealogic relationship. On the basis of this interpretation one may estimate the approximate evolutionary age of the mechanism of genetic sex determination. It is concluded that in all tetrapod vertebrates these mechanisms originated during the Jurassic period. Environmental conditions seem to affect the progress of this evolution. PMID:13675759

  6. Debris generation from Mechanical degradation of MLI and thermo-control coating

    NASA Astrophysics Data System (ADS)

    Duzellier, Sophie; Drolshagen, Gerhard; Pons, Claude; Rey, Romain; Gordo, Paulo; Horstmann, Andre

    2016-07-01

    Space environment is a harsh environment for exposed materials. Amongst all environmental constraints, ionizing radiation in GEO (particles, UV), atomic oxygen in LEO and temperature variation through synergy mechanisms may lead to serious damage and loss of performance of surface materials (thermo-optical or mechanical properties). Optical and radar observations from the ground as well as analysis of retrieved hardware have shown an abundance of space debris objects that seem to result from the degradation of outer spacecraft surfaces. Recent surveys of the GEO and GTO region have found many objects with high area-to-mass ratio (HAMR debris, see T. Childknecht et al. 2003, 2004, 2005) indicating that they must consist of relatively thin material, like foils. This paper explores the cause, amount and characteristics of space debris objects resulting from spacecraft surface degradation in order to improve space debris population models and support the selection of materials in the context of debris mitigation measures. 20-year GEO dose profile along with thermal cycling has been applied to a set of MLI assemblies and painting samples. The material degradation was monitored through in and ex situ characterizations (visual observation, mechanical and thermo-optical). No self-flaking was observed for paintings nor for MLIs. However, paint surfaces became very brittle, whereas reclosable fasteners of MLIs and Mylar inner foils were strongly damaged as well. Potential scenarios for delamination of MLI foils could be defined.

  7. Stochastic mechanical degradation of multi-cracked fiber bundles with elastic and viscous interactions.

    PubMed

    Manca, Fabio; Giordano, Stefano; Palla, Pier Luca; Cleri, Fabrizio

    2015-05-01

    The mechanics of fiber bundles has been largely investigated in order to understand their complex failure modes. Under a mechanical load, the fibers fail progressively while the load is redistributed among the unbroken fibers. The classical fiber bundle model captures the most important features of this rupture process. On the other hand, the homogenization techniques are able to evaluate the stiffness degradation of bulk solids with a given population of cracks. However, these approaches are inadequate to determine the effective response of a degraded bundle where breaks are induced by non-mechanical actions. Here, we propose a method to analyze the behavior of a fiber bundle, undergoing a random distribution of breaks, by considering the intrinsic response of the fibers and the visco-elastic interactions among them. We obtain analytical solutions for simple configurations, while the most general cases are studied by Monte Carlo simulations. We find that the degradation of the effective bundle stiffness can be described by two scaling regimes: a first exponential regime for a low density of breaks, followed by a power-law regime at increasingly higher break density. For both regimes, we find analytical effective expressions described by specific scaling exponents. PMID:25998172

  8. Elements for the expected mechanisms on 'reduced emissions from deforestation and degradation, REDD' under UNFCCC

    NASA Astrophysics Data System (ADS)

    Mollicone, D.; Freibauer, A.; Schulze, E. D.; Braatz, S.; Grassi, G.; Federici, S.

    2007-10-01

    Carbon emissions from deforestation and degradation account for about 20% of global anthropogenic emissions. Strategies and incentives for reduced emissions from deforestation and degradation (REDD) have emerged as one of the most active areas in the international climate change negotiations under the United Nations Framework Convention on Climate Change (UNFCCC). While the current negotiations focus on a REDD mechanism in developing countries, it should be recognized that risks of carbon losses from forests occur in all climate zones and also in industrialized countries. A future climate change agreement would be more effective if it included all carbon losses and gains from land use in all countries and climate zones. The REDD mechanism will be an important step towards reducing emissions from land use change in developing countries, but needs to be followed by steps in other land use systems and regions. A national approach to REDD and significant coverage globally are needed to deal with the risk that deforestation and degradation activities are displaced rather than avoided. Favourable institutional and governance conditions need to be established that guarantee in the long-term a stable incentive and control system for maintaining forest carbon stocks. Ambitious emission reductions from deforestation and forest degradation need sustained financial incentives, which go beyond positive incentives for reduced emissions but also give incentives for sustainable forest management. Current data limitations need—and can be—overcome in the coming years to allow accurate accounting of reduced emissions from deforestation and degradation. A proper application of the conservativeness approach in the REDD context could allow a simplified reporting of emissions from deforestation in a first phase, consistent with the already agreed UNFCCC reporting principles.

  9. An intrinsic mechanism of secreted protein aging and turnover

    PubMed Central

    Yang, Won Ho; Aziz, Peter V.; Heithoff, Douglas M.; Mahan, Michael J.; Smith, Jeffrey W.; Marth, Jamey D.

    2015-01-01

    The composition and functions of the secreted proteome are controlled by the life spans of different proteins. However, unlike intracellular protein fate, intrinsic factors determining secreted protein aging and turnover have not been identified and characterized. Almost all secreted proteins are posttranslationally modified with the covalent attachment of N-glycans. We have discovered an intrinsic mechanism of secreted protein aging and turnover linked to the stepwise elimination of saccharides attached to the termini of N-glycans. Endogenous glycosidases, including neuraminidase 1 (Neu1), neuraminidase 3 (Neu3), beta-galactosidase 1 (Glb1), and hexosaminidase B (HexB), possess hydrolytic activities that temporally remodel N-glycan structures, progressively exposing different saccharides with increased protein age. Subsequently, endocytic lectins with distinct binding specificities, including the Ashwell–Morell receptor, integrin αM, and macrophage mannose receptor, are engaged in N-glycan ligand recognition and the turnover of secreted proteins. Glycosidase inhibition and lectin deficiencies increased protein life spans and abundance, and the basal rate of N-glycan remodeling varied among distinct proteins, accounting for differences in their life spans. This intrinsic multifactorial mechanism of secreted protein aging and turnover contributes to health and the outcomes of disease. PMID:26489654

  10. Investigation of degradation mechanisms of perovskite-based photovoltaic devices using laser beam induced current mapping

    NASA Astrophysics Data System (ADS)

    Song, Zhaoning; Watthage, Suneth C.; Phillips, Adam B.; Liyanage, Geethika K.; Khanal, Rajendra R.; Tompkins, Brandon L.; Ellingson, Randy J.; Heben, Michael J.

    2015-09-01

    Solution processed thin film photovoltaic devices incorporating organohalide perovskites have progressed rapidly in recent years and achieved energy conversion efficiencies greater than 20%. However, an important issue limiting their commercialization is that device efficiencies often drop within the first few hundred hours of operation. To explore the origin of the device degradation and failure in perovskite solar cells, we investigated the spatial uniformity of current collection at different stages of aging using two-dimensional laser beam induced current (LBIC) mapping. We validated that the local decomposition of the perovskite material is likely due to interactions with moisture in the air by comparing photocurrent collection in perovskite devices that were maintained in different controlled environments. We show that the addition of a poly(methyl methacrylate)/single-wall carbon nanotube (PMMA/SWCNT) encapsulation layer prevents degradation of the device in moist air. This suggests a route toward perovskite solar cells with improved operational stability and moisture resistance.

  11. Mechanical behaviour׳s evolution of a PLA-b-PEG-b-PLA triblock copolymer during hydrolytic degradation.

    PubMed

    Breche, Q; Chagnon, G; Machado, G; Girard, E; Nottelet, B; Garric, X; Favier, D

    2016-07-01

    PLA-b-PEG-b-PLA is a biodegradable triblock copolymer that presents both the mechanical properties of PLA and the hydrophilicity of PEG. In this paper, physical and mechanical properties of PLA-b-PEG-b-PLA are studied during in vitro degradation. The degradation process leads to a mass loss, a decrease of number average molecular weight and an increase of dispersity index. Mechanical experiments are made in a specific experimental set-up designed to create an environment close to in vivo conditions. The viscoelastic behaviour of the material is studied during the degradation. Finally, the mechanical behaviour is modelled with a linear viscoelastic model. A degradation variable is defined and included in the model to describe the hydrolytic degradation. This variable is linked to physical parameters of the macromolecular polymer network. The model allows us to describe weak deformations but become less accurate for larger deformations. The abilities and limits of the model are discussed. PMID:26919565

  12. Molecular and Cellular Mechanisms of Muscle Aging and Sarcopenia and Effects of Electrical Stimulation in Seniors

    PubMed Central

    Barberi, Laura; Scicchitano, Bianca Maria

    2015-01-01

    The prolongation of skeletal muscle strength in aging and neuromuscular disease has been the objective of numerous studies employing a variety of approaches. It is generally accepted that cumulative failure to repair damage related to an overall decrease in anabolic processes is a primary cause of functional impairment in muscle. The functional performance of skeletal muscle tissues declines during post- natal life and it is compromised in different diseases, due to an alteration in muscle fiber composition and an overall decrease in muscle integrity as fibrotic invasions replace functional contractile tissue. Characteristics of skeletal muscle aging and diseases include a conspicuous reduction in myofiber plasticity (due to the progressive loss of muscle mass and in particular of the most powerful fast fibers), alteration in muscle-specific transcriptional mechanisms, and muscle atrophy. An early decrease in protein synthetic rates is followed by a later increase in protein degradation, to affect biochemical, physiological, and morphological parameters of muscle fibers during the aging process. Alterations in regenerative pathways also compromise the functionality of muscle tissues. In this review we will give an overview of the work on molecular and cellular mechanisms of aging and sarcopenia and the effects of electrical stimulation in seniors.. PMID:26913161

  13. Mass spectrometric analysis for high molecular weight synthetic polymers using ultrasonic degradation and the mechanism of degradation.

    PubMed

    Kawasaki, Hideya; Takeda, Yoshiki; Arakawa, Ryuichi

    2007-06-01

    We have investigated ultrasonic degradations of poly(ethylene oxide) (PEG) and poly(methyl methacrylate) (PMMA) in aqueous media by means of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The ultrasonic degradation of polymers was monitored as a function of ultrasonication duration to examine the structural details of ultrasonic degradation polymers. PEG solution ultrasonication produced five types of oligomers (M approximately 1000 Da) with different end groups, irrespective of the initial average molecular masses (M=2, 6, 20, and 2000 kDa). Several degradation pathways with free radical reactions have been suggested to explain these degradation products: the ultrasonic degradation of PEG is initiated by breaking of the C-O bond in the PEG chain, generating polymeric radicals with two terminal groups, i.e., X*( approximately CH2CH2*) and Y*( approximately CH2CH2O*), followed by termination with extraction or release of a hydrogen atom. However, PMMA (M=1630 Da) ultrasonication generated only one type of degradation oligomer, which has a hydrogen group at both ends, the same as that of the original oligomer. It has been suggested that the presence of the radical terminal groups X*( approximately CH2*) and Y*( approximately (CH3)CCOO(CH3)C*) is due to selective C-C bond breaking in the chain during the ultrasonic degradation of PMMA. The MALDI-TOFMS combined with the ultrasonic degradation technique (UD/MALDI-TOFMS) developed in this study could be extended to the analysis of synthetic polymer structures with high molecular weights. PMID:17461552

  14. Aging and Neurodegeneration: A Tangle of Models and Mechanisms.

    PubMed

    Chakrabarti, Sasanka; Mohanakumar, Kochupurackal P

    2016-03-01

    The research on aging and age-related diseases, especially the neurodegenerative diseases, is on the fast track. However, the results have so far not been translated to actual benefit for the patients in terms of treatment or diagnosis of age-related degenerative diseases including those of the CNS. As far as the prevention of the cognitive decline during non-pathological aging is concerned, there is nothing much to offer other than calorie restriction and physical exercise. Needless to say, the benefits are not up to our expectations. However, over the years at the experimental level it has been possible to identify several cellular and molecular mechanisms that are intricately associated with aging in general and neurodegenerative diseases in particular. These include oxidative stress and altered redox-signaling, mitochondrial dysfunction, inflammation, proteotoxicity and altered gene expressions. These inter-dependent pathways mediate cellular senescence and often culminate in programmed cell death like apoptosis and autophagy, and in the context of brain these changes are manifested clinically as cognitive decline and pathologically as neurodegeneration. This special issue provides the readers with glimpses of this complex scenario from different angles primarily in the context of brain and also attempts to identify the potential drug targets against neurodegenerative diseases. PMID:27114843

  15. Aging and Neurodegeneration: A Tangle of Models and Mechanisms

    PubMed Central

    Chakrabarti, Sasanka; Mohanakumar, Kochupurackal P.

    2016-01-01

    The research on aging and age-related diseases, especially the neurodegenerative diseases, is on the fast track. However, the results have so far not been translated to actual benefit for the patients in terms of treatment or diagnosis of age-related degenerative diseases including those of the CNS. As far as the prevention of the cognitive decline during non-pathological aging is concerned, there is nothing much to offer other than calorie restriction and physical exercise. Needless to say, the benefits are not up to our expectations. However, over the years at the experimental level it has been possible to identify several cellular and molecular mechanisms that are intricately associated with aging in general and neurodegenerative diseases in particular. These include oxidative stress and altered redox-signaling, mitochondrial dysfunction, inflammation, proteotoxicity and altered gene expressions. These inter-dependent pathways mediate cellular senescence and often culminate in programmed cell death like apoptosis and autophagy, and in the context of brain these changes are manifested clinically as cognitive decline and pathologically as neurodegeneration. This special issue provides the readers with glimpses of this complex scenario from different angles primarily in the context of brain and also attempts to identify the potential drug targets against neurodegenerative diseases. PMID:27114843

  16. Laccase-catalyzed decolorization of malachite green: performance optimization and degradation mechanism.

    PubMed

    Yang, Jie; Yang, Xiaodan; Lin, Yonghui; Ng, Tzi Bun; Lin, Juan; Ye, Xiuyun

    2015-01-01

    Malachite green (MG) was decolorized by laccase (LacA) of white-rot fungus Cerrena sp. with strong decolorizing ability. Decolorization conditions were optimized with response surface methodology. A highly significant quadratic model was developed to investigate MG decolorization with LacA, and the maximum MG decolorization ratio of 91.6% was predicted under the conditions of 2.8 U mL(-1) LacA, 109.9 mg L(-1) MG and decolorization for 172.4 min. Kinetic studies revealed the Km and kcat values of LacA toward MG were 781.9 mM and 9.5 s(-1), respectively. UV-visible spectra confirmed degradation of MG, and the degradation mechanism was explored with liquid chromatography-mass spectrometry (LC-MS) analysis. Based on the LC-MS spectra of degradation products, LacA catalyzed MG degradation via two simultaneous pathways. In addition, the phytotoxicity of MG, in terms of inhibition on seed germination and seedling root elongation of Nicotiana tabacum and Lactuca sativa, was reduced after laccase treatment. These results suggest that laccase of Cerrena was effective in decolorizing MG and promising in bioremediation of wastewater in food and aquaculture industries. PMID:26020270

  17. Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

    SciTech Connect

    Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; Austin, Kevin N.; Chambers, Robert S.

    2015-08-06

    The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted for by the glass transition temperature, Tg, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, Tref, by the same amount as the Tg depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive Tg depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.

  18. Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

    DOE PAGESBeta

    Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; Austin, Kevin N.; Chambers, Robert S.

    2015-08-06

    The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted formore » by the glass transition temperature, Tg, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, Tref, by the same amount as the Tg depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive Tg depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.« less

  19. Laccase-Catalyzed Decolorization of Malachite Green: Performance Optimization and Degradation Mechanism

    PubMed Central

    Yang, Jie; Yang, Xiaodan; Lin, Yonghui; Ng, Tzi Bun; Lin, Juan; Ye, Xiuyun

    2015-01-01

    Malachite green (MG) was decolorized by laccase (LacA) of white-rot fungus Cerrena sp. with strong decolorizing ability. Decolorization conditions were optimized with response surface methodology. A highly significant quadratic model was developed to investigate MG decolorization with LacA, and the maximum MG decolorization ratio of 91.6% was predicted under the conditions of 2.8 U mL-1 LacA, 109.9 mg L-1 MG and decolorization for 172.4 min. Kinetic studies revealed the Km and kcat values of LacA toward MG were 781.9 mM and 9.5 s-1, respectively. UV–visible spectra confirmed degradation of MG, and the degradation mechanism was explored with liquid chromatography–mass spectrometry (LC-MS) analysis. Based on the LC-MS spectra of degradation products, LacA catalyzed MG degradation via two simultaneous pathways. In addition, the phytotoxicity of MG, in terms of inhibition on seed germination and seedling root elongation of Nicotiana tabacum and Lactuca sativa, was reduced after laccase treatment. These results suggest that laccase of Cerrena was effective in decolorizing MG and promising in bioremediation of wastewater in food and aquaculture industries. PMID:26020270

  20. Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

    PubMed

    Kim, Tae-Kyoung; Moon, Bo-Ram; Kim, Taeyeon; Kim, Moon-Kyung; Zoh, Kyung-Duk

    2016-11-01

    We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates. PMID:27494316

  1. Mechanism of Silicon Electrode Aging upon Cycling in Full Lithium-Ion Batteries.

    PubMed

    Delpuech, Nathalie; Dupre, Nicolas; Moreau, Philippe; Bridel, Jean-Sebastian; Gaubicher, Joel; Lestriez, Bernard; Guyomard, Dominique

    2016-04-21

    Understanding the aging mechanism of silicon-based negative electrodes for lithium-ion batteries upon cycling is essential to solve the problem of low coulombic efficiency and capacity fading and further to implement this new high-capacity material in commercial cells. Nevertheless, such studies have so far focused on half cells in which silicon is cycled versus an infinite reservoir of lithium. In the present work, the aging mechanism of silicon-based electrodes is studied upon cycling in a full Li-ion cell configuration with LiCoO2 as the positive electrode. Postmortem analyses of both electrodes clearly indicate that neither one of them contains lithium and that no discernible degradation results from the cycling. The aging mechanism can be explained by the reduction of solvent molecules. Electrons extracted from the positive electrode are responsible for an internal imbalance in the cell, which results in progressive slippage of the electrodes and reduces the compositional range of cyclable lithium ions for both electrodes. PMID:26915951

  2. A complementary role of intracortical inhibition in age-related tactile degradation and its remodelling in humans.

    PubMed

    Pleger, Burkhard; Wilimzig, Claudia; Nicolas, Volkmar; Kalisch, Tobias; Ragert, Patrick; Tegenthoff, Martin; Dinse, Hubert R

    2016-01-01

    Many attempts are currently underway to restore age-related degraded perception, however, the link between restored perception and remodeled brain function remains elusive. To understand remodeling of age-related cortical reorganization we combined functional magnetic resonance imaging (fMRI) with assessments of tactile acuity, perceptual learning, and computational modeling. We show that aging leads to tactile degradation parallel to enhanced activity in somatosensory cortex. Using a neural field model we reconciled the empirical age-effects by weakening of cortical lateral inhibition. Using perceptual learning, we were able to partially restore tactile acuity, which however was not accompanied by the expected attenuation of cortical activity, but by a further enhancement. The neural field model reproduced these learning effects solely through a weakening of the amplitude of inhibition. These findings suggest that the restoration of age-related degraded tactile acuity on the cortical level is not achieved by re-strengthening lateral inhibition but by further weakening intracortical inhibition. PMID:27302219

  3. A complementary role of intracortical inhibition in age-related tactile degradation and its remodelling in humans

    PubMed Central

    Pleger, Burkhard; Wilimzig, Claudia; Nicolas, Volkmar; Kalisch, Tobias; Ragert, Patrick; Tegenthoff, Martin; Dinse, Hubert R.

    2016-01-01

    Many attempts are currently underway to restore age-related degraded perception, however, the link between restored perception and remodeled brain function remains elusive. To understand remodeling of age-related cortical reorganization we combined functional magnetic resonance imaging (fMRI) with assessments of tactile acuity, perceptual learning, and computational modeling. We show that aging leads to tactile degradation parallel to enhanced activity in somatosensory cortex. Using a neural field model we reconciled the empirical age-effects by weakening of cortical lateral inhibition. Using perceptual learning, we were able to partially restore tactile acuity, which however was not accompanied by the expected attenuation of cortical activity, but by a further enhancement. The neural field model reproduced these learning effects solely through a weakening of the amplitude of inhibition. These findings suggest that the restoration of age-related degraded tactile acuity on the cortical level is not achieved by re-strengthening lateral inhibition but by further weakening intracortical inhibition. PMID:27302219

  4. Insight into the Mechanism of Graphene Oxide Degradation via the Photo-Fenton Reaction.

    PubMed

    Bai, Hao; Jiang, Wentao; Kotchey, Gregg P; Saidi, Wissam A; Bythell, Benjamin J; Jarvis, Jacqueline M; Marshall, Alan G; Robinson, Renã A S; Star, Alexander

    2014-05-15

    Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150-1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed. PMID:24860637

  5. Insight into the Mechanism of Graphene Oxide Degradation via the Photo-Fenton Reaction

    PubMed Central

    2015-01-01

    Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150–1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed. PMID:24860637

  6. Degradation mechanism of a low band gap polymer PTB7 by oxidation

    NASA Astrophysics Data System (ADS)

    Park, Soohyung; Jeong, Junkyeong; Lee, Hyunbok; Yi, Yeonjin

    Recently, the PCE of OPVs is at the 10% mark by using donor materials having a low band gap, such as poly(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl) (PTB7) and its analogues. In spite of the significant PCE improvement, the lifetime issue still remains open problem. To solve these technical limitations fundamentally, the degradation mechanism should be understood. It can be revealed by investigating the electronic structures of polymers with controlled exposure of oxygen, moisture and light. In this study, ultraviolet, X-ray and inverse photoelectron spectroscopy measurements were performed with step-by-step exposure of controlled oxygen, moisture and light to investigate the degradation mechanism of each polymer film. Theoretical calculations using density functional theory (DFT) were also performed to understand detailed degradation process. From the experimental results, we demonstrate that push-pull polymers are more sensitive to environmental conditions, compared with non-push-pull (conventional) polymers such as poly (3-hexylthiophene-2,5-diyl) (P3HT). In addition, we show high photo-oxidation of PTB7 is originated from the structural reason.

  7. [Research progress on the degradation mechanisms and restoration of riparian ecosystem].

    PubMed

    Huang, Kai; Guo, Huai-cheng; Liu, Yong; Yu, Ya-juan; Zhou, Feng

    2007-06-01

    Restoration and reconstruction of degraded riparian ecosystem caused by natural and anthropogenic disturbances is one of the important issues in restoration ecology and watershed ecology. The disturbances on riparian ecosystem include flow regime alteration, direct modification and watershed disturbance, which have different affecting mechanisms. Flow regime alteration affects riparian ecosystem by changing riparian soil humidity, oxidation-reduction potential, biotaliving environment, and sediment transfer; direct modification affects riparian vegetation diversity through human activities and exotic plants invasion; and watershed disturbance mainly manifests in the channel degradation, aggradation or widening, the lowering of groundwater table, and the modification in fluvial process. The assessment objects of riparian restoration are riparian ecosystem components, and the assessment indicators are shifted from ecological to synthetic indices. Riparian restoration should be based on the detailed understanding of the biological and physical processes which affect riparian ecosystem, and implemented by vegetation restoration and hydrological adjustment at watershed or landscape scale. To extend the research scales and objects and to apply interdisciplinary approaches should be the key points in the further studies on the degradation mechanisms and restoration of riparian ecosystem. PMID:17763745

  8. Towards understanding intrinsic degradation and breakdown mechanisms in SiOCH low-k dielectrics

    SciTech Connect

    Wu, C. De Wolf, I.; Li, Y.; Ciofi, I.; Kauerauf, Th.; Bömmels, J.; Tőkei, Zs.; Croes, K.

    2015-02-14

    The degradation and breakdown mechanisms of a SiOCH low-k material with k = 2.3 (25% porosity) and thicknesses ranging from 90 nm to 20 nm were investigated. By combining the time dependent dielectric breakdown data at positive/negative bias stress with the thickness scaling results, dielectric failure is proven to be intrinsic and not influenced by copper drift or metal barrier deposition induced dielectric damage. It is shown that stress induced leakage current (SILC) can be used as a measure of dielectric degradation. Therefore, low field lifetimes can be safely estimated using SILC extrapolation. Based on our results, both the impact damage model and the power law model have a good accuracy for low field lifetime prediction. Recovery and anneal experiments are used to study the physical nature causing the observed negative flatband voltage shifts in our metal-insulator-semiconductor planar capacitor structures, where hydrogen induced unstable fast and slow donor type interface states are hypothesized to be the root cause of the observed shifts. We suggest that atomic hydrogen is released from the dielectric during electron injection and migrates to the interfacial region. Our model is further supported by an observed irreversible SILC change during the recovery and anneal studies. The degradation mechanism proposed in this work, supported by the low field lifetime data, provides a feasible explanation for intrinsic low-k dielectric failure.

  9. Towards understanding intrinsic degradation and breakdown mechanisms in SiOCH low-k dielectrics

    NASA Astrophysics Data System (ADS)

    Wu, C.; Li, Y.; Ciofi, I.; Kauerauf, Th.; Bömmels, J.; De Wolf, I.; Tőkei, Zs.; Croes, K.

    2015-02-01

    The degradation and breakdown mechanisms of a SiOCH low-k material with k = 2.3 (25% porosity) and thicknesses ranging from 90 nm to 20 nm were investigated. By combining the time dependent dielectric breakdown data at positive/negative bias stress with the thickness scaling results, dielectric failure is proven to be intrinsic and not influenced by copper drift or metal barrier deposition induced dielectric damage. It is shown that stress induced leakage current (SILC) can be used as a measure of dielectric degradation. Therefore, low field lifetimes can be safely estimated using SILC extrapolation. Based on our results, both the impact damage model and the power law model have a good accuracy for low field lifetime prediction. Recovery and anneal experiments are used to study the physical nature causing the observed negative flatband voltage shifts in our metal-insulator-semiconductor planar capacitor structures, where hydrogen induced unstable fast and slow donor type interface states are hypothesized to be the root cause of the observed shifts. We suggest that atomic hydrogen is released from the dielectric during electron injection and migrates to the interfacial region. Our model is further supported by an observed irreversible SILC change during the recovery and anneal studies. The degradation mechanism proposed in this work, supported by the low field lifetime data, provides a feasible explanation for intrinsic low-k dielectric failure.

  10. Mechanism of Calcium Lactate Facilitating Phytic Acid Degradation in Soybean during Germination.

    PubMed

    Hui, Qianru; Yang, Runqiang; Shen, Chang; Zhou, Yulin; Gu, Zhenxin

    2016-07-13

    Calcium lactate facilitates the growth and phytic acid degradation of soybean sprouts, but the mechanism is unclear. In this study, calcium lactate (Ca) and calcium lactate with lanthanum chloride (Ca+La) were used to treat soybean sprouts to reveal the relevant mechanism. Results showed that the phytic acid content decreased and the availability of phosphorus increased under Ca treatment. This must be due to the enhancement of enzyme activity related to phytic acid degradation. In addition, the energy metabolism was accelerated by Ca treatment. The energy status and energy metabolism-associated enzyme activity also increased. However, the transmembrane transport of calcium was inhibited by La(3+) and concentrated in intercellular space or between the cell wall and cell membrane; thus, Ca+La treatment showed reverse results compared with those of Ca treatment. Interestingly, gene expression did not vary in accordance with their enzyme activity. These results demonstrated that calcium lactate increased the rate of phytic acid degradation by enhancing growth, phosphorus metabolism, and energy metabolism. PMID:27324823

  11. Determination of the in vivo degradation mechanism of PEGDA hydrogels3

    PubMed Central

    Browning, M.B.; Cereceres, S.N.; Luong, P.T.; Cosgriff-Hernandez, E.M.

    2014-01-01

    Poly(ethylene glycol) (PEG) hydrogels are one of the most extensively utilized biomaterials systems due to their established biocompatibility and highly tunable properties. It is widely acknowledged that traditional acrylate-derivatized PEG (PEGDA) hydrogels are susceptible to slow degradation in vivo and are therefore unsuitable for long-term implantable applications. However, there is speculation whether the observed degradation is due to hydrolysis of endgroup acrylate esters or oxidation of the ether backbone both of which are possible in the foreign body response to implanted devices. PEG diacrylamide (PEGDAA) is a polyether-based hydrogel system with similar properties to PEGDA but with amide linkages in place of the acrylate esters. This provides a hydrolytically-stable control that can be used to isolate the relative contributions of hydrolysis and oxidation to the in vivo degradation of PEGDA. Here we show that PEGDAA hydrogels remained stable over 12 weeks of subcutaneous implantation in a rat model while PEGDA hydrogels underwent significant degradation as indicated by both increased swelling ratio and decreased modulus. As PEGDA and PEGDAA have similar susceptibility to oxidation, these results demonstrate for the first time that the primary in vivo degradation mechanism of PEGDA is hydrolysis of the endgroup acrylate ester. Additionally, the maintenance of PEGDAA hydrogel properties in vivo indicates their suitability for long-term implants. These studies serve to elucidate key information about a widely used biomaterial system to allow for better implantable device design and to provide a biostable replacement option for PEGDA in applications that require long-term stability. PMID:24464985

  12. Molecular mechanisms in aging and current strategies to counteract sarcopenia.

    PubMed

    Sakuma, Kunihiro; Yamaguchi, Akihiko

    2010-07-01

    Sarcopenia, the progressive loss of muscle mass with age, is characterized by a deterioration of muscle quantity and quality leading to a gradual slowing of movement and a decline in strength and power. Sarcopenia is a highly significant public health problem. Since these age-related changes in skeletal muscle are largely attributed to various molecular mediators affecting fiber size, mitochondrial homeostatis, and apoptosis, the mechanisms responsible for these deleterious changes present numerous therapeutic targets for drug discovery. We and other researchers demonstrated that a disruption of Akt-mTOR and RhoA-SRF signaling but not Atrogin-1 or MuRF1 contributes to sarcopenia. In addition, sarcopenia seems to include a marked loss of fibers attributable to apoptosis. This review deals with molecular mechanisms of muscle atrophy and provides an update on current strategies (resistance training, myostatin inhibition, treatment with amino acids or testosterone, calorie restriction, etc) for counteracting this loss. Resistance training in combination with amino acid-containing nutrition would be the best candidate to attenuate, prevent, or ultimately reverse age-related muscle wasting and weakness. PMID:20158492

  13. Aging mechanisms for steel components of high-level waste storage tanks

    SciTech Connect

    Weeks, J.; Bandyopadhyay, K.; Bush, S.; Kassir, M.; Mather, B.; Shewmon, P.; Streicher, M.; Thompson, B.; van Rooyen, D.

    1995-05-01

    High level storage tanks in service at the present time were fabricated from either carbon steel or low-carbon stainless steel, in each case surrounded by a concrete vault. A variety of potential degradation mechanisms may affect these steel tanks, including corrosion, stress-corrosion cracking, fatigue, radiation, erosion, and hydrogen embrittlement. Historically, some of the non-stress-relieved carbon steel tanks have leaked; in the only failure analysis performed to date, stress corrosion cracking in the heat-affected zone (HAZ) of the weld was identified as the cause. Potentially significant aging mechanisms include general corrosion, pitting and/or crevice corrosion stress-corrosion cracking, microbiologically-induced corrosion, concentration cell attack, and corrosion of external tank surfaces by in-leakage of ground water. Aging mechanisms which are deemed non-significant include thermal and radiation embrittlement, creep and stress relaxation, fatigue, erosion and erosion/corrosion wear, and hydrogen embrittlement. Justification for the potential significance or non-significance for each mechanism is provided, based on the current understanding of these processes and the environments to which the tanks are exposed.

  14. Peroxisome homeostasis: Mechanisms of division and selective degradation of peroxisomes in mammals.

    PubMed

    Honsho, Masanori; Yamashita, Shun-ichi; Fujiki, Yukio

    2016-05-01

    Peroxisome number and quality are maintained by its biogenesis and turnover and are important for the homeostasis of peroxisomes. Peroxisomes are increased in number by division with dynamic morphological changes including elongation, constriction, and fission. In the course of peroxisomal division, peroxisomal morphogenesis is orchestrated by Pex11β, dynamin-like protein 1 (DLP1), and mitochondrial fission factor (Mff). Conversely, peroxisome number is reduced by its degradation. Peroxisomes are mainly degraded by pexophagy, a type of autophagy specific for peroxisomes. Upon pexophagy, an adaptor protein translocates on peroxisomal membrane and connects peroxisomes to autophagic machineries. Molecular mechanisms of pexophagy are well studied in yeast systems where several specific adaptor proteins are identified. Pexophagy in mammals also proceeds in a manner dependent on adaptor proteins. In this review, we address the recent progress in studies on peroxisome morphogenesis and pexophagy. PMID:26434997

  15. Mechanical degradation of cold-worked 304 stainless steel in salt spray environments

    NASA Astrophysics Data System (ADS)

    Chiang, M. F.; Hsu, H. H.; Young, M. C.; Huang, J. Y.

    2012-03-01

    Saline corrosion is one of the major degradation mechanisms for stainless steel 304 (SS304) spent fuel canisters during the dry storage period. Slow strain rate tensile tests (SSRT) were conducted to determine the tensile strength and notched tensile strength (NTS) of cold-rolled SS304 in 0.5 and 5 wt% saline spray environments at 358 K. The YS and UTS of the steels did not decrease significantly in the 0.5 wt% saline spray environment, but a remarkable decrease in elongation was observed in the 5 wt% saline spray. Furthermore, a notch could exacerbate the saline corrosion degradation and aggravate the hydrogen embrittlement of SS304. The cold work of higher degrees could slightly improve SCC resistance of the SS304 under the lower chloride containing spray. However, the NaCl concentration is a crucial factor affecting the SCC susceptibility of SS304.

  16. Comparison of different low-temperature aging protocols: its effects on the mechanical behavior of Y-TZP ceramics.

    PubMed

    Pereira, G K R; Muller, C; Wandscher, V F; Rippe, M P; Kleverlaan, C J; Valandro, L F

    2016-07-01

    This study evaluated the effect of different protocols of low-temperature degradation simulation on the mechanical behavior (structural reliability and flexural strength), the surface topography (roughness), and phase transformation of a Y-TZP ceramic. Disc-shaped specimens (1.2mm×12mm, Lava Frame, 3M ESPE, Seefeld, Germany) were manufactured according to ISO:6872-2008 and divided (n=30) according to the aging protocol executed: "Ctrl" - as-sintered - without any treatment; "Dist Water" - stored at distilled water at 37°C for 365 days; "MC" mechanical cycling into two steps: First - 200N, 2.2Hz for 2.000.000 cycles, Second - 450N, 10Hz for 1.000.000 cycles; "Aut" - steam autoclave at 134°C, 2bar (200kPa) for 20h; "Aut+MC"- Aut and MC methods. Roughness analysis (μm) showed, for Ra parameter, higher statistically significant values for Ctrl 0.68 (0.27), while for Rz parameter, the highest values were observed for Ctrl 4.43(1.53) and Aut 2.24 (0.62). Surface topography analysis showed that none aging method promoted surface alterations when compared to control group. Phase transformation analysis showed that all aging methods promoted an increase in m-phase content (Ctrl: 0.94%, Dist Water: 20.73%, MC: 9.47%, Aut: 53.33% and Aut+MC: 61.91%). Weibull Analysis showed higher statistical characteristic strength values for Aut (1033.36MPa) and Dist Water (1053.76MPa). No aging method promoted deleterious impact either on the biaxial flexural strengths or on the structural reliabilities (Weibull moduli). Also, none of the aging methods promoted reduction of Y-TZP mechanical properties; thus the development of new methodologies and the association between mechanical stimuli and hydrothermal degradation should be considered to better understand the mechanism of low-temperature degradation. PMID:26921592

  17. Mechanism of Inflammation in Age-Related Macular Degeneration

    PubMed Central

    Parmeggiani, Francesco; Romano, Mario R.; Costagliola, Ciro; Semeraro, Francesco; Incorvaia, Carlo; D'Angelo, Sergio; Perri, Paolo; De Palma, Paolo; De Nadai, Katia; Sebastiani, Adolfo

    2012-01-01

    Age-related macular degeneration (AMD) is a multifactorial disease that represents the most common cause of irreversible visual impairment among people over the age of 50 in Europe, the United States, and Australia, accounting for up to 50% of all cases of central blindness. Risk factors of AMD are heterogeneous, mainly including increasing age and different genetic predispositions, together with several environmental/epigenetic factors, that is, cigarette smoking, dietary habits, and phototoxic exposure. In the aging retina, free radicals and oxidized lipoproteins are considered to be major causes of tissue stress resulting in local triggers for parainflammation, a chronic status which contributes to initiation and/or progression of many human neurodegenerative diseases such as AMD. Experimental and clinical evidences strongly indicate the pathogenetic role of immunologic processes in AMD occurrence, consisting of production of inflammatory related molecules, recruitment of macrophages, complement activation, microglial activation and accumulation within those structures that compose an essential area of the retina known as macula lutea. This paper reviews some attractive aspects of the literature about the mechanisms of inflammation in AMD, especially focusing on those findings or arguments more directly translatable to improve the clinical management of patients with AMD and to prevent the severe vision loss caused by this disease. PMID:23209345

  18. Mechanical, degradation and cytocompatibility properties of magnesium coated phosphate glass fibre reinforced polycaprolactone composites.

    PubMed

    Liu, Xiaoling; Hasan, Muhammad S; Grant, David M; Harper, Lee T; Parsons, Andrew J; Palmer, Graham; Rudd, Chris D; Ahmed, Ifty

    2014-11-01

    Retention of mechanical properties of phosphate glass fibre reinforced degradable polyesters such as polycaprolactone and polylactic acid in aqueous media has been shown to be strongly influenced by the integrity of the fibre/polymer interface. A previous study utilising 'single fibre' fragmentation tests found that coating with magnesium improved the fibre and matrix interfacial shear strength. Therefore, the aim of this study was to investigate the effects of a magnesium coating on the manufacture and characterisation of a random chopped fibre reinforced polycaprolactone composite. Short chopped strand non-woven phosphate glass fibre mats were sputter coated with degradable magnesium to manufacture phosphate glass fibre/polycaprolactone composites. The degradation behaviour (water uptake, mass loss and pH change of the media) of these polycaprolactone composites as well as of pure polycaprolactone was investigated in phosphate buffered saline. The Mg coated fibre reinforced composites revealed less water uptake and mass loss during degradation compared to the non-coated composites. The cations released were also explored and a lower ion release profile for all three cations investigated (namely Na(+), Mg(2+) and Ca(2+)) was seen for the Mg coated composite samples. An increase of 17% in tensile strength and 47% in tensile modulus was obtained for the Mg coated composite samples. Both flexural and tensile properties were investigated and a higher retention of mechanical properties was obtained for the Mg coated fibre reinforced composite samples up to 10 days immersion in PBS. Cytocompatibility study showed both composite samples (coated and non-coated) had good cytocompatibility with human osteosarcoma cell line. PMID:25028389

  19. Molecular and Mechanical Causes of Microtubule Catastrophe and Aging.

    PubMed

    Zakharov, Pavel; Gudimchuk, Nikita; Voevodin, Vladimir; Tikhonravov, Alexander; Ataullakhanov, Fazoil I; Grishchuk, Ekaterina L

    2015-12-15

    Tubulin polymers, microtubules, can switch abruptly from the assembly to shortening. These infrequent transitions, termed "catastrophes", affect numerous cellular processes but the underlying mechanisms are elusive. We approached this complex stochastic system using advanced coarse-grained molecular dynamics modeling of tubulin-tubulin interactions. Unlike in previous simplified models of dynamic microtubules, the catastrophes in this model arise owing to fluctuations in the composition and conformation of a growing microtubule tip, most notably in the number of protofilament curls. In our model, dynamic evolution of the stochastic microtubule tip configurations over a long timescale, known as the system's "aging", gives rise to the nonexponential distribution of microtubule lifetimes, consistent with experiment. We show that aging takes place in the absence of visible changes in the microtubule wall or tip, as this complex molecular-mechanical system evolves slowly and asymptotically toward the steady-state level of the catastrophe-promoting configurations. This new, to our knowledge, theoretical basis will assist detailed mechanistic investigations of the mechanisms of action of different microtubule-binding proteins and drugs, thereby enabling accurate control over the microtubule dynamics to treat various pathologies. PMID:26682815

  20. Outcome at school-age after neonatal mechanical ventilation.

    PubMed

    Gunn, T R; Lepore, E; Outerbridge, E W

    1983-06-01

    103 school-age children (5 to 12 years) who survived mechanical ventilation for neonatal respiratory failure were evaluated for growth, neurological, intellectual, psychological and school function in order to determine those children most at risk for handicap. A major handicap occurred in seven children, preventing attendance at normal school or normal classes. Neurological sequelae were significantly associated with perinatal asphyxia and with birthweights of 1500g or less, and neurological sequelae and socio-economic factors were the major determinants of ability. The effects of the Neonatal Intensive Care Unit (NICU) experience on parents and subsequent parent-child relationships were also investigated: 67 per cent of the mothers were very upset by the experience and many continue to worry excessively about the health of their child. Parents who visited their child in the NICU frequently were significantly more anxious and overprotective, restricting many activities even when the child was of school age. PMID:6873492

  1. Temperature dependent ageing mechanisms in Lithium-ion batteries - A Post-Mortem study

    NASA Astrophysics Data System (ADS)

    Waldmann, Thomas; Wilka, Marcel; Kasper, Michael; Fleischhammer, Meike; Wohlfahrt-Mehrens, Margret

    2014-09-01

    The effects of temperatures in the range of -20 °C to 70 °C on the ageing behaviour of cycled Lithium-ion batteries are investigated quantitatively by electrochemical methods and Post-Mortem analysis. Commercial 18650-type high-power cells with a LixNi1/3Mn1/3Co1/3O2/LiyMn2O4 blend cathode and graphite/carbon anode were used as test system. The cells were cycled at a rate of 1 C until the discharge capacity falls below 80% of the initial capacity. Interestingly, an Arrhenius plot indicates two different ageing mechanisms for the ranges of -20 °C to 25 °C and 25 °C to 70 °C. Below 25 °C, the ageing rates increase with decreasing temperature, while above 25 °C ageing is accelerated with increasing temperature. The aged 18650 cells are inspected via scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), inductively coupled plasma (ICP), measurements of electrode thickness and X-ray diffraction (XRD) after disassembly to learn more about the chemical reasons of the degradation. The effect of different temperatures on the electrode polarizations are evaluated by assembling electrodes in pouch cells with reference electrode as a model system. We find that the dominating ageing mechanism for T < 25 °C is Lithium plating, while for T > 25 °C the cathodes show degeneration and the anodes will be increasingly covered by SEI layers.

  2. Effect of hydrogen on degradation mechanism of zirconium: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Chakraborty, Poulami; Moitra, Amitava; Saha-Dasgupta, Tanusri

    2015-11-01

    Using large scale molecular dynamics simulation, we investigate the deleterious effect of hydrogen in Zr. We consider both dilute and concentrated limit of H. In the dilute and concentrated H limits, we study the effect of 1-5 atomic percentage of hydrogen, and that of ε-ZrH2 precipitate having 5-10 nm diameters, respectively. From the stress-strain curves and micro-structure analysis at different strain values, we characterize the deformation behavior and correlate our result with previously reported mechanisms. We show hydrogen atoms in dilute limit help in dislocation multiplication, following the hydrogen-enhanced localized plasticity mechanism. In the concentrated limit, on the other hand, dislocations and cracks nucleate from precipitate-matrix interface, indicating the decohesion mechanism as primary method for Zr degradation. These findings are corroborated with a nucleation and growth model as expressed in Kolmogorov-Johnson-Mehl-Avrami equation.

  3. Investigation of accelerated stress factors and failure/degradation mechanisms in terrestrial solar cells

    NASA Technical Reports Server (NTRS)

    Lathrop, J. W.

    1983-01-01

    Results of an ongoing research program into the reliability of terrestrial solar cells are presented. Laboratory accelerated testing procedures are used to identify failure/degradation modes which are then related to basic physical, chemical, and metallurgical phenomena. In the most recent tests, ten different types of production cells, both with and without encapsulation, from eight different manufacturers were subjected to a variety of accelerated tests. Results indicated the presence of a number of hitherto undetected failure mechanisms, including Schottky barrier formation at back contacts and loss of adhesion of grid metallization. The mechanism of Schottky barrier formation is explained by hydrogen, formed by the dissociation of water molecules at the contact surface, diffusing to the metal semiconductor interface. This same mechanism accounts for the surprising increase in sensitivity to accelerated stress conditions that was observed in some cells when encapsulated.

  4. Irradiation imposed degradation of the mechanical and electrical properties of electrical insulation for future accelerator magnets

    SciTech Connect

    Polinski, J.; Chorowski, M.; Bogdan, P.; Strychalski, M.; Rijk, G. de

    2014-01-27

    Future accelerators will make extensive use of superconductors made of Nb{sub 3}Sn, which allows higher magnetic fields than NbTi. However, the wind-and-react technology of Nb{sub 3}Sn superconducting magnet production makes polyimide Kapton® non applicable for the coils' electrical insulation. A Nb{sub 3}Sn technology compatible insulation material should be characterized by high radiation resistivity, good thermal conductivity, and excellent mechanical properties. Candidate materials for the electrical insulation of future accelerator's magnet coils have to be radiation certified with respect to potential degradation of their electrical, thermal, and mechanical properties. This contribution presents procedures and results of tests of the electrical and mechanical properties of DGEBA epoxy + D400 hardener, which is one of the candidates for the electrical insulation of future magnets. Two test sample types have been used to determine the material degradation due to irradiation: a untreated one (unirradiated) and irradiated at 77 K with 11 kGy/min intense, 4MeV energy electrons beam to a total dose of 50 MGy.

  5. Prediction of aging degradation of cast stainless steel components in LWR systems

    SciTech Connect

    Chopra, O.K.

    1992-03-01

    A procedure and correlations are presented for predicting Charpy-impact energy, tensile flow stress, fracture toughness J-R curve, and J{sub IC} of aged cast stainless steels from known material information. The ``saturation`` impact strength and fracture toughness of a specific cast stainless steel, i.e., the minimum value that would be achieved for the material after long-term service, is estimated from the chemical composition of the steel. Mechanical properties as a function of time and temperature of reactor service are estimated from impact energy and flow stress of the unaged material and the kinetics of embrittlement, which are also determined from chemical composition. The J{sub IC} values are determined from the estimated J-R curve and flow stress. Examples of estimating mechanical properties of of cast stainless steel components during reactor service are presented. A common ``predicted lower-bound` J-R curve for cast stainless steels of unknown chemical composition is also defined for a given grade of steel, ferrite content, and temperature.

  6. Prediction of aging degradation of cast stainless steel components in LWR systems

    SciTech Connect

    Chopra, O.K.

    1992-03-01

    A procedure and correlations are presented for predicting Charpy-impact energy, tensile flow stress, fracture toughness J-R curve, and J{sub IC} of aged cast stainless steels from known material information. The saturation'' impact strength and fracture toughness of a specific cast stainless steel, i.e., the minimum value that would be achieved for the material after long-term service, is estimated from the chemical composition of the steel. Mechanical properties as a function of time and temperature of reactor service are estimated from impact energy and flow stress of the unaged material and the kinetics of embrittlement, which are also determined from chemical composition. The J{sub IC} values are determined from the estimated J-R curve and flow stress. Examples of estimating mechanical properties of of cast stainless steel components during reactor service are presented. A common predicted lower-bound' J-R curve for cast stainless steels of unknown chemical composition is also defined for a given grade of steel, ferrite content, and temperature.

  7. Microstructural degradation mechanisms during creep in strength enhanced high Cr ferritic steels and their evaluation by hardness measurement

    NASA Astrophysics Data System (ADS)

    Ghassemi Armaki, Hassan; Chen, Ruiping; Kano, Satoshi; Maruyama, Kouichi; Hasegawa, Yasushi; Igarashi, Masaaki

    2011-09-01

    There are two creep regions with different creep characteristics: short-term creep region "H", where precipitates and subgrains are thermally stable, and long-term creep region "L", where thermal coarsening of precipitates and subgrains appear. In region "H", the normalized subgrain size (λ-λ0)/(λ∗-λ0) has a linear relation with creep strain and its slope is 10 ɛ-1. But, region L is the time range in which the static recovery and the strain-induced recovery progress simultaneously. In this region, the static recovery accelerates the strain-induced recovery, and subgrain size is larger than that line which neglects the contribution of the static recovery. In region "L", the Δλ/Δλ∗-strain present a linear relation with a slope 35 ɛ-1. There is a linear relation between hardness and subgrain size. Hardness drop, H0 - H, as a function of Larson-Miller parameter can be a good measure method for assessment of hardness drop and consequently degradation of microstructure. Hardness drop shows an identical slope in creep region "H", whereas hardness drop due to thermal aging and creep in region "L" show together a similar slope. In region "H", degradation of microstructure is mainly due to recovery of subgrains controlled by creep plastic deformation, and precipitates do not have a major role. However, in creep region "L", there are three degradation mechanisms that accelerate creep failure; (1) strain-induced recovery of subgrains due to creep plastic deformation, (2) static-recovery of subgrains and precipitates and (3) strain-induced coarsening of precipitates due to the appearance of static-recovery.

  8. Mechanism of strength degradation for hot corrosion of alpha-SiC

    NASA Technical Reports Server (NTRS)

    Smialek, J. L.; Jacobson, N. S.

    1984-01-01

    Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000%. This hot corrosion attack reduced room temperature strengths by as much as 50%. Strength degradation was porportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is consistent with published values.

  9. Chemical durability and degradation mechanisms of HT9 based alloy waste forms with variable Zr content

    SciTech Connect

    Olson, L. N.

    2015-10-30

    In Corrosion studies were undertaken on alloy waste forms that can result from advanced electrometallurgical processing techniques to better classify their durability and degradation mechanisms. The waste forms were based on the RAW3-(URe) composition, consisting primarily of HT9 steel and other elemental additions to simulate nuclear fuel reprocessing byproducts. The solution conditions of the corrosion studies were taken from an electrochemical testing protocol, and meant to simulate conditions in a repository. The alloys durability was examined in alkaline and acidic brines.

  10. Investigation of Aging Mechanisms in Lean NOx Traps

    SciTech Connect

    Mark Crocker

    2010-03-31

    Lean NO{sub x} traps (LNTs) represent a promising technology for the abatement of NO{sub x} under lean conditions. Although LNTs are starting to find commercial application, the issue of catalyst durability remains problematic. LNT susceptibility to sulfur poisoning is the single most important factor determining effective catalyst lifetime. The NO{sub x} storage element of the catalyst has a greater affinity for SO{sub 3} than it does for NO{sub 2}, and the resulting sulfate is more stable than the stored nitrate. Although this sulfate can be removed from the catalyst by means of high temperature treatment under rich conditions, the required conditions give rise to deactivation mechanisms such as precious metal sintering, total surface area loss, and solid state reactions between the various oxides present. The principle objective of this project was to improve understanding of the mechanisms of lean NO{sub x} trap aging, and to understand the effect of washcoat composition on catalyst aging characteristics. The approach utilized involved detailed characterization of model catalysts prior to and after aging, in tandem with measurement of catalyst performance in NO{sub x} storage and reduction. In this manner, NO{sub x} storage and reduction characteristics were correlated with the evolution of catalyst physico-chemical properties upon aging. Rather than using poorly characterized proprietary catalysts, or simple model catalysts of the Pt/BaO/Al{sub 2}O{sub 3} type (representing the first generation of LNTs), Pt/Rh/BaO/Al{sub 2}O{sub 3} catalysts were employed which also incorporated CeO{sub 2} or CeO{sub 2}-ZrO{sub 2}, representing a model system which more accurately reflects current LNT formulations. Catalysts were prepared in which the concentration of each of the main components was systematically varied: Pt (50, 75 or 100 g/ft{sup 3}), Rh (10 or 20 g/ft{sup 3}), BaO (15, 30 or 45 g/L), and either CeO{sub 2} (0, 50 or 100 g/L) or CeO{sub 2}-ZrO{sub 2} (0, 50

  11. Anticataractogenesis Mechanisms of Curcumin and a Comparison of Its Degradation Products: An in Vitro Study.

    PubMed

    Liao, Jiahn-Haur; Huang, Yi-Shiang; Lin, Yu-Ching; Huang, Fu-Yung; Wu, Shih-Hsiung; Wu, Tzu-Hua

    2016-03-16

    Curcumin (Cur) exhibits anticataractogenesis activity. This study aimed to compare the activities of Cur with those of its degradation products in a series of in vitro lens protein turbidity assays. The results show that Cur (200 μM) ameliorates selenite-induced crystallin aggregation, and the mean OD value was 0.10 ± 0.02 (p < 0.05), which was significantly different from controls (0.15 ± 0.01) after incubating for 3 days. However, Cur did not significantly inhibit calcium-induced proteolysis after incubating for 3 days. Such results were supported by isothermal titration calorimetry observation that Cur binds with selenite but not with calcium. Presence of Cur and the degradation products examined (ferulic acid, cinnamic acid, vanillin, and vanillic acid) indicates significantly protective activities on lens γ-crystallins after UVC exposure for 3 h. Among the compounds examined, only ferulic acid exhibited a significant inhibitory effect against UVB-induced turbidity with a mean OD of 0.32 ± 0.01 (p < 0.05), which was significantly different from controls (0.49 ± 0.02). The previously reported anticataract effects of Cur may stem not only from Cur but also from its degradation products through various cataractogenesis mechanisms in vitro. PMID:26905955

  12. Experimental approach to evaluating environmental degradation mechanisms in bisphenol-A polycarbonate films on metallic substrates

    SciTech Connect

    Webb, J.D.

    1983-11-01

    A technique is presented for in situ study of degradative changes in bisphenol-A polycarbonate (BPA-PC) coatings on metallic substrates. The technique uses a controlled environmental exposure chamber in conjunction with a Fourier transform infrared spectrophotometer. The chamber design permits collection of infrared reflection-absorbance (IR-RA) spectra from a sample undergoing exposure to controlled ultraviolet radiation, gas mixtures, and temperatures. A technique for relating the IR-RA band heights measured with the apparatus to the concentration of polymeric functional groups and reaction products in the coatings is presented. Comparison of the results of uv and ir spectroscopy with those obtained using gel permeation chromatography to determine changes in the molecular weight distribution of the BPA-PC films following exposure enabled identification of several degradation pathways. The major mechanisms, in order of importance, appear to be the first and second photo-Fries rearrangements at carbonyl, and chain scission, also at carbonyl. The quantum yield of the first photo-Fries reaction product, measured using IR-RA, was 0.020+-0.004. Some evidence for photooxidation of the BPA-PC methyl functional groups is also presented. The techniques presented should be applicable to the study of both surface and interfacial degradation, especially with samples having polymer film thicknesses within the optimum range (0.1 to 1.0 ..mu..m).

  13. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    PubMed

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively. PMID:25956186

  14. Cycling stability and degradation mechanism of LiMnPO4 based electrodes

    NASA Astrophysics Data System (ADS)

    Moskon, J.; Pivko, M.; Jerman, I.; Tchernychova, E.; Logar, N. Zabukovec; Zorko, M.; Selih, V. S.; Dominko, R.; Gaberscek, M.

    2016-01-01

    Long term stability of LiMnPO4 particles with a crystallite size between ˜20 and 50 nm covered with a dense native carbon coating (14 wt.%) is demonstrated. More than 500 cycles at a rate of C/20, in the potential window of 2.7-4.5 V and a temperature of 55 °C were achieved. During most of the cycling the average capacity decay was less than 0.06% per cycle. After about 500 cycles a sudden capacity drop was observed. Degradation processes in various stages of cycling were thoroughly examined using a range of techniques. Severe surface film formation, manganese dissolution and degradation of LixMnPO4 accompanied by formation of Li4P2O7 were clearly identified. The good long term stability seems to be due to dense, protective carbon coating. Decomposition is most likely initiated at local defects in the microstructure of pyrolytic carbon coating around LiMnPO4 particles. In addition to known degradation mechanisms of LiMnPO4 we observed pronounced gradual amorphization of the olivine crystallites during long-term cycling at 55 °C. Finally, changes in morphology of the carbon black additive after prolonged cycling are reported and commented.

  15. Degradation mechanisms of nylon separator materials for a nickel-cadmium cell in KOH electrolytes

    SciTech Connect

    Lim, H.S.; Margerum, J.D.; Verzwyvelt, S.A.; Lackner, A.M.; Knechtli, R.C.

    1989-03-01

    Degradation reactions of a nylon 6 battery separator material have been studied in 4-34% aqueous KOH electrolytes at 35/sup 0/-110/sup 0/C. In a Ni/Cd cell, this degradation involves a slow hydrolysis reaction followed by fast electrochemical oxidations of the hydrolysis reaction products. Arrhenius activation energy of the hydrolysis reaction in 34% KOH was 20.0 +- 0.3 kcal/mole. A plot of the hydrolysis rate at 100/sup 0/C vs. hydroxyl ion concentration gave a rate maximum at about 16% KOH, and the mechanism for this effect is discussed. Electrochemical oxidations of the hydrolysis product, 6-aminocaproate ion, appear to proceed rapidly in several sequential steps at a nickel oxide electrode. In a Ni/Cd cell, the combination of nylon separator hydrolysis followed by electrochemical oxidation of the products can seriously degrade the battery lifetime. The rate of the hydrolysis of nylon 66 separator material was approximately one half of that of the nylon 6 material.

  16. Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism.

    PubMed

    Zhao, Weirong; Shi, Huixiang; Wang, Dahui

    2004-12-01

    Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen. PMID:15504479

  17. Biomimetic remineralization as a progressive dehydration mechanism of collagen matrices – implications in the aging of resin-dentin bonds

    PubMed Central

    Kim, Young Kyung; Mai, Sui; Mazzoni, Annalisa; Liu, Yan; Tezvergil-Mutluay, Arzu; Takahashi, Kei; Zhang, Kai; Pashley, David H.; Tay, Franklin R.

    2010-01-01

    Biomineralization is a dehydration process in which water from the intrafibrillar compartments of collagen fibrils are progressively replaced by apatites. As water is an important element that precipitates the lack of durability of resin-dentin bonds, this study examined the use of a biomimetic remineralization strategy as a progressive dehydration mechanism for preserving joint integrity and maintaining adhesive strength after aging. Human dentin surfaces were bonded with dentin adhesives, restored with resin composites and sectioned into sticks containing the adhesive joint. Experimental specimens were aged in a biomimetic analog-containing remineralizing medium and control specimens in simulated body fluid for up to 12 months. Specimens retrieved from the designated periods were examined by transmission electron microscopy for manifestation of water-rich regions using a silver tracer and for collagen degradation within the adhesive joints. Tensile testing was performed to determine the potential loss of bond integrity after aging. Control specimens exhibited severe collagen degradation within the adhesive joint after aging. Remineralized specimens exhibited progressive dehydration as manifested by silver tracer reduction and partial remineralization of water-filled micro-channels within the adhesive joint, as well as intrafibrillar remineralization of collagen fibrils that were demineralized initially as part of the bonding procedure. Biomimetic remineralization as a progressive dehydration mechanism of water-rich, resin-sparse collagen matrices enables those adhesive joints to resist degradation over the 12-month aging period, as verified by the conservation of their tensile bond strengths. The ability of the proof-of-concept biomimetic remineralization strategy to prevent bond degradation warrants further development of clinically-relevant delivery systems. PMID:20304110

  18. Stability and Degradation Mechanisms of Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis.

    PubMed

    Albert, Albert; Lochner, Tim; Schmidt, Thomas J; Gubler, L

    2016-06-22

    Radiation-grafted membranes are a promising alternative to commercial membranes for water electrolyzers, since they exhibit lower hydrogen crossover and area resistance, better mechanical properties, and are of potentially lower cost than perfluoroalkylsulfonic acid membranes, such as Nafion. Stability is an important factor in view of the expected lifetime of 40 000 h or more of an electrolyzer. In this study, combinations of styrene (St), α-methylstyrene (AMS), acrylonitrile (AN), and 1,3-diisopropenylbenzene (DiPB) are cografted into 50 μm preirradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) base film, followed by sulfonation to produce radiation-grafted membranes. The stability of the membranes with different monomer combinations is compared under an accelerated stress test (AST), and the degradation mechanisms are investigated. To mimic the conditions in an electrolyzer, in which the membrane is always in contact with liquid water at elevated temperature, the membranes are immersed in water for 5 days at 90 °C, so-called thermal stress test (TST). In addition to testing in air atmosphere tests are also carried out under argon to investigate the effect of the absence of oxygen. The water is analyzed with UV-vis spectroscopy and ion chromatography. The ion exchange capacity (IEC), swelling degree, and Fourier transform infrared (FTIR) spectra of the membranes are compared before and after the test. Furthermore, energy-dispersive X-ray (EDX) spectroscopic analysis of the membrane cross-section is performed. Finally, the influence of the TST to the membrane area resistance and hydrogen crossover is measured. The stability increases along the sequence St/AN, St/AN/DiPB, AMS/AN, and AMS/AN/DiPB grafted membrane. The degradation at the weak-link, oxygen-induced degradation, and hydrothermal degradation are proposed in addition to the "swelling-induced detachment" reported in the literature. By mitigating the possible paths of degradation, the AMS

  19. Evaluation of Ultrasonic and Thermal Nondestructive Evaluation for the Characterization of Aging Degradation in Braided Composite Materials

    NASA Technical Reports Server (NTRS)

    Martin, Richard E.

    2010-01-01

    This paper examines the ability of traditional nondestructive evaluation (NDE) techniques to measure the degradation of braided polymer composite materials subjected to thermal-humidity cycling to simulate aging. A series of braided composite coupons were examined using immersion ultrasonic and pulsed thermography techniques in the as received condition. These same specimens were then examined following extended thermal-humidity cycling. Results of this examination did not show a significant change in the resulting (NDE) signals.

  20. Differing mechanisms of simple nitrile formation on glucosinolate degradation in Lepidium sativum and Nasturtium officinale seeds.

    PubMed

    Williams, David J; Critchley, Christa; Pun, Sharon; Chaliha, Mridusmita; O'Hare, Timothy J

    2009-01-01

    Glucosinolates are sulphur-containing glycosides found in brassicaceous plants that can be hydrolysed enzymatically by plant myrosinase or non-enzymatically to form primarily isothiocyanates and/or simple nitriles. From a human health perspective, isothiocyanates are quite important because they are major inducers of carcinogen-detoxifying enzymes. Two of the most potent inducers are benzyl isothiocyanate (BITC) present in garden cress (Lepidium sativum), and phenylethyl isothiocyanate (PEITC) present in watercress (Nasturtium officinale). Previous studies on these salad crops have indicated that significant amounts of simple nitriles are produced at the expense of the isothiocyanates. These studies also suggested that nitrile formation may occur by different pathways: (1) under the control of specifier protein in garden cress and (2) by an unspecified, non-enzymatic path in watercress. In an effort to understand more about the mechanisms involved in simple nitrile formation in these species, we analysed their seeds for specifier protein and myrosinase activities, endogenous iron content and glucosinolate degradation products after addition of different iron species, specific chelators and various heat treatments. We confirmed that simple nitrile formation was predominantly under specifier protein control (thiocyanate-forming protein) in garden cress seeds. Limited thermal degradation of the major glucosinolate, glucotropaeolin (benzyl glucosinolate), occurred when seed material was heated to >120 degrees C. In the watercress seeds, however, we show for the first time that gluconasturtiin (phenylethyl glucosinolate) undergoes a non-enzymatic, iron-dependent degradation to a simple nitrile. On heating the seeds to 120 degrees C or greater, thermal degradation of this heat-labile glucosinolate increased simple nitrile levels many fold. PMID:19747700

  1. [Photocatalytic degradation kinetics of perfluorooctanoic acid (PFOA) in TiO2 dispersion and its mechanism].

    PubMed

    Li, Ming-Jie; Yu, Ze-Bin; Chen, Ying; Wang, Li; Liu, Qing; Liu, Yu-Xin; He, Li-Li

    2014-07-01

    Decomposition of perfluorooctanoic acid (PFOA) is of prime importance since it is recognized as a persistent organic pollutant and is widespread in the environment. Heterogeneous photocatalytic decomposition of PFOA by TiO2 (P25) was investigated under 254 nm UV light. Experimental conditions including initial pH, TiO2 content and PFOA concentration, were varied to demonstrate their effects on the decomposition of PFOA. It was observed that the photocatalytic degradation kinetics of PFOA could be fitted to the quasi-first-order equation. The pH played a determinant role in the decomposition of PFOA and the presence of O2 increased the degradation rate. Optimal conditions for a complete removal were obtained using 1.5 g x L(-1) TiO2 at pH 3 in air atmosphere, with a rate constant of 0.420 6 h(-1). The contribution experiments of various reactive species produced during the photocatalysis were also investigated with the addition of different scavengers and it was found that photogenerated holes (h+) was the major reactive species which was responsible for 66.1% of the degradation rate, and the *OH was involved in PFOA degradation as well. In addition, the photocatalytic experiment with the addition of NaF indicated that the adsorption of PFOA was of primary importance for the photocatalytic decomposition. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length as intermediates and products were identified with UPLC-QTOF/MS, and a possible mechanism for PFOA decomposition was proposed. PMID:25244845

  2. Bicycle injuries: a matter of mechanism and age.

    PubMed

    Siman-Tov, Maya; Jaffe, Dena H; Peleg, Kobi

    2012-01-01

    Bicycle riding is a popular form of recreation with positive health and environmental effects. These road users are vulnerable to serious injuries, especially when motor vehicles are involved. The goal of this study was to characterize cyclist-related injuries according to motor vehicle involvement for adults versus children. A retrospective study was carried out using data from 11 trauma centers in the Israeli National Trauma Registry (2001-2007). Injuries were classified according to whether a motor vehicle was involved, and differences in injury characteristics were assessed for adults (18+ years) versus children (1-17 years). A total of 5529 patients were hospitalized for bicycle injuries, of whom 1765 were adults and 3764 were children. Thirty percent (n=1662) of all bicycle injuries involved motor vehicles, although the rate of injuries resulting in hospitalization was 37% among adults and 27% among children. Injury characteristics and hospital resource utilization differed substantially by age group. Cyclists struck by a motor vehicle presented with more severe injuries requiring more hospital resources and resulting in poorer outcomes than those not involved with motor vehicles. The interaction effect between motor vehicle involvement and age was significant for torso injuries and need for medical imaging. We found that injury characteristics, hospital resource utilization and health-related outcomes for bicycle injuries are highly dependent on patient's age and mechanism of injury. Effect modification of motor vehicle involvement by age may in part reflect physicians' attitudes toward pediatric imaging. The risks identified in this study should be used for preparedness and management of trauma hospitalizations from bicycle injuries. PMID:22062347

  3. Distinct mechanisms of impairment in cognitive ageing and Alzheimer's disease.

    PubMed

    Mapstone, Mark; Dickerson, Kathryn; Duffy, Charles J

    2008-06-01

    Similar manifestations of functional decline in ageing and Alzheimer's disease obscure differences in the underlying cognitive mechanisms of impairment. We sought to examine the contributions of top-down attentional and bottom-up perceptual factors to visual self-movement processing in ageing and Alzheimer's disease. We administered a novel heading discrimination task requiring subjects to determine direction of simulated self-movement from left or right offset optic flow fields of several sizes (25 degrees, 40 degrees or 60 degrees in diameter) to 18 Alzheimer's disease subjects (mean age = 75.3, 55% female), 21 older adult control subjects (mean age = 72.4, 67% female), and 26 younger control subjects (mean age = 26.5, 63% female). We also administered computerized measures of processing speed and divided and selective attention, and psychophysical measures of visual motion perception to all subjects. Both older groups showed significant difficulty in judging the direction of virtual self-movement [F(2,194) = 40.5, P < 0.001] and optic flow stimulus size had little effect on heading discrimination for any group. Both older groups showed impairments on measures of divided [F(2,62) = 22.2, P < 0.01] and selective [F(2,62) = 63.0, P < 0.001] attention relative to the younger adult control group, while the Alzheimer's disease group showed a selective impairment in outward optic flow perception [F(2,64) = 6.3, P = 0.003] relative to both control groups. Multiple linear regression revealed distinct attentional and perceptual contributions to heading discrimination performance for the two older groups. In older adult control subjects, poorer heading discrimination was attributable to attentional deficits (R(2) adj = 0.41, P = 0.001) whereas, in Alzheimer's disease patients, it was largely attributable to deficits of visual motion perception (R(2) adj = 0.57, P < 0.001). These findings suggest that successive attentional and perceptual deficits play independent roles in

  4. Determination of the degradation mechanism for polychlorinated biphenyl congeners using mechanically alloyed magnesium/palladium in methanol

    NASA Astrophysics Data System (ADS)

    Devor, Robert William

    Polychlorinated biphenyls are a ubiquitous environmental contaminant that can be found today throughout the world in soils and sediments, lakes and rivers, and flora and fauna. PCBs have percolated throughout the food chain, so that almost every human being has a detectable amount of the contaminant within their blood stream. Existing remediation methods include incineration, dredging and landfilling, and microbial degradation, but all of these methods have drawbacks that limit their effectiveness as treatment options. Recently, the use of zero-valent metals as a means of reductive dechlorination has been explored. Using a combination of zerovalent magnesium and catalytic palladium, a successful bimetallic system capable of degrading PCBs has been created and optimized. Determining the mechanism for the reductive dechlorination has proven to be an arduous task, but experimental evidence has suggested three possible radical-type mechanisms for the use Mg/Pd specifically in methanol (as compared to aqueous systems). These possible mechanisms differ in the type of hydrogen species that replaces the chlorine atom on the PCB. Thermodynamic information has also aided in narrowing down which of the suggested pathways is most likely. It appears likely that the hydrogen involved in the dechlorination has the form of a "hydride-like" radical, which is a form of electron-rich atomic hydrogen. According to the literature, Pd catalysts create this species within the first few subsurface layers of the palladium in the presence of molecular hydrogen. Further work will be necessary to confirm that the "hydride-like" radical is actually the species involved in the dechlorination.

  5. Spermidine mediates degradation of ornithine decarboxylase by a non-lysosomal, ubiquitin-independent mechanism

    SciTech Connect

    Glass, J.R.; Gerner, E.W.

    1987-01-01

    The mechanism of spermidine-induced ornithine decarboxylase (OCD, E.C. 4.1.1.17) inactivation was investigated using Chinese hamster ovary (CHO) cells, maintained in serum-free medium, which display a stabilization of ODC owing to the lack of accumulation of putrescine and spermidine. Treatment of cells with 10 ..mu..M exogenous spermidine leads to rapid decay of ODC activity accompanied by a parallel decrease in enzyme protein. Analysis of the decay of (/sup 35/S)methionine-labeled ODC and separation by two-dimensional electrophoresis revealed no detectable modification in ODC structure during enhanced degradation. Spermidine-mediated inactivation of ODC occurred in a temperature-dependent manner exhibiting pseudo-first-order kinetics over a temperature range of 22-37/sup 0/C. In cultures treated continuously, an initial lag was observed after treatment with spermidine, followed by a rapid decline in activity as an apparent critical concentration of intracellular spermidine was achieved. Treating cells at 22/sup 0/C for 3 hours with 10 ..mu.. M spermidine, followed by removal of exogenous polyamine, and then shifting to varying temperatures, resulted in rates of ODC inactivation identical with that determined with a continuous treatment. Arrhenius analysis showed that polyamine mediated inactivation of ODC occurred with an activation energy of approximately 16 kcal/mol. Treatment of cells with lysosomotrophic agents had no effect of ODC degradation. ODC turnover was not dependent on ubiquitin-dependent proteolysis. These data support the hypothesis that spermidine regulates ODC degradation via a mechanism requiring new protein synthesis, and that this occurs via a non-lysosomal, ubiquitin-independent pathway.

  6. Mechanical Properties Degradation of Teflon(Trademark) FEP Returned from the Hubble Space Telescope

    NASA Technical Reports Server (NTRS)

    Dever, Joyce A.; deGroh, Kim K.; Townsend, Jacqueline A.; Wang, L. Len

    1998-01-01

    After 6.8 years on orbit, degradation has been observed in the mechanical properties of second-surface metalized Teflon(Reg) FEP (fluorinated ethylene propylene) used on the Hubble Space Telescope (HST) on the outer surface of the multi-layer insulation (MLI) blankets and on radiator surfaces. Cracking of FEP surfaces on HST was first observed upon close examination of samples with high solar exposure retrieved during the first servicing mission (SM1) conducted 3.6 years after HST was put into orbit. Astronaut observations and photographs from the second servicing mission (SM2), conducted after 6.8 years on orbit, revealed severe cracks in the FEP surfaces of the MLI on many locations around the telescope. This paper describes results of mechanical properties testing of FEP surfaces exposed for 3.6 years and 6.8 years to the space environment on HST. These tests include tensile testing, surface micro-hardness testing, and bend testing.

  7. Reaction mechanisms and rate constants of waste degradation in landfill bioreactor systems with enzymatic-enhancement.

    PubMed

    Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S

    2014-06-01

    Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. PMID:24759644

  8. Degradation and corresponding failure mechanism for GaN-based LEDs

    NASA Astrophysics Data System (ADS)

    Fu, Jiajia; Zhao, Lixia; Cao, Haicheng; Sun, Xuejiao; Sun, Baojuan; Wang, Junxi; Li, Jinmin

    2016-05-01

    The degradation behaviors of high power GaN-based vertical blue LEDs on Si substrates were measured using in-situ accelerated life test. The results show that the dominant failure mechanism would be different during the operation. Besides that, the corresponding associated failure mechanisms were investigated systematically by using different analysis technologies, such as Scan Electron Microscopy, Reflectivity spectroscopy, Transient Thermal Analysis, Raman Spectra, etc. It is shown that initially, the failure modes were mainly originated from the semiconductor die and interconnect, while afterwards, the following serious deterioration of the radiant fluxes was attributed to the package. The interface material and quality, such as die attach and frame, play an important role in determining the thermal performance and reliability. In addition, the heating effect during the operation will also release the compressive strain in the chip. These findings will help to improve the reliability of GaN-based LEDs, especially for the LEDs with vertical structure.

  9. Degradation mechanism of Cu(In,Ga)Se2 solar cells induced by exposure to air

    NASA Astrophysics Data System (ADS)

    Nishinaga, Jiro; Kamikawa, Yukiko; Koida, Takashi; Shibata, Hajime; Niki, Shigeru

    2016-07-01

    The degradation mechanism of unencapsulated Cu(In,Ga)Se2 (CIGS) solar cells upon exposure to air has been investigated. Exposure to air at room temperature slightly reduces the conversion efficiency of CIGS solar cells. However, this conversion efficiency decreases significantly under damp heat testing at 85 °C and a relative humidity of 85% for 15 h. The shunt resistance and conversion efficiency are completely recovered after removing the side edges of the CIGS solar cells by mechanical scribing. This result suggests that low-resistive layers are formed on the sidewalls of the solar cells during damp heat testing. In addition, alkaline solution etching has been confirmed to be an effective way of removing the low-resistive layers. The low-resistive layers on the sidewalls are identified to be molybdenum oxides and sodium molybdate by Auger electron spectroscopy. After etching the oxides on the sidewalls, the saturation current density and ideality factor are confirmed to be improved.

  10. Trimethylene carbonate and epsilon-caprolactone based (co)polymer networks: mechanical properties and enzymatic degradation.

    PubMed

    Bat, Erhan; Plantinga, Josée A; Harmsen, Martin C; van Luyn, Marja J A; Zhang, Zheng; Grijpma, Dirk W; Feijen, Jan

    2008-11-01

    High molecular weight trimethylene carbonate (TMC) and epsilon-caprolactone (CL) (co)polymers were synthesized. Melt pressed (co)polymer films were cross-linked by gamma irradiation (25 kGy or 50 kGy) in vacuum, yielding gel fractions of up to 70%. The effects of copolymer composition and irradiation dose on the cytotoxicity, surface properties, degradation behavior, and mechanical and thermal properties of these (co)polymers and networks were investigated. Upon incubation with cell culture medium containing extracts of (co)polymers and networks, human foreskin fibroblasts remained viable. For all (co)polymers and networks, cell viabilities were determined to be higher than 94%. The formed networks were flexible, with elastic moduli ranging from 2.7 to 5.8 MPa. Moreover, these form-stable networks were creep resistant under dynamic conditions. The permanent deformation after 2 h relaxation was as low as 1% after elongating to 50% strain for 20 times. The in vitro enzymatic erosion behavior of these hydrophobic (co)polymers and networks was investigated using aqueous lipase solutions. The erosion rates in lipase solution could be tuned linearly from 0.8 to 45 mg/(cm (2) x day) by varying the TMC to CL ratio and the irradiation dose. The copolymers and networks degraded essentially by a surface erosion mechanism. PMID:18855440

  11. Radiation induced oxidative degradation of polymers—III. Effect of radiation on mechanical properties

    NASA Astrophysics Data System (ADS)

    Seguchi, Tadao; Arakawa, Kazuo; Ito, Masayuki; Hayakawa, Naohiro; Machi, Sueo

    The changes of mechanical properties of various kinds of polyethylene (PE) and ethylene-propylene copolymer (EPR) with the irradiation in air, in oxygen of 10 atm, and under vacuum were investigated. The decrease in the elongation ( E b) and the tensile strength ( T b) of PE by the irradiation in oxygen is larger than under vacuum. The changes of E b well reflect the degradation of PE. In case of EPR, the T b decreases sharply with dose in any environments, and the E b decreases under vacuum to a larger extent than in oxygen. The modulus at 200% elongation of EPR increases with dose under vacuum, but decreases in oxygen. When the samples were irradiated in air, the changes of the mechanical properties were the intermediate between oxygen and vacuum and dependent on the ratio of oxidation and non-oxidation layers in the film. The antioxidant (Irganox 1010 or DPPD) mixed in polymers was found to retard effectively the polymer degradation by the irradiation in oxygen.

  12. New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms.

    PubMed

    Ji, Yuefei; Dong, Changxun; Kong, Deyang; Lu, Junhe

    2015-03-21

    The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides. PMID:25544494

  13. Mechanical degradation of biological heart valve tissue induced by low diameter crimping: an early assessment.

    PubMed

    Khoffi, Foued; Heim, Frederic

    2015-04-01

    Transcatheter aortic valve implantation (TAVI) has become today an increasingly attractive procedure to relieve patients from aortic valve disease. However, the procedure requires crimping biological tissue within a metallic stent for low diameter catheter insertion purpose. This step induces specific stress in the leaflets especially when the crimping diameter is small. One concern about crimping is the potential degradations undergone by the biological tissue, which may limit the durability of the valve once implanted. The purpose of the present work is to study the effect of low diameter crimping on the mechanical performances of pericardium valve prototypes. The prototypes were compressed to a diameter of 1mm within braided stents for 20 min. SEM observations performed on crimped material show that crimped leaflets undergo degradations characterized by apparent surface defects. Moreover mechanical extension tests were performed on pericardium strips before and after crimping. The strips (15 mm long, 5mm wide) were taken from both crimped and native leaflets considering 2 different valve diameters, 19 and 21 mm. In order to prevent the premature drying of the pericardium tissue during the procedure, the biological tissue was kept in contact with a formaldehyde solution. Results show that the ultimate strength value decreases nearly by up to 50%. The modifications observed in the material may jeopardize the long term durability of the device. However, further tests are necessary with a larger amount of samples to confirm these early results. PMID:25621851

  14. An investigation on focused electron/ion beam induced degradation mechanisms of conjugated polymers.

    PubMed

    Sezen, Meltem; Plank, Harald; Fisslthaler, Evelin; Chernev, Boril; Zankel, Armin; Tchernychova, Elena; Blümel, Alexander; List, Emil J W; Grogger, Werner; Pölt, Peter

    2011-12-01

    Irradiation damage, caused by the use of beams in the electron microscopes, leads to undesired physical/chemical material property changes or uncontrollable modification of structures that are being processed. Particularly, soft matter such as polymers or biological materials is highly susceptible and very much prone to react on irradiation by electron and ion beams. The effect is even higher when materials are subjected to energetic species such as ions that possess high momentum and relatively low mean path due to their mass. Especially when Ga(+) ions (used as the ion source in Focused Ion Beam (FIB) instruments) are considered, the end-effect might even be the total loss of the material's properties. This paper will discuss the possible types of degradation mechanisms and defect formations that can take place during ion and electron beam irradiation of the conjugated polymers: e.g. polyfluorene (PF) and poly-3-hexylthiophene (P3HT) thin films. For the investigation of the irradiation induced degradation mechanisms in this study, complementary analytical techniques such as Raman Spectroscopy (RS), Infrared Spectroscopy (IR), Electron Energy Loss Spectroscopy (EELS), Atomic Force Microscopy (AFM), and Fluorescence Microscopy including Photoluminescence (PL) and Electroluminescence (EL) Microscopy were applied. PMID:21993473

  15. Degradation and formation of polycyclic aromatic compounds during bioslurry treatment of an aged gasworks soil.

    PubMed

    Lundstedt, Staffan; Haglund, Peter; Oberg, Lars

    2003-07-01

    The goals of this study were to investigate the relative degradation rates of polycyclic aromatic compounds (PACs) in contaminated soil, and to assess whether persistent oxidation products are formed during their degradation. Samples were taken on five occasions during a pilot-scale bioslurry treatment of soil from a former gasworks site. More than 100 PACs were identified in the soil, including unsubstituted polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs), heterocyclic PACs, and oxygenated PAHs (oxy-PAHs), such as ketones, quinones, and coumarins. During the treatment, the low molecular weight PAHs and heterocyclics were degraded faster than the high molecular weight compounds. The unsubstituted PAHs also appear to have degraded more quickly than the corresponding alkyl-PAHs and nitrogen-containing heterocyclics. No new oxidation products that were not present in the untreated soil were identified after the soil treatment. However, oxy-PAHs that were present in the untreated soil were generally degraded more slowly than the parent compounds, suggesting that they were formed during the treatment or that they are more persistent. Two oxidation products, 1-acenaphthenone and 4-oxapyrene-5-one, were found at significantly higher concentrations at the end of the study. Because oxy-PAHs can be acutely toxic, mutagenic, or carcinogenic, we suggest that this group of compounds should also be monitored during the treatment of PAH-contaminated soil. PMID:12836964

  16. Rapid Proteasomal Degradation of Mutant Proteins Is the Primary Mechanism Leading to Tumorigenesis in Patients With Missense AIP Mutations

    PubMed Central

    Hernández-Ramírez, Laura C.; Martucci, Federico; Morgan, Rhodri M. L.; Trivellin, Giampaolo; Tilley, Daniel; Ramos-Guajardo, Nancy; Iacovazzo, Donato; D'Acquisto, Fulvio; Prodromou, Chrisostomos

    2016-01-01

    Context: The pathogenic effect of mutations in the aryl hydrocarbon receptor interacting protein (AIP) gene (AIPmuts) in pituitary adenomas is incompletely understood. We have identified the primary mechanism of loss of function for missense AIPmuts. Objective: This study sought to analyze the mechanism/speed of protein turnover of wild-type and missense AIP variants, correlating protein half-life with clinical parameters. Design and Setting: Half-life and protein–protein interaction experiments and cross-sectional analysis of AIPmut positive patients' data were performed in a clinical academic research institution. Patients: Data were obtained from our cohort of pituitary adenoma patients and literature-reported cases. Interventions: Protein turnover of endogenous AIP in two cell lines and fifteen AIP variants overexpressed in HEK293 cells was analyzed via cycloheximide chase and proteasome inhibition. Glutathione-S-transferase pull-down and quantitative mass spectrometry identified proteins involved in AIP degradation; results were confirmed by coimmunoprecipitation and gene knockdown. Relevant clinical data was collected. Main Outcome Measures: Half-life of wild-type and mutant AIP proteins and its correlation with clinical parameters. Results: Endogenous AIP half-life was similar in HEK293 and lymphoblastoid cells (43.5 and 32.7 h). AIP variants were divided into stable proteins (median, 77.7 h; interquartile range [IQR], 60.7–92.9 h), and those with short (median, 27 h; IQR, 21.6–28.7 h) or very short (median, 7.7 h; IQR, 5.6–10.5 h) half-life; proteasomal inhibition rescued the rapid degradation of mutant proteins. The experimental half-life significantly correlated with age at diagnosis of acromegaly/gigantism (r = 0.411; P = .002). The FBXO3-containing SKP1–CUL1–F-box protein complex was identified as the E3 ubiquitin-ligase recognizing AIP. Conclusions: AIP is a stable protein, driven to ubiquitination by the SKP1–CUL1–F-box protein complex

  17. Aggrecanolysis and in vitro matrix degradation in the immature bovine meniscus: mechanisms and functional implications

    PubMed Central

    2009-01-01

    Introduction Little is known about endogenous or cytokine-stimulated aggrecan catabolism in the meniscal fibrocartilage of the knee. The objectives of this study were to characterize the structure, distribution, and processing of aggrecan in menisci from immature bovines, and to identify mechanisms of extracellular matrix degradation that lead to changes in the mechanical properties of meniscal fibrocartilage. Methods Aggrecanase activity in the native immature bovine meniscus was examined by immunolocalization of the aggrecan NITEGE neoepitope. To investigate mechanisms of cytokine-induced aggrecan catabolism in this tissue, explants were treated with interleukin-1α (IL-1) in the absence or presence of selective or broad spectrum metalloproteinase inhibitors. The sulfated glycosaminoglycan (sGAG) and collagen contents of explants and culture media were quantified by biochemical methods, and aggrecan catabolism was examined by Western analysis of aggrecan fragments. The mechanical properties of explants were determined by dynamic compression and shear tests. Results The aggrecanase-generated NITEGE neoepitope was preferentially localized in the middle and outer regions of freshly isolated immature bovine menisci, where sGAG density was lowest and blood vessels were present. In vitro treatment of explants with IL-1 triggered the accumulation of NITEGE in the inner and middle regions. Middle region explants stimulated with IL-1 exhibited substantial decreases in sGAG content, collagen content, and mechanical properties. A broad spectrum metalloproteinase inhibitor significantly reduced sGAG loss, abrogated collagen degradation, and preserved tissue mechanical properties. In contrast, an inhibitor selective for ADAMTS-4 and ADAMTS-5 was least effective at blocking IL-1-induced matrix catabolism and loss of mechanical properties. Conclusions Aggrecanase-mediated aggrecanolysis, typical of degenerative articular cartilage, may play a physiologic role in the development

  18. Latent Fingermark Aging Patterns (Part I): Minutiae Count as One Indicator of Degradation.

    PubMed

    De Alcaraz-Fossoul, Josep; Mestres Patris, Cristina; Barrot Feixat, Carme; McGarr, Luke; Brandelli, Donna; Stow, Karen; Gené Badia, Manel

    2016-03-01

    The authors are exploring degradation patterns of latent fingermarks over time which can be quantitatively determined in a predictable manner by visual means. Several physical degradation parameters for assessing this hypothesis are evaluated. This article analyzes the parameter "minutiae count" as a function of time. Experiment variables included were secretion type (sebaceous-rich and eccrine-rich), substrate (glass and plastic), and exposure to light (dark, shade, and direct light). Depositions were sequentially visualized with Titanium Dioxide powder over a period of 6 months, photographed, and number of minutiae recorded. Results revealed a significant decrease of minutiae for eccrine-rich marks on glass but insignificant for sebaceous-rich marks on the same surface. However, significant degradation was observed for both types of secretions on plastic. The authors conclude that the distinctive prevalence of minutiae changes over time indicates with a high degree of certainty the hypothesis is valid and deserves additional exploration. PMID:27404605

  19. Physical mechanisms affecting hot carrier-induced degradation in gallium nitride HEMTs

    NASA Astrophysics Data System (ADS)

    Mukherjee, Shubhajit

    Gallium Nitride or GaN-based high electron mobility transistors (HEMTs) is currently the most promising device technology in several key military and civilian applications due to excellent high-power as well as high-frequency performance. Even though the performance figures are outstanding, GaN-based HEMTs are not as mature as some competing technologies, which means that establishing the reliability of the technology is important to enable use in critical applications. The objective of this research is to understand the physical mechanisms affecting the reliability of GaN HEMTs at moderate drain biases (typically VDS < 30 V in the devices considered here). The degradation in device performance is believed to be due to the formation or modification of charged defects near the interface by hydrogen depassivation processes (due to electron-activated hydrogen removal) from energetic carriers. A rate-equation describing the defect generation process is formulated based on this assumption. A combination of ensemble Monte-Carlo (EMC) simulation statistics, ab-initio density functional theory (DFT) calculations, and accelerated stress experiments is used to relate the candidate defects to the overall degradation behavior (VT and gm). The focus of this work is on the 'semi-ON' mode of transistor operation in which the degradation is usually observed to be at its highest. This semi-ON state is reasonably close to the biasing region of class-AB high power amplifiers, which are popular because of the combination of high efficiency and low distortion that is associated with this configuration. The carrier-energy distributions are obtained using an EMC simulator that was developed specifically for III-V HFETs. The rate equation is used to model the degradation at different operating conditions as well as longer stress times from the result of one short duration stress test, by utilizing the carrier-energy distribution obtained from EMC simulations for one baseline condition

  20. Polysorbate 20 Degradation in Biopharmaceutical Formulations: Quantification of Free Fatty Acids, Characterization of Particulates, and Insights into the Degradation Mechanism.

    PubMed

    Tomlinson, Anthony; Demeule, Barthélemy; Lin, Baiwei; Yadav, Sandeep

    2015-11-01

    Polysorbate 20 (PS20), a commonly used surfactant in biopharmaceuticals, showed degradation upon long-term (∼18-36 months) storage of two monoclonal antibody (mAb, mAb-A, and mAb-B) drug products at 2-8 °C. The PS20 degradation resulted in the accumulation of free fatty acids (FFA), which ultimately precipitated to form particles upon long-term storage. This study documents the development, qualification, and application of a method for FFA quantification in soluble and insoluble fraction of protein formulation. The method was applied to the quantification of capric acid, lauric acid, myristic acid, palmitic/oleic acid, and stearic acid in placebo as well as active protein formulations on stability. Quantification of FFA in both the soluble and insoluble fraction of mAb-A and mAb-B provided a better mechanistic understanding of PS20 degradation and the dynamics of subsequent fatty acid particle formation. Additionally, the use of this method for monitoring and quantitation of the FFA on real time storage stability appears to aid in identifying batches with higher probability for particulate formation upon extended storage at 5 °C. PMID:26419339

  1. SORPTION-DESORPTION OF "AGED" ISOXAFLUTOLE AND DIKETONITRILE DEGRADATE IN SOIL

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Isoxaflutole is a relatively new herbicide used for the control of weeds in field corn. The objective of this research was to increase the understanding of the behavior and environmental fate of isoxaflutole and a diketonitrile degradate in soil, particularly to determine the strength of sorption to...

  2. Genome-wide analysis reveals mechanisms modulating autophagy in normal brain aging and in Alzheimer's disease

    PubMed Central

    Lipinski, Marta M.; Zheng, Bin; Lu, Tao; Yan, Zhenyu; Py, Bénédicte F.; Ng, Aylwin; Xavier, Ramnik J.; Li, Cheng; Yankner, Bruce A.; Scherzer, Clemens R.; Yuan, Junying

    2010-01-01

    Dysregulation of autophagy, a cellular catabolic mechanism essential for degradation of misfolded proteins, has been implicated in multiple neurodegenerative diseases. However, the mechanisms that lead to the autophagy dysfunction are still not clear. Based on the results of a genome-wide screen, we show that reactive oxygen species (ROS) serve as common mediators upstream of the activation of the type III PI3 kinase, which is critical for the initiation of autophagy. Furthermore, ROS play an essential function in the induction of the type III PI3 kinase and autophagy in response to amyloid β peptide, the main pathogenic mediator of Alzheimer's disease (AD). However, lysosomal blockage also caused by Aβ is independent of ROS. In addition, we demonstrate that autophagy is transcriptionally down-regulated during normal aging in the human brain. Strikingly, in contrast to normal aging, we observe transcriptional up-regulation of autophagy in the brains of AD patients, suggesting that there might be a compensatory regulation of autophagy. Interestingly, we show that an AD drug and an AD drug candidate have inhibitory effects on autophagy, raising the possibility that decreasing input into the lysosomal system may help to reduce cellular stress in AD. Finally, we provide a list of candidate drug targets that can be used to safely modulate levels of autophagy without causing cell death. PMID:20660724

  3. Arthritis Induces Early Bone High Turnover, Structural Degradation and Mechanical Weakness

    PubMed Central

    Vidal, Bruno; Cascão, Rita; Vale, Ana Catarina; Cavaleiro, Inês; Vaz, Maria Fátima; Brito, José Américo Almeida; Canhão, Helena; Fonseca, João Eurico

    2015-01-01

    Background We have previously found in the chronic SKG mouse model of arthritis that long standing (5 and 8 months) inflammation directly leads to high collagen bone turnover, disorganization of the collagen network, disturbed bone microstructure and degradation of bone biomechanical properties. The main goal of the present work was to study the effects of the first days of the inflammatory process on the microarchitecture and mechanical properties of bone. Methods Twenty eight Wistar adjuvant-induced arthritis (AIA) rats were monitored during 22 days after disease induction for the inflammatory score, ankle perimeter and body weight. Healthy non-arthritic rats were used as controls for compar-ison. After 22 days of disease progression rats were sacrificed and bone samples were collected for histomorphometrical, energy dispersive X-ray spectroscopical analysis and 3-point bending. Blood samples were also collected for bone turnover markers. Results AIA rats had an increased bone turnover (as inferred from increased P1NP and CTX1, p = 0.0010 and p = 0.0002, respectively) and this was paralleled by a decreased mineral content (calcium p = 0.0046 and phos-phorus p = 0.0046). Histomorphometry showed a lower trabecular thickness (p = 0.0002) and bone volume (p = 0.0003) and higher trabecular sepa-ration (p = 0.0009) in the arthritic group as compared with controls. In addition, bone mechanical tests showed evidence of fragility as depicted by diminished values of yield stress and ultimate fracture point (p = 0.0061 and p = 0.0279, re-spectively) in the arthritic group. Conclusions We have shown in an AIA rat model that arthritis induc-es early bone high turnover, structural degradation, mineral loss and mechanical weak-ness. PMID:25617902

  4. Changes in pattern completion – a key mechanism to explain age-related recognition memory deficits?

    PubMed Central

    Vieweg, Paula; Stangl, Matthias; Howard, Lorelei R.; Wolbers, Thomas

    2016-01-01

    Accurate memory retrieval from partial or degraded input requires the reactivation of memory traces, a hippocampal mechanism termed pattern completion. Age-related changes in hippocampal integrity have been hypothesized to shift the balance of memory processes in favor of the retrieval of already stored information (pattern completion), to the detriment of encoding new events (pattern separation). Using a novel behavioral paradigm, we investigated the impact of cognitive aging (1) on recognition performance across different levels of stimulus completeness, and (2) on potential response biases. Participants were required to identify previously learned scenes among new ones. Additionally, all stimuli were presented in gradually masked versions to alter stimulus completeness. Both young and older adults performed increasingly poorly as the scenes became less complete, and this decline in performance was more pronounced in elderly participants indicative of a pattern completion deficit. Intriguingly, when novel scenes were shown, only the older adults showed an increased tendency to identify these as familiar scenes. In line with theoretical models, we argue that this reflects an age-related bias towards pattern completion. PMID:25597525

  5. Mechanism of mechanical strength increase of soda-lime glass by aging

    SciTech Connect

    Han, W.T.; Tomozawa, M. . Dept. of Materials Engineering)

    1989-10-01

    This paper reports on two models proposed to explain the mechanical strength increase of abraded or indented soda-lime glasses upon aging, namely, crack tip blunting and the release of residual tensile stress near the crack tip. To clarify the mechanism, the time dependence of the strengthening of an abraded soda-lime glass was investigated. Effects of aging media, such as moist air, distilled water, 1N HCl and 1N NaOH solutions, as well as the abrasion flaw depth, were determined. The strength increase rate in water of abraded soda-lime glass was compared with those of borosilicate and high-silica glasses. The effect of stressing during aging was also investigated. It was found that the rate of strength increase was faster with decreasing abrasion flaw depth and with decreasing chemical durability. For a given flaw depth, an acidic solution produced the fastest strengthening. The strengthening rate was found to accelerate because of the coaxing effect of stressing during aging. From these observations, it was concluded that the strengthening rates relate to the diffusion process and chemical reactions, especially the alkali-hydrogen (or hydronium) ion-exchange reaction, near the crack tip.

  6. Degradation Mechanisms of an Advanced Jet Engine Service-Retired TBC Component

    NASA Astrophysics Data System (ADS)

    Wu, Rudder T.; Osawa, Makoto; Yokokawa, Tadaharu; Kawagishi, Kyoko; Harada, Hiroshi

    Current use of TBCs is subjected to premature spallation failure mainly due to the formation of thermally grown oxides (TGOs). Although extensive research has been carried out to gain better understanding of the thermo - mechanical and -chemical characteristics of TBCs, laboratory-scale studies and simulation tests are often carried out in conditions significantly differed from the complex and extreme environment typically of a modern gas-turbine engine, thus, failed to truly model service conditions. In particular, the difference in oxygen partial pressure and the effects of contaminants present in the engine compartment have often been neglected. In this respect, an investigation is carried out to study the in-service degradation of an EB-PVD TBC coated nozzle-guide vane. Several modes of degradation were observed due to three factors: 1) presence of residual stresses induced by the thermal-expansion mismatches, 2) evolution of bond coat microstructure and subsequent formation of oxide spinels, 3) deposition of CMAS on the surface of TBC.

  7. Lattice distortion mechanism study of TiO{sub 2} nanoparticles during photocatalysis degradation and reactivation

    SciTech Connect

    Wu, Wenhui; Xue, Xudong; Jiang, Xudong; Zhang, Yupeng; Wu, Yichu; Pan, Chunxu

    2015-05-15

    In this paper, the photocatalytic process of TiO{sub 2} (P25) is directly characterized by using a positron annihilation lifetime spectroscopy (PALS), high-resolution transmission electron microscopy (HRTEM), Photoluminescence spectroscopy (PL) and UV Raman spectroscopy (Raman). The experimental results reveal that: 1) From PALS measurements, because τ{sub 1} and τ{sub 2} values and their intensity (I{sub 1} and I{sub 2}) assigned to the different size and amounts of defects, respectively, their variations indicate the formation of different types and amounts of defects during the absorption and degradation. 2) HRTEM observations show that the lattice images become partly blurring when the methylene blue is fully degradated, and clear again after exposed in the air for 30 days. According to the results, we propose a mechanism that the lattice distortion induces the defects as electron capture sites and provides energy for improving photocatalytic process. Meanwhile, the lattice distortion relaxation after exposing in the air for 30 days perfectly explains the gradual deactivation of TiO{sub 2}, because the smaller vacancy defects grow and agglomerate through the several photocatalytic processes. The instrumental PL and Raman are also used to analyze the samples and approved the results of PALS and HRTEM.

  8. Ozonation of parabens in aqueous solution: kinetics and mechanism of degradation.

    PubMed

    Tay, Kheng Soo; Rahman, Noorsaadah Abd; Abas, Mhd Radzi Bin

    2010-12-01

    This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed. PMID:20875662

  9. Mechanism of the enhanced degradation of pentachlorophenol by ultrasound in the presence of elemental iron.

    PubMed

    Dai, Youzhi; Li, Fenfang; Ge, Fei; Zhu, Fei; Wu, Lanyan; Yang, Xiangzheng

    2006-10-11

    Ultrasound combined with elemental iron (US/Fe(0)) is effective in oxidizing organic contaminants in water. The sonolysis degradation of pentachlorophenol (PCP) was significantly enhanced by a factor of 4.2 with the addition of elemental iron, mainly via reaction with hydroxyl radicals (OH radicals), and the synergistic mechanism of the enhancement in the combined system was investigated. Experiments were performed with (1) sole ultrasonic treatment; (2) ultrasound in presence of iron; (3) ultrasound combined with copper powder as the same particle size as iron powder; (4) ultrasound in presence of Fe(II). It was observed that PCP degradation and OH radicals production were both enhanced in these combined methods, and the pitting on the sonicated iron surface was apparent. These results indicated that the rate enhancements in US/Fe(0) system were attributed to (1) the iron solid effect and the catalysis of Fe(II) produced from corroded-iron with promoting the production of OH radicals; (2) the increased surface area of iron particles by acoustic cavitation with promoting the adsorption process. PMID:16762499

  10. Sequential RNA degradation pathways provide a fail-safe mechanism to limit the accumulation of unspliced transcripts in Saccharomyces cerevisiae

    PubMed Central

    Sayani, Shakir; Chanfreau, Guillaume F.

    2012-01-01

    The nuclear exosome and the nonsense-mediated mRNA decay (NMD) pathways have been implicated in the degradation of distinct unspliced transcripts in Saccharomyces cerevisiae. In this study we show that these two systems can act sequentially on specific unspliced pre-mRNAs to limit their accumulation. Using steady-state and decay analyses, we show that while specific unspliced transcripts rely mostly on NMD or on the nuclear exosome for their degradation, some unspliced RNAs are stabilized only when both the nuclear exosome and NMD are inactivated. We found that the mechanism of degradation of these unspliced pre-mRNAs is not influenced by promoter identity. However, the specificity in the pre-mRNAs degradation pathways can be manipulated by changing the rate of export or retention of these mRNAs. For instance, reducing the nuclear export of pre-mRNAs mostly degraded by NMD results in a higher fraction of unspliced transcripts degraded by the nuclear exosome. Reciprocally, inactivating the Mlp retention factors results in a higher fraction of unspliced transcripts degraded by NMD for precursors normally targeted by the nuclear exosome. Overall, these results demonstrate that a functional redundancy exists between nuclear and cytoplasmic degradation pathways for unspliced pre-mRNAs, and suggest that the degradation routes of these species are mainly determined by the efficiency of their nuclear export rates. The presence of these two sequential degradation pathways for unspliced pre-mRNAs underscores the importance of limiting their accumulation and might serve as a fail-safe mechanism to prevent the expression of these nonfunctional RNAs. PMID:22753783

  11. Mechanical properties and in vitro degradation of self-reinforced radiopaque bioresorbable polylactide fibres.

    PubMed

    Nuutinen, Juha-Pekka; Clerc, Claude; Törmälä, Pertti

    2003-01-01

    The aim of this study was to evaluate the effect of the radiopaque filler, barium sulfate (BaSO4), on the mechanical properties of self-reinforced bioresorbable fibres. The bioresorbable polymer was a copolymer of L- and D-lactide with an L/D monomer ratio of 96:4 (96L/4D PLA). The fibres were manufactured using an extrusion and a drawing process. Three different methods of processing the composites were studied. The materials were blended prior to extrusion. In the first method, the BaSO4 powder was mixed with the polymer granulates by hand (manual blending). The blend was then processed using a twin-screw extruder. The second and third methods utilized a single-screw extruder. In the second method, the BaSO4 powder was manually mixed with the polymer prior to extrusion. In the third method, the BaSO4 powder was mechanically attached on the polymer granulates (mechanical blending) prior to extrusion. The mechanical and chemical properties of the radiopaque bioresorbable fibres were measured after processing and during in vitro degradation. The fibres were gamma, plasma or EtO sterilized. There was no statistical difference in the mechanical properties of the fibres when manufactured using the twin-screw extrusion with manual blending or the single-screw extrusion with mechanical blending. The gamma sterilization markedly decreased the initial intrinsic viscosity of all fibres, whereas the plasma and EtO sterilization methods had no effect on the initial intrinsic viscosity. During in vitro testing, the loss in the intrinsic viscosity occurred at the same rate whether the fibres were loaded with the barium sulfate or not. PMID:12903735

  12. Heterogeneous electro-Fenton using modified iron-carbon as catalyst for 2,4-dichlorophenol degradation: influence factors, mechanism and degradation pathway.

    PubMed

    Zhang, Chao; Zhou, Minghua; Ren, Gengbo; Yu, Xinmin; Ma, Liang; Yang, Jie; Yu, Fangke

    2015-03-01

    Modified iron-carbon with polytetrafluoroethylene (PTFE) was firstly investigated as heterogeneous electro-Fenton (EF) catalyst for 2,4-dichlorophenol (2,4-DCP) degradation in near neutral pH condition. The catalyst was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), and the effects of some important operating parameters such as current intensity and pH on the 2,4-DCP degradation were investigated. After the catalyst modification with 20% PTFE, the degradation performance maintained well with much lower iron leaching, and at current intensity 100 mA, initial pH 6.7, catalyst loading 6 g/L, the degradation efficiency of 2,4-DCP could exceed 95% within 120 min treatment. Two-stage pseudo first-order kinetics of 2,4-DCP degradation was observed, including a slow anodic oxidation stage (first-stage) and much faster heterogeneous EF oxidation (second-stage), in which the automatic drop of pH in the first-stage initiated the Fe(2+) release from micro-electrolysis and thus benefited to the subsequent EF reaction. Aromatic intermediates such as 3,5-dichlorocatechol, 4,6-dichlororesorcinol and 2-chlorohydroquinone were detected by GC-MS. Oxalic acid, acetic acid, formic acid and Cl(-) were quantified by ion chromatograph. Based on these analysis as well as the detection of H₂O₂ and OH, a possible mechanism and degradation pathway for 2,4-DCP were proposed. This work demonstrated that such a heterogeneous EF using cheap modified Fe-C catalyst was promising for organic wastewater treatment in initial neutral pH condition. PMID:25559487

  13. AB044. AGE/RAGE/Akt pathway contributes to prostate cancer cell proliferation by promoting Rb phosphorylation and degradation

    PubMed Central

    Bao, Jiming; Bao, Yawei; Zhao, Shanchao; He, Minyi; Luo, Haihua; Ren, Zhonglu; Lv, Yongjie; Hong, Yingqia

    2016-01-01

    Objective Metabolomic research has revealed that metabolites play an important role in prostate cancer development and progression. Previous studies have suggested that prostate cancer cell proliferation is induced by advanced glycation end products (AGEs) exposure, but the mechanism of this induction remains unknown. This study aim to investigate the molecular mechanisms underlying the proliferative response of prostate cancer cell to the interaction of AGEs and the receptor for advanced glycation end products (RAGE). Methods To investigate this mechanism, we used Western blotting to evaluate the responses of the retinoblastoma (Rb), p-Rb and PI3K/Akt pathway to AGEs stimulation. We also examined the effect of knocking down Rb and blocking the PI3K/Akt pathway on AGEs induced PC-3 cell proliferation. Results Our results indicated that AGE-RAGE interaction enhanced Rb phosphorylation and subsequently decreased total Rb levels. Bioinformatics analysis further indicated a negative correlation between RAGE and RB1 expression in prostate cancer tissue. Furthermore, we observed that AGEs stimulation activated the PI3K/Akt signaling pathway and that blocking PI3K/Akt signaling abrogated AGEs-induced cell proliferation. Conclusions We report, for the first time, that AGE-RAGE interaction enhances prostate cancer cell proliferation by phosphorylation of Rb via the PI3K/Akt signaling pathway.

  14. Degradation Mechanisms of Solution-Processed Planar Perovskite Solar Cells: Thermally Stimulated Current Measurement for Analysis of Carrier Traps.

    PubMed

    Qin, Chuanjiang; Matsushima, Toshinori; Fujihara, Takashi; Potscavage, William J; Adachi, Chihaya

    2016-01-20

    Degradation mechanisms of CH3 NH3 PbI3 -based planar perovskite solar cells (PSCs) are investigated using a thermally stimulated current technique. Hole traps lying above the valence-band edge of the CH3 NH3 PbI3 are detected in PSCs degraded by continuous simulated solar illumination. One source of the hole traps is the photodegradation of CH3 NH3 PbI3 in the presence of water. PMID:26598398

  15. Degradation kinetics and mechanism of antibiotic ceftiofur in recycled water derived from a beef farm.

    PubMed

    Li, Xiaolin; Zheng, Wei; Machesky, Michael L; Yates, Scott R; Katterhenry, Michael

    2011-09-28

    Ceftiofur is a third-generation cephalosporin antibiotic that has been widely used to treat bacterial infections in concentrated animal feeding operations (CAFOs). Land application of CAFO waste may lead to the loading of ceftiofur residues and its metabolites to the environment. To understand the potential contamination of the antibiotic in the environment, the degradation kinetics and mechanisms of ceftiofur in solutions blended with and without the recycled water derived from a beef farm were investigated. The transformation of ceftiofur in aqueous solutions in the presence of the CAFO recycled water was the combined process of hydrolysis and biodegradation. The total degradation rates of ceftiofur at 15 °C, 25 °C, 35 °C, and 45 °C varied from 0.4-2.8×10(-3), 1.4-4.4×10(-3), 6.3-11×10(-3), and 11-17×10(-3) h(-1), respectively, in aqueous solutions blended with 1 to 5% CAFO recycled water. Hydrolysis of ceftiofur increased with incubation temperature from 15 to 45 °C. The biodegradation rates of ceftiofur were also temperature-dependent and increased with the application amounts of the recycled CAFO water. Cef-aldehyde and desfuroylceftiofur (DFC) were identified as the main biodegradation and hydrolysis products, respectively. This result suggests that the primary biodegradation mechanism of ceftiofur was the cleavage of the β-lactam ring, while hydrolytic cleavage occurred at the thioester bond. Unlike DFC and ceftiofur, cef-aldehyde does not contain a β-lactam ring and has less antimicrobial activity, indicating that the biodegradation of ceftiofur in animal wastewater may mitigate the potentially adverse impact of the antibiotic to the environment. PMID:21863813

  16. Processing and mechanical behavior of lamellar structured degradable magnesium-hydroxyapatite implants.

    PubMed

    Ratna Sunil, B; Ganapathy, C; Sampath Kumar, T S; Chakkingal, Uday

    2014-12-01

    Multilayered (laminated) composites exhibit tunable mechanical behavior compared to bulk materials due to the presence of more interfaces and therefore magnesium based composites are gaining wide popularity as biodegradable materials targeted for temporary implant applications. The objective of the present work is to fabricate magnesium based lamellar metal matrix composites (MMCs) for degradable implant applications. Nano-hydroxyapatite (HA) powder was selected as the secondary phase and lamellar structured magnesium-nano-hydroxyapatite (Mg-HA) composites of 8, 10 and 15wt% HA were fabricated by ball milling and spark plasma sintering. It was found that HA particles were coated on the Mg flakes after 20h of ball milling carried out using tungsten carbide (WC) as the milling media. Spark plasma sintering of the milled powders resulted in the formation of lamellar structure of Mg with the presence of HA and magnesium oxide (MgO) at the inter-lamellar sites of the composites. Phase analysis of the milled powder by an X-ray diffraction (XRD) method confirms the presence of HA and MgO along with Mg after sintering. Corrosion behavior of the composites investigated by potentiodynamic polarization tests shows a reduction in the inter-lamellar corrosion with increase in HA content and the best corrosion resistance is found for the Mg-10% HA composite. This composite also exhibits maximum Vickers hardness. Young׳s modulus and fracture toughness measured by nano-indentation method were higher for the Mg-8% HA composite. The results thus suggest that lamellar structured Mg composites with 8% and 10% HA show promise for temporary degradable orthopedic implant applications because of their improved corrosion resistance and superior mechanical properties. PMID:25241282

  17. Potential corrosion and degradation mechanisms of Zircaloy cladding on spent nuclear fuel in a tuff repository

    SciTech Connect

    Rothman, A.J.

    1984-09-01

    A literature review and analysis were made of corrosion and degradation processes applicable to Zircaloy cladding on spent nuclear fuel in a tuff repository. In particular, lifetime sought for the Zircaloy is 10,000 years. Among the potential failure mechanisms examined were: oxidation by steam, air, and water, including the effects of ions whose presence is anticipated in the water; mechanical overload; stress (creep) rupture; stress-corrosion cracking (SCC); and delayed failure due to hydride cracking. The conclusion is that failure due to oxidation is not credible, although a few experiments are suggested to confirm the effect of aqueous fluoride on the Zircaloy cladding. Mechanical overload is not a problem, and failure from stress-rupture does not appear likely based on a modified Larson-Miller analysis. Analysis shows that delayed hydride cracking is not anticipated for the bulk of spent fuel pins. However, for a minority of pins under high stress, there is some uncertainty in the analysis as a result of: (1) uncertainty about crack depths in spent fuel claddings and (2) the effect of slow cooling on the formation of radially oriented hydride precipitates. Experimental resolution is called for. Finally, insufficient information is currently available on stress-corrosion cracking. While evidence is presented that SCC failure is not likely to occur, it is difficult to demonstrate this conclusively because the process is not clearly understood and data are limited. Further experimental work on SCC susceptibility is especially needed.

  18. Thermochemical Degradation Mechanisms for the Reinforced Carbon/Carbon Panels on the Space Shuttle

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Rapp, Robert A.

    1995-01-01

    The wing leading edge and nose cone of the Space Shuttle are fabricated from a reinforced carbon/carbon material (RCC). The material attains its oxidation resistance from a diffusion coating of SiC and a glass sealant. During re-entry, the RCC material is subjected to an oxidizing high temperature environment, which leads to degradation via several mechanisms. These mechanisms include oxidation to form a silica scale, reaction of the SiO2 with the SiC to evolve gaseous products, viscous flow of the glass, and vaporization of the glass. Each of these is discussed in detail. Following extended service and many missions, the leading-edge wing surfaces have exhibited small pinholes. A chloridation/oxidation mechanism is proposed to arise from the NaCl deposited on the wings from the sea-salt laden air in Florida. This involves a local chloridation reaction of the SiC and subsequent re-oxidation at the external surface. Thermodynamic calculations indicate the feasibility of these reactions at active pits. Kinetic calculations predict pore depths close to those observed.

  19. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms.

    PubMed

    Rasmussen, Helena; Sørensen, Hanne R; Meyer, Anne S

    2014-02-19

    The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes for the formation of HMF from glucose and three routes for furfural formation from xylose are possible. In addition, new findings show that biomass monosaccharides themselves can react further to form pseudo-lignin and humins as well as a wide array of other compounds when exposed to high temperatures. Hence, several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing strategies and forms an important basis for the development of new biorefinery products from lignocellulosic biomass as well. PMID:24412507

  20. Degradation mechanism of SiC/super {alpha}{sub 2} composite due to interfacial reaction

    SciTech Connect

    Ochiai, S.; Inoue, T.; Fujita, T.; Hojo, M.; Dudek, H.J.; Leucht, R.

    1999-10-01

    The degradation mechanism of SiC(SCS-6)/Super {alpha}{sub 2} composite due to the interfacial reaction was studied using single-fiber composite specimens fabricated by the sputtering method, heat treated at 1,273 K for various times, and tensile tested at room temperature. The main results are summarized as follows. (1) The tensile strength was reduced with progress of interfacial reaction by the formed defects on the fiber surface, while the formation of the reaction layers in the matrix side was not the direct reason for the reduction. (2) From the fracture mechanical analysis of the experimentally observed relation of the size and shape of the surface defects to the fiber strength, the fracture toughness of the fiber employed in the present work was estimated to be 2 to 4 MPa {radical}m. (3) The change in distribution of strength of the reacted fiber with progressing reaction was simulated successfully by combining the Monte Carlo method with the Weibull distribution function for the strength of the unreacted fiber, the Gumbell distribution function for the maximum effective size of the surface defect of the reacted fiber, and the fracture mechanics.

  1. A synopsis on aging-Theories, mechanisms and future prospects.

    PubMed

    da Costa, João Pinto; Vitorino, Rui; Silva, Gustavo M; Vogel, Christine; Duarte, Armando C; Rocha-Santos, Teresa

    2016-08-01

    Answering the question as to why we age is tantamount to answering the question of what is life itself. There are countless theories as to why and how we age, but, until recently, the very definition of aging - senescence - was still uncertain. Here, we summarize the main views of the different models of senescence, with a special emphasis on the biochemical processes that accompany aging. Though inherently complex, aging is characterized by numerous changes that take place at different levels of the biological hierarchy. We therefore explore some of the most relevant changes that take place during aging and, finally, we overview the current status of emergent aging therapies and what the future holds for this field of research. From this multi-dimensional approach, it becomes clear that an integrative approach that couples aging research with systems biology, capable of providing novel insights into how and why we age, is necessary. PMID:27353257

  2. Capillary electrophoresis with electrospray ionisation-mass spectrometry for the characterisation of degradation products in aged papers.

    PubMed

    Dupont, Anne-Laurence; Seemann, Agathe; Lavédrine, Bertrand

    2012-01-30

    A methodology for capillary electrophoresis/electrospray ionisation mass spectrometry (CE/ESI-MS) was developed for the simultaneous analysis of degradation products from paper among two families of compounds: low molar mass aliphatic organic acids, and aromatic (phenolic and furanic) compounds. The work comprises the optimisation of the CE separation and the ESI-MS parameters for improved sensitivity with model compounds using two successive designs of experiments. The method was applied to the analysis of lignocellulosic paper at different stages of accelerated hygrothermal ageing. The compounds of interest were identified. Most of them could be quantified and several additional analytes were separated. PMID:22284496

  3. The effects of aging for 50,000 hours at 343{degree}C on the mechanical properties of Type 308 stainless steel weldments

    SciTech Connect

    Alexander, D.J.; Nanstad, R.K.

    1995-12-01

    The effects of long-term aging at intermediate temperature on the mechanical properties of type 308 stainless steel weld metals have been studied. Three multipass shielded metal-arc welds with ferrite levels of 4, 8, or 12% were aged up to 50,000 h at 343{degrees}C. Tensile and Charpy V-notch specimens were used to determine the effects of aging on the mechanical properties of the weld metal. Aging had little effect on the yield strength of the weld metal, but did result in a slight increase (approximately 5%) in the ultimate tensile strength. The ferrite content had little effect on the yield strength of the materials, but the ultimate tensile strength increased slightly with higher ferrite content. In contrast to the small effect on the tensile properties, the impact properties were significantly degraded by aging. The extent of the degradation increased with increasing ferrite content and continued to increase with increasing aging time, Spinodal decomposition and the precipitation of G-phase particles in the ferrite phase are believed to be responsible for the degradation of the mechanical properties.

  4. LWR Aging Management Using a Proactive Approach to Control Materials Degradation

    SciTech Connect

    Bond, Leonard J.; Doctor, Steven R.; Cumblidge, Stephen E.; Bruemmer, Stephen M.; Taylor, W Boyd; Hull, Amy; Malik, Shah

    2009-05-12

    Material issues can be the limiting factor for the operation of nuclear power plants. There is growing interest in new and improved philosophies and methodolgies for plant life management, which include the migration from reliance on periodic inservice inspection to include condition-based maintenance. A further step in the development of plant management is the move from proactive responses based on ISI to become proactive, through the investigation of the potential for implementation of a proactive management of materials degradation program and its potential impact on the managements of LWRs

  5. Surface degradation of polymer insulators under accelerated climatic aging in weather-ometer

    SciTech Connect

    Xu, G.; McGrath, P.B.; Burns, C.W.

    1996-12-31

    Climatic aging experiments were conducted on two types of outdoor polymer insulators by using a programmable weather-ometer. The housing materials for the insulators were silicone rubber (SR) and ethylene propylene diene monomer (EPDM). The accelerated aging stresses were comprised of ultraviolet radiation, elevated temperature, temperature cycling, thermal shock and high humidity. Their effects on the insulator surface conditions and electrical performance wee examined through visual inspection and SEM studies, contact angle measurements, thermogravimetric analysis (TGA), energy dispersive spectroscopy (EDS) analysis, and 50% impulse flashover voltage tests. The results showed a significant damage on the insulator surface caused by some of the imposed aging stresses. The EDS analysis suggested a photooxidation process that happened on the insulator surface during the aging period.

  6. Aquaporin-1 Translocation and Degradation Mediates the Water Transportation Mechanism of Acetazolamide

    PubMed Central

    Gao, Junwei; Han, Jing; Pan, Xueyang; Pan, Yan; Tie, Lu; Li, Xuejun

    2012-01-01

    Background Diuretic agents are widely used on the treatment of water retention related diseases, among which acetazolamide (AZA) acts originally as a carbonic anhydrase (CA) inhibitor. Aquaporin-1 (AQP1) being located in renal proximal tubules is required for urine concentration. Previously our lab has reported AZA putatively modulated AQP1. Aim of this study is to testify our hypothesis that regulating AQP1 may mediate diuretic effect of AZA. Methodology/Principal Findings For in vivo study, we utilized Sprague Dawley rats, as well as AQP1 knock-out (AQP1−/−) mice to examine urine volume, and human kidney-2 (HK-2) cell line was used for in vitro mechanism study. In our present study we found that AZA decreased CAs activity initially but the activity gradually recovered. Contrarily, diuretic effect was consistently significant. AQP1 protein expression was significantly decreased on day 7 and 14. By utilizing AQP1−/− mice, we found diuretic effect of AZA was cancelled on day 14, while urine volume continuously increased in wild-type mice. Surface plasmon resonance (SPR) results indicated AQP1 was physiologically bound by myosin heavy chain (MHC), immunoprecipitation and immunofluorescence results confirmed this protein interaction. In vitro study results proved AZA facilitated AQP1 translocation onto cell membrane by promoting interaction with MHC, dependent on ERK/ myosin light chain kinase (MLCK) pathway activation. MHC inhibitor BDM and ERK inhibitor U0126 both abolished above effect of AZA. Eventually AZA induced AQP1 ubiquitination, while proteasome inhibitor MG132 reversed AZA's down-regulating effect upon AQP1. Conclusions/Significance Our results identified AZA exerted diuretic effect through an innovative mechanism by regulating AQP1 and verified its inhibitory mechanism was via promoting MHC-dependent translocation onto cell membrane and then ubiquitin mediated degradation, implicating a novel mechanism and target for diuretic agent discovering

  7. Rapid degradation of phenol by ultrasound-dispersed nano-metallic particles (NMPs) in the presence of hydrogen peroxide: A possible mechanism for phenol degradation in water.

    PubMed

    Singh, Jiwan; Yang, Jae-Kyu; Chang, Yoon-Young

    2016-06-15

    The present study was carried out to investigate the degradation of phenol by ultrasonically dispersed nano-metallic particles (NMPs) in an aqueous solution of phenol. Leaching liquor from automobile shredder residue (ASR) was used to obtain the NMPs. The prepared NMPs were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and by X-ray diffraction (XRD). The SEM images show that the diameters of the NMPs were less than 50 nm. An SEM-EDX elemental analysis reveals that Fe was the most commonly found element (weight %) in the NMPs. The FTIR and XRD peaks indicate the presence of metals oxides on the surfaces of the NMPs. The results of the XPS analysis indicate that various elements (e.g., C, O, Zn, Cu, Mn, Fe) are present on the surfaces of the NMPs. The effects of the NMP dose, the initial solution pH, and of different concentrations of phenol and H2O2 on the phenol degradation characteristics were evaluated. The results of this study demonstrate that phenol degradation can be improved by increasing the amount of NMPs, whereas it is reduced with an increase in the phenol concentration. The degradation of phenol by ultrasonically dispersed NMPs followed the pseudo-first-order kinetics. The probable mechanism of phenol degradation by ultrasonically dispersed NMPs was the oxidation of phenol caused by the hydroxyl radicals produced during the reaction between H2O2 and the NMPs during the ultrasonication process. PMID:27038433

  8. Terrestrial ages of Antarctic meteorites: Implications for concentration mechanisms

    NASA Technical Reports Server (NTRS)

    Schultz, L.

    1986-01-01

    Antarctic meteorites differ from meteorites fallen in other places in their mean terrestrial ages. Boeckl estimated the terrestrial half-life for the disintegration of stone meteorites by weathering under the climatic conditions of the Western United States to be about 3600 years. Antarctic meteorites, however, have terrestrial ages up to 70000 years, indicating larger weathering half-lives. The terrestrial ages of meteorites are determined by their concentration of cosmic-ray-produced radionuclides with suitable half-lives (C-14, Al-26, and Cl-36). These radionuclides have yielded reliable ages for the Antarctic meteorites. The distribution of terrestrial ages of Allan Hills and Yamato meteorites are examined.

  9. Mechanical degradation of TiO2 nanotubes with and without nanoparticulate silver coating.

    PubMed

    Shivaram, Anish; Bose, Susmita; Bandyopadhyay, Amit

    2016-06-01

    The primary objective of this research was to evaluate the extent of mechanical degradation on TiO2 nanotubes on Ti with and without nano-particulate silver coating using two different lengths of TiO2 nanotubes-300nm and ~1µm, which were fabricated on commercially pure Titanium (cp-Ti) rods using anodization method using two different electrolytic mediums-(1) deionized (DI) water with 1% HF, and (2) ethylene glycol with 1% HF, 0.5wt% NH4F and 10% DI water. Nanotubes fabricated rods were implanted into equine cadaver bone to evaluate mechanical damage at the surface. Silver was electrochemically deposited on these nanotubes and using a release study, silver ion concentrations were measured before and after implantation, followed by surface characterization using a Field Emission Scanning Electron Microscope (FESEM). In vitro cell-material interaction study was performed using human fetal osteoblast cells (hFOB) to understand the effect of silver coating using an MTT assay for proliferation and to determine any cytotoxic effect on the cells and to study its biocompatibility. No significant damage due to implantation was observed for nanotubes up to ~1µm length under current experimental conditions. Cell-materials interaction showed no cytotoxic effects on the cells due to silver coating and anodization of samples. PMID:27017285

  10. A conserved mechanism of TOR-dependent RCK-mediated mRNA degradation regulates autophagy

    PubMed Central

    Park, Yoon-Dong; Qiu, Jin; Vural, Ali; Zhang, Nannan; Waterman, Scott R.; Blewett, Nathan H.; Myers, Timothy G.; Maraia, Richard J.; Kehrl, John H.; Uzel, Gulbu; Klionsky, Daniel J.; Williamson, Peter R.

    2015-01-01

    Autophagy is an essential eukaryotic pathway requiring tight regulation to maintain homeostasis and preclude disease. Using yeast and mammalian cells, we report a conserved mechanism of autophagy regulation by RNA helicase RCK family members in association with the decapping enzyme Dcp2. Under nutrient-replete conditions, Dcp2 undergoes TOR-dependent phosphorylation and associates with RCK members to form a complex with autophagy-related (ATG) mRNA transcripts, leading to decapping, degradation and autophagy suppression. Simultaneous with the induction of ATG mRNA synthesis, starvation reverses the process, facilitating ATG mRNA accumulation and autophagy induction. This conserved post-transcriptional mechanism modulates fungal virulence and the mammalian inflammasome, the latter providing mechanistic insight into autoimmunity reported in a patient with a PIK3CD/p110δ gain-of-function mutation. We propose a dynamic model wherein RCK family members, in conjunction with Dcp2, function in controlling ATG mRNA stability to govern autophagy, which in turn modulates vital cellular processes affecting inflammation and microbial pathogenesis. PMID:26098573

  11. Lithium chloride prevents interleukin‐1β induced cartilage degradation and loss of mechanical properties

    PubMed Central

    Yasmin, Habiba; Varone, Anna; Wiles, Anna; Poole, C. Anthony; Knight, Martin M.

    2015-01-01

    ABSTRACT Osteoarthritis is a chronic degenerative disease that affects the articular cartilage. Recent studies have demonstrated that lithium chloride exhibits significant efficacy as a chondroprotective agent, blocking cartilage degradation in response to inflammatory cytokines. However, conflicting literature suggests lithium may affect the physicochemical properties of articular cartilage and thus long‐term exposure may negatively affect the mechanical functionality of this tissue. This study aims to investigate the effect of lithium chloride on the biomechanical properties of healthy and interleukin‐1β treated cartilage in vitro and examines the consequences of long‐term exposure to lithium on cartilage health in vivo. Bovine cartilage explants were treated with lithium chloride for 12 days. Chondrocyte viability, matrix catabolism and the biomechanical properties of bovine cartilage explants were not significantly altered following treatment. Consistent with these findings, long term‐exposure (9 months) to dietary lithium did not induce osteoarthritis in rats, as determined by histological staining. Moreover, lithium chloride did not induce the expression of catabolic enzymes in human articular chondrocytes. In an inflammatory model of cartilage destruction, lithium chloride blocked interleukin‐1β signaling in the form of nitric oxide and prostaglandin E2 release and prevented matrix catabolism such that the loss of mechanical integrity observed with interleukin‐1β alone was inhibited. This study provides further support for lithium chloride as a novel compound for the treatment of osteoarthritis. © 2015 The Authors. Journal of Orthopaedic Research published by Wiley Periodicals, Inc. J Orthop Res 33:1552–1559, 2015. PMID:26174175

  12. Thermal Degradation, Mechanical Properties and Morphology of Wheat Straw Flour Filled Recycled Thermoplastic Composites

    PubMed Central

    Mengeloglu, Fatih; Karakus, Kadir

    2008-01-01

    Thermal behaviors of wheat straw flour (WF) filled thermoplastic composites were measured applying the thermogravimetric analysis and differential scanning calorimetry. Morphology and mechanical properties were also studied using scanning electron microscope and universal testing machine, respectively. Presence of WF in thermoplastic matrix reduced the degradation temperature of the composites. One for WF and one for thermoplastics, two main decomposition peaks were observed. Morphological study showed that addition of coupling agent improved the compatibility between WFs and thermoplastic. WFs were embedded into the thermoplastic matrix indicating improved adhesion. However, the bonding was not perfect because some debonding can also be seen on the interface of WFs and thermoplastic matrix. In the case of mechanical properties of WF filled recycled thermoplastic, HDPE and PP based composites provided similar tensile and flexural properties. The addition of coupling agents improved the properties of thermoplastic composites. MAPE coupling agents performed better in HDPE while MAPP coupling agents were superior in PP based composites. The composites produced with the combination of 50-percent mixture of recycled HDPE and PP performed similar with the use of both coupling agents. All produced composites provided flexural properties required by the ASTM standard for polyolefin-based plastic lumber decking boards.

  13. Rationalizing the mechanism of HMDS degradation in air and effective control of the reaction byproducts

    NASA Astrophysics Data System (ADS)

    Seguin, Kevin; Dallas, Andrew J.; Weineck, Gerald

    2008-03-01

    The concern over molecular contamination on the surfaces of optics continues to grow. Most recently, this concern has focused on siloxane contamination resulting from hexamethyldisilazane (HMDS) which is commonly used as a wafer treatment to improve photoresist adhesion onto wafers. From this process, HMDS vapor can be found within FABs and process tools where it has been linked to issues related to lens hazing. This type of surface contamination is significantly detrimental to the imaging process and is generally corrected by extensive surface cleaning or even lens replacement. Additionally, this type of repair also requires adjustment of the optical axis, thereby contributing to an extended downtime. HMDS is known to be very sensitive to the presence of water and is therefore believed to degrade in humid airstreams. This research focuses on rationalizing the reaction mechanisms of HMDS in dry and humid airstreams and in the presence of several adsorbent surfaces. It is shown that HMDS hydrolyzes in humid air to trimethylsilanol (TMS) and ammonia (NH 3). Furthermore, it is shown that TMS can dimerize in air, or on specific types of adsorption media, to form hexamethyldisiloxane (HMDSO). Additionally, we report on the relative impact of these reaction mechanisms on the removal of both HMDS and its hydrolysis products (TMS, HMDSO and NH 3).

  14. Dynamic mechanical analysis and esterase degradation of dentin adhesives containing a branched methacrylate

    PubMed Central

    Park, Jong-Gu; Ye, Qiang; Topp, Elizabeth M.; Lee, Chi H.; Kostoryz, Elisabet L.; Misra, Anil; Spencer, Paulette

    2010-01-01

    A study of the dynamic mechanical properties and the enzymatic degradation of new dentin adhesives containing a multifunctional methacrylate are described. Adhesives contained 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]-propane (BisGMA), and a new multifunctional methacrylate with a branched side chain-trimethylolpropane mono allyl ether dimethacrylate (TMPEDMA). Adhesives were photopolymerized in the presence of 0, 8 and 16 wt% water to simulate wet bonding conditions in the mouth and compared to control adhesives. The degree of conversion as a function of irradiation time was comparable for experimental and control adhesives. In dynamic mechanical analysis (DMA), broad tan δ peaks were obtained for all samples, indicating that the polymerized networks are heterogeneous; comparison of the full-width-at-half-maximum values obtained from the tan δ curves indicated increased heterogeneity for samples cured in the presence of water and/or containing TMPEDMA. The experimental adhesive showed higher Tg and higher rubbery modulus indicating increased crosslink density as compared to the control. The improvement in esterase resistance afforded by adhesives containing the TMPEDMA is greater when this material is photopolymerized in the presence of water, suggesting better performance in the moist environment of the mouth. The improved esterase resistance of the new adhesive could be explained in terms of the densely crosslinked network structure and/or the steric hindrance of branched alkyl side chains. PMID:19358261

  15. Material Degradation during Isothermal Aging and Thermal Cycling of Hybrid Mica Seal with Ag Interlayer under SOFC Exposure Conditions

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Hardy, John S.; Singh, Prabhakar

    2006-11-01

    Hybrid phlogopite mica seals with silver interlayers were evaluated in terms of materials degradation in a combined isothermal ageing and thermal cycling test. The hybrid mica seal was composed of a phlogopite mica paper sandwiched between two Ag foils. The hybrid micas were first aged at 800oC for ~1,000 hrs in a moist, dilute hydrogen fuel (~2.7% H2/bal. Ar + ~3% H2O), followed by short-term thermal cycling between ~100oC and 800oC. The combined test was repeated for 3 times for a total of 4,000 hrs ageing at 800oC and 119 thermal cycles. The results of high temperature leak rate tests showed very good thermal stability and thermal cycle stability with 800oC leak rates of ~0.02-0.03 sccm/cm. A hybrid mica seal tested in a high water content fuel (30 v% H2O/70 v% H2) demonstrated similar leakage during isothermal ageing and subsequent thermal cycles. Post-mortem analyses showed no extensive reaction between Ag and phlogopite mica as well as no significant mica degradation. Simple calculations to estimate the effect of measured leakage on the open circuit voltage and the total fuel loss for various SOFC stack sizes suggest very small fuel losses for the current hybrid mica seals, indicating that they are good candidates for SOFC sealing applications. Corresponding author: Yeong-Shyung Chou Tel: 509-375-2527, Fax: 509-375-2186, E-mail: yeong-shyung.chou@pnl.gov

  16. Photocatalytic degradation and removal mechanism of ibuprofen via monoclinic BiVO4 under simulated solar light.

    PubMed

    Li, Fuhua; Kang, Yapu; Chen, Min; Liu, Guoguang; Lv, Wenying; Yao, Kun; Chen, Ping; Huang, Haoping

    2016-05-01

    Characterized as by X-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra techniques, BiVO4 photocatalyst was hydrothermally synthesized. The photocatalytic degradation mechanisms of ibuprofen (IBP) were evaluated in aqueous media via BiVO4. Results demonstrated that the prepared photocatalyst corresponded to phase-pure monoclinic scheelite BiVO4. The synthesized BiVO4 showed superior photocatalytic properties under the irradiation of visible-light. The photocatalytic degradation rate of IBP decreased with an increase in the initial IBP concentration. The degradation process followed first-order kinetics model. At an IBP concentration of 10 mg L(-1), while a BiVO4 concentration of 5.0 g L(-1) with pH value of 4.5, the rate of IBP degradation was obtained as 90% after 25 min. The photocatalytic degradation of IBP was primarily accomplished via the generation of superoxide radical (O2(•-)) and hydroxyl radicals ((•)OH). During the process of degradation, part of the (•)OH was converted from the O2(•-). The direct oxidation of holes (h(+)) made a minimal contribution to the degradation of IBP. PMID:26901469

  17. Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

    NASA Technical Reports Server (NTRS)

    Zellner, Reinhard

    1990-01-01

    The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

  18. Type I collagen degradation during tissue repair: comparison of mechanisms following fracture and acute coronary syndromes.

    PubMed

    Stansfield, Rachel; Gossiel, Fatma; Morton, Allison; Newman, Christopher; Eastell, Richard

    2014-12-01

    There is turnover of type I collagen during tissue repair. The degradation of type I collagen by matrix metalloproteinases (MMPs) is reflected by serum ICTP and that by cathepsins by CTX-I. There is evidence for increases in ICTP after acute coronary syndromes (ACS) and in CTX-I during fracture repair. The involvement of the MMP pathway in fracture repair and cathepsins after myocardial infarction is unclear. We studied 74 men; 22 were admitted to the hospital on the day of their ACS (ST or non-ST elevation myocardial infarction) (mean age 56 years, range 39 to 82) and 9 attended hospital on the day of their tibial shaft fracture (mean age 33 years, range 21 to 79); we had 43 age-matched controls (mean age 54 years, range 20 to 82). Subjects with ACS and tibial shaft fracture were followed up for up to one year; control subjects were used to establish a reference interval. We measured serum ICTP by ELISA (reference interval 1.1 to 17.6 ng/mL) and CTX-I by chemiluminescence (reference interval 0.094 to 0.991 ng/mL). After ACS, the mean ICTP increased from 5.41 to 6.60 ng/mL within one day of admission (p<0.05); the mean CTX-I increased from 0.263 to 0.414 ng/mL (p<0.05). In two cases, the CTX increased to above the reference interval. After tibial shaft fracture, the mean ICTP increased from 5.51 to maximum of 8.71 ng/mL within 28 days of admission (p<0.01); the mean CTX increased from 0.200 to 0.374 ng/mL (p<0.001). In four cases, the CTX increased to above the reference interval. We conclude that the MMP and cathepsin pathways are both implicated in tissue repair in the bone and heart. This may have clinical implications; drugs that block either pathway (TIMPs, cathepsin K inhibitors) may affect the repair of both tissues. PMID:25193029

  19. The mechanism study of efficient degradation of hydrophobic nonylphenol in solution by a chemical-free technology of sonophotolysis.

    PubMed

    Xu, L J; Chu, W; Lee, Po-Heng; Wang, Jian

    2016-05-01

    Nonylphenol is a hydrophobic endocrine disrupting compound, which can inhibit the growth of sewage bacteria in biological processes. This study investigated the degradation of 4-n-nonylphenol (NP) in water by a chemical-free technology of sonophotolysis with emphasis on the impacts of several important parameters, including light intensity, solution pH, two commonly seen inorganic ions (i.e. NO3(-) and HCO3(-)), and principally on the examination of degradation mechanisms. It was found that, solution pH could significantly influence both NP degradation efficiency and the synergistic effect of sonophotolytic process, where higher synergistic effect was obtained at more acidic condition. In addition, the presence of NO3(-) accelerated NP degradation by both acting as a photosensitizer and providing NO2 radicals, while HCO3(-) had little effect on NP degradation. Identification of intermediates of NP degradation indicated that NP sonophotolysis was mainly initiated by the formation of hydroxy-NP, and a new intermediate di-hydroxy-NP was identified for the first time ever in this study. Through thermodynamic analysis, results indicated that both ortho- and meta-hydroxy-NP species can coexist in the solution but the ortho-4-NBZQ (4-nonyl-benzoquinone) is dominant. In addition, the mechanism of ortho-hydroxy-NP formation was suggested by the addition of HO and H radicals. PMID:26855185

  20. Effect of ozone on degradation and mRNA levels of Rubisco in relation to potato leaf age

    SciTech Connect

    Eckardt, N.A.; Pell, E.J. )

    1993-05-01

    Leaf senescence is characterized by loss of the major photosynthetic enzyme, Ribulose bisphosphate carboxylase (Rubisco). Exposure to ozone (O[sub 3]) is often associated with a premature decline in the quantity of this enzyme. Declines in Rubisco quantity could arise through inhibition of synthesis or enhancement of degradation. Several experiments were conducted to investigate the effect of O[sub 3] on these events in immature and mature leaves of potato. The effect of O[sub 3] on Rubisco synthesis was investigated indirectly by measuring the relative quantities of mRNA for the rubisco large (rbcL) and small (rbcS) subunits following a 5 hour exposure to 0.309 [mu]L L[sup [minus]1] O[sup 3] or charcoal-filtered air. O[sup 3] treatment was associated with a significant loss in rbcS mRNA in immature and mature potato leaves sampled immediately following the exposure. After the O[sup 3] exposure, a set of plants was placed in the dark at 30 C for two days. Levels of rbcS mRNA declined rapidly during the first twelve hours of dark incubation, thus declines in Rubisco quantity following two days of dark incubation were ascribed to degradation. Enhanced degradation due to O[sub 3] during the dark incubation was observed in the mature leaves, but not in the immature leaves. We conclude that O[sub 3] can cause both inhibited synthesis and enhanced degradation of Rubisco, and the response in dependent on leaf age.

  1. Effect of UV aging on degradation of Ethylene-vinyl Acetate (EVA) as encapsulant in photovoltaic (PV) modules

    NASA Astrophysics Data System (ADS)

    Badiee, Amir; Wildman, Ricky; Ashcroft, Ian

    2014-10-01

    A lifetime of 20-30 years is generally regarded as necessary for photovoltaic modules to achieve economic break even. As a consequence, understanding how to improve the durability and reliability of the modules is becoming a necessity. Photovoltaic modules are exposed to extremely harsh conditions of heat, humidity, and ultraviolet (UV) radiation which affect the properties of the encapsulant material and cause yellowing, delamination and degradation of the material, which knock on effects on the performance and the long-term reliability of photovoltaic modules. This study addresses the impact of UV on the photochemical degradation of Ethylene-vinyl Acetate (EVA). Fourier Transform Infrared Spectroscopy in Attenuated Total Reflectance (FTIR-ATR) mode was performed on aged samples. The samples were exposed to UV light from a xenon lamp at 0.68 W/m2 at 340 nm with exposure up to 1000 hours. The FTIR-ATR measurement shows significant changes in the absorption at 1740 cm-1, 1720 cm-1 and 910 cm-1 which correspond to acetate, carboxylic acid and vinyl group respectively. It is shown that the UV exposure is the most significant aging factor. The rate of the photooxidation of EVA is compared by measuring the changes of absorbance at 1720 cm-1 with the UV irradiation time.

  2. Differential Effect of Endurance Training on Mitochondrial Protein Damage, Degradation, and Acetylation in the Context of Aging.

    PubMed

    Johnson, Matthew L; Irving, Brian A; Lanza, Ian R; Vendelbo, Mikkel H; Konopka, Adam R; Robinson, Matthew M; Henderson, Gregory C; Klaus, Katherine A; Morse, Dawn M; Heppelmann, Carrie; Bergen, H Robert; Dasari, Surendra; Schimke, Jill M; Jakaitis, Daniel R; Nair, K Sreekumaran

    2015-11-01

    Acute aerobic exercise increases reactive oxygen species and could potentially damage proteins, but exercise training (ET) enhances mitochondrial respiration irrespective of age. Here, we report a differential impact of ET on protein quality in young and older participants. Using mass spectrometry we measured oxidative damage to skeletal muscle proteins before and after 8 weeks of ET and find that young but not older participants reduced oxidative damage to both total skeletal muscle and mitochondrial proteins. Young participants showed higher total and mitochondrial derived semitryptic peptides and 26S proteasome activity indicating increased protein degradation. ET however, increased the activity of the endogenous antioxidants in older participants. ET also increased skeletal muscle content of the mitochondrial deacetylase SIRT3 in both groups. A reduction in the acetylation of isocitrate dehydrogenase 2 was observed following ET that may counteract the effect of acute oxidative stress. In conclusion aging is associated with an inability to improve skeletal muscle and mitochondrial protein quality in response to ET by increasing degradation of damaged proteins. ET does however increase muscle and mitochondrial antioxidant capacity in older individuals, which provides increased buffering from the acute oxidative effects of exercise. PMID:25504576

  3. Solar photocatalytic degradation of chlorophenols mixture (4-CP and 2,4-DCP): Mechanism and kinetic modelling.

    PubMed

    Abeish, Abdulbasit M; Ang, Ha Ming; Znad, Hussein

    2015-01-01

    The solar-photocatalytic degradation mechanisms and kinetics of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) using TiO2 have been investigated both individually and combined. The individual solar-photocatalytic degradation of both phenolic compounds showed that the reaction rates follow pseudo-first-order reaction. During the individual photocatalytic degradation of both 4-CP and 2,4-DCP under the same condition of TiO2 (0.5 g L(-1)) and light intensities (1000 mW cm(-2)) different intermediates were detected, three compounds associated with 4-CP (hydroquinone (HQ), phenol (Ph) and 4-chlorocatechol (4-cCat)) and two compounds associated with 2,4-DCP (4-CP and Ph). The photocatalytic degradation of the combined mixture (4-CP and 2,4-DCP) was also investigated at the same conditions and different 2,4-DCP initial concentrations. The results showed that the degradation rate of 4-CP decreases when the 2,4-DCP concentration increases. Furthermore, the intermediates detected were similar to that found in the individual degradation but with high Ph concentration. Therefore, a possible reaction mechanism for degradation of this combined mixture was proposed. Moreover, a modified Langmuir-Hinshelwood (L-H) kinetic model considering all detected intermediates was developed. A good agreement between experimental and estimated results was achieved. This model can be useful for scaling-up purposes more accurately as its considering the intermediates formed, which has a significant effect on degrading the main pollutants (4-CP and 2,4-DCP). PMID:25560258

  4. Fracture mechanics applied to the analysis of the degradation of anti-corrosion glass/resin pipes as a function of the fiber/matrix interface quality

    SciTech Connect

    Krawczak, P.; Pabiot, J.

    1995-10-01

    The aim of this paper is to propose a characterization method of the damage of glass/epoxy pipes, based on mode 1 fracture mechanics, making it possible to separate the cracks initiation and cracks propagation mechanisms that exist in practice. In a first part, it is shown that this technique is highly sensitive (in factors 4 to 5) to the fiber/matrix interface quality, the latter being either modified by the use of different sizings or degraded by hydrothermal aging. In a second part, the application of this method to pipes under pressure shows that mode I fracture mechanics tests performed on unidirectionally fiber reinforced flat test pieces monoaxially loaded allow the explanation of the short term as well as long term behavior and damage of complex composite structures under biaxial loading, and this on the basis of the participation of the fiber/matrix interface to the observed phenomena.

  5. Degradation of sucralose in groundwater and implications for age dating contaminated groundwater.

    PubMed

    Robertson, W D; Van Stempvoort, D R; Spoelstra, J; Brown, S J; Schiff, S L

    2016-01-01

    The artificial sweetener sucralose has been in use in Canada and the US since about 2000 and in the EU since 2003, and is now ubiquitous in sanitary wastewater in many parts of the world. It persists during sewage treatment and in surface water environments and as such, has been suggested as a powerful tracer of wastewater. In this study, longer-term persistence of sucralose was examined in groundwater by undertaking a series of three sampling snapshots of a well constrained wastewater plume in Canada (Long Point septic system) over a 6-year period from 2008 to 2014. A shrinking sucralose plume in 2014, compared to earlier sampling, during this period when sucralose use was likely increasing, provides clear evidence of degradation. However, depletion of sucralose from a mean of 40 μg/L in the proximal plume zone, occurred at a relatively slow rate over a period of several months to several years. Furthermore, examination of septic tank effluent and impacted groundwater at six other sites in Canada, revealed that sucralose was present in all samples of septic tank effluent (6-98 μg/L, n = 32) and in all groundwater samples (0.7-77 μg/L, n = 64). Even though sucralose degradation is noted in the Long Point plume, its ubiquitous presence in the groundwater plumes at all seven sites implies a relatively slow rate of decay in many groundwater septic plume environments. Thus, sucralose has the potential to be used as an indicator of 'recent' wastewater contamination. The presence of sucralose identifies groundwater that was recharged after 2000 in Canada and the US and after 2003 in the EU and many Asian countries. PMID:26575474

  6. Investigation of path dependence in commercial lithium-ion cells for pure electric bus applications: Aging mechanism identification

    NASA Astrophysics Data System (ADS)

    Ma, Zeyu; Jiang, Jiuchun; Shi, Wei; Zhang, Weige; Mi, Chunting Chris

    2015-01-01

    There is a growing need to provide more realistic and accurate State of Health estimations for batteries in electric vehicles. Thus, it is necessary to research various lithium-ion cell aging processes, including cell degradation and related path dependence. This paper focuses on quantitative analyses of cell aging path dependence in a repeatable laboratory setting, considering the influence of duty cycles, depth of discharge (DOD), and the frequency and severity of the thermal cycle, as reflected in pure electric buses operated in Beijing. Incremental capacity analysis (ICA) and differential voltage analysis (DVA) are applied to infer cell degradation mechanisms and quantify the attributions to capacity fade. It was observed that the cells experienced a higher rate of aging at 80% DOD and an accelerated aging at 40 °C in the thermal cycling, as a result of possible loss of active material (LAM) in both electrodes, in addition to the loss of lithium inventory (LLI) and inhibited kinetics. The slight capacity fade from low-temperature extremes likely caused by LLI due to lithium plating, whereas the noticeable fade after the high-temperature excursion was likely caused by LAM and hindrance to kinetics. These results may lead to improved battery management in EV applications.

  7. Insulin, Aging, and the Brain: Mechanisms and Implications

    PubMed Central

    Akintola, Abimbola A.; van Heemst, Diana

    2015-01-01

    There is now an impressive body of literature implicating insulin and insulin signaling in successful aging and longevity. New information from in vivo and in vitro studies concerning insulin and insulin receptors has extended our understanding of the physiological role of insulin in the brain. However, the relevance of these to aging and longevity remains to be elucidated. Here, we review advances in our understanding of the physiological role of insulin in the brain, how insulin gets into the brain, and its relevance to aging and longevity. Furthermore, we examine possible future therapeutic applications and implications of insulin in the context of available models of delayed and accelerated aging. PMID:25705204

  8. Mechanical degradation under hydrogen of yttrium doped barium zirconate electrolyte material prepared with NiO additive

    NASA Astrophysics Data System (ADS)

    Ciria, D.; Ben Hassine, M.; Jiménez-Melendo, M.; Iakovleva, A.; Haghi-Ashtiani, P.; Aubin, V.; Dezanneau, G.

    2016-07-01

    Recently, a novel process was presented to fabricate dense yttrium-doped barium zirconate electrolytes with high proton conductivity. This process was based on the use of a NiO additive during reactive sintering. We show here that materials made from this process present a fast degradation of mechanical properties when put in hydrogen-rich conditions, while material made from conventional sintering without NiO aid remains intact in the same conditions. The fast degradation of samples made from reactive sintering, leading to sample failure under highly compressive conditions, is due to the reduction of NiO nanoparticles at grain boundaries as shown from structural and chemical analyses using Transmission Electron Microscopy. By the present study, we alert about the potential risk of cell failure due to this mechanical degradation.

  9. Age of Acquisition: Its Neural and Computational Mechanisms

    ERIC Educational Resources Information Center

    Hernandez, Arturo E.; Li, Ping

    2007-01-01

    The acquisition of new skills over a life span is a remarkable human ability. This ability, however, is constrained by age of acquisition (AoA); that is, the age at which learning occurs significantly affects the outcome. This is most clearly reflected in domains such as language, music, and athletics. This article provides a perspective on the…

  10. Aging and Cortical Mechanisms of Speech Perception in Noise

    ERIC Educational Resources Information Center

    Wong, Patrick C. M.; Jin, James Xumin; Gunasekera, Geshri M.; Abel, Rebekah; Lee, Edward R.; Dhar, Sumitrajit

    2009-01-01

    Spoken language processing in noisy environments, a hallmark of the human brain, is subject to age-related decline, even when peripheral hearing might be intact. The present study examines the cortical cerebral hemodynamics (measured by fMRI) associated with such processing in the aging brain. Younger and older subjects identified single words in…

  11. Aging and Exercise Affect Hippocampal Neurogenesis via Different Mechanisms.

    PubMed

    Yang, Ting-Ting; Lo, Chen-Peng; Tsai, Pei-Shan; Wu, Shih-Ying; Wang, Tzu-Feng; Chen, Yun-Wen; Jiang-Shieh, Ya-Fen; Kuo, Yu-Min

    2015-01-01

    The rate of neurogenesis is determined by 1) the number of neural stem/progenitor cells (NSCs), 2) proliferation of NSCs, 3) neuron lineage specification, and 4) survival rate of the newborn neurons. Aging lowers the rate of hippocampal neurogenesis, while exercise (Ex) increases this rate. However, it remains unclear which of the determinants are affected by aging and Ex. We characterized the four determinants in different age groups (3, 6, 9, 12, 21 months) of mice that either received one month of Ex training or remained sedentary. Bromodeoxyuridine (BrdU) was injected two hours before sacrificing the mice to label the proliferating cells. The results showed that the number of newborn neurons massively decreased (>95%) by the time the mice reached nine months of age. The number of NSC was mildly reduced during aging, while Ex delayed such decline. The proliferation rates were greatly decreased by the time the mice were 9-month-old and Ex could not improve the rates. The rates of neuron specification were decreased during aging, while Ex increased the rates. The survival rate was not affected by age or Ex. Aging greatly reduced newborn neuron maturation, while Ex potently enhanced it. In conclusion, age-associated decline of hippocampal neurogenesis is mainly caused by reduction of NSC proliferation. Although Ex increases the NSC number and neuron specification rates, it doesn't restore the massive decline of NSC proliferation rate. Hence, the effect of Ex on the rate of hippocampal neurogenesis during aging is limited, but Ex does enhance the maturation of newborn neurons. PMID:26147302

  12. Aging and Exercise Affect Hippocampal Neurogenesis via Different Mechanisms

    PubMed Central

    Yang, Ting-Ting; Lo, Chen-Peng; Tsai, Pei-Shan; Wu, Shih-Ying; Wang, Tzu-Feng; Chen, Yun-Wen; Jiang-Shieh, Ya-Fen; Kuo, Yu-Min

    2015-01-01

    The rate of neurogenesis is determined by 1) the number of neural stem/progenitor cells (NSCs), 2) proliferation of NSCs, 3) neuron lineage specification, and 4) survival rate of the newborn neurons. Aging lowers the rate of hippocampal neurogenesis, while exercise (Ex) increases this rate. However, it remains unclear which of the determinants are affected by aging and Ex. We characterized the four determinants in different age groups (3, 6, 9, 12, 21 months) of mice that either received one month of Ex training or remained sedentary. Bromodeoxyuridine (BrdU) was injected two hours before sacrificing the mice to label the proliferating cells. The results showed that the number of newborn neurons massively decreased (>95%) by the time the mice reached nine months of age. The number of NSC was mildly reduced during aging, while Ex delayed such decline. The proliferation rates were greatly decreased by the time the mice were 9-month-old and Ex could not improve the rates. The rates of neuron specification were decreased during aging, while Ex increased the rates. The survival rate was not affected by age or Ex. Aging greatly reduced newborn neuron maturation, while Ex potently enhanced it. In conclusion, age-associated decline of hippocampal neurogenesis is mainly caused by reduction of NSC proliferation. Although Ex increases the NSC number and neuron specification rates, it doesn't restore the massive decline of NSC proliferation rate. Hence, the effect of Ex on the rate of hippocampal neurogenesis during aging is limited, but Ex does enhance the maturation of newborn neurons. PMID:26147302

  13. Degradation Mechanism of Cyanobacterial Toxin Cylindrospermopsin by Hydroxyl Radicals in Homogeneous UV/H2O2 Process

    EPA Science Inventory

    The degradation of cylindrospermopsin (CYN), a widely distributed and highly toxic cyanobacterial toxin (cyanotoxin), remains poorly elucidated. In this study, the mechanism of CYN destruction by UV-254 nm/H2O2 advanced oxidation process (AOP) was investigated by mass spectrometr...

  14. Chelation: A Fundamental Mechanism of Action of AGE Inhibitors, AGE Breakers, and Other Inhibitors of Diabetes Complications

    SciTech Connect

    Nagai, Rhoji; Murray, David B.; Metz, Thomas O.; Baynes, John

    2012-03-01

    Advanced glycation or glycoxidation end-products (AGE) increase in tissue proteins with age, and their rate of accumulation is increased in diabetes, nephropathy and inflammatory diseases. AGE inhibitors include a range of compounds that are proposed to act by trapping carbonyl and dicarbonyl intermediates in AGE formation. However, some among the newer generation of AGE inhibitors lack reactive functional groups that would trap reaction intermediates, indicating an alternative mechanism of action. We propose that AGE inhibitors function primarily as chelators, inhibiting metal-catalyzed oxidation reactions. The AGE-inhibitory activity of angiotensin-converting enzyme inhibitors and angiotensin receptor blockers is also consistent with their chelating activity. Finally, compounds described as AGE breakers, or their hydrolysis products, also have strong chelating activity, suggesting that these compounds also act through their chelating activity. We conclude that chelation is the common, and perhaps the primary, mechanism of action of AGE inhibitors and breakers, and that chronic, mild chelation therapy should prove useful in treatment of diabetes and age-related diseases characterized by oxidative stress, inflammation and increased chemical modification of tissue proteins by advanced glycoxidation and lipoxidation end-products.

  15. Degradation mechanism of alkyl carbonate solvents used in lithium-ion cells during initial charging

    NASA Astrophysics Data System (ADS)

    Yoshida, H.; Fukunaga, T.; Hazama, T.; Terasaki, M.; Mizutani, M.; Yamachi, M.

    The degradation mechanism of electrolytes in the lithium-ion cell with LiCoO 2 and graphite electrodes was investigated by analyzing: (i) the composition of generated gases; (ii) thin films formed on the electrode, and (iii) the compositional change of the electrolyte during the initial charging. The solvents in this work were ethylene carbonate (EC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC). LiPF 6 was used as a salt. In the one- to three-component systems containing EC, carbon monoxide and ethane were detected, whereas Li 2CO 3, RCOOLi and (CH 2OLi) 2 were the main components of the surface film on the negative electrode. From these results, it can be assumed that the decomposition of the systems was mainly due to the reductive reaction of EC at the initial charging. Through the additional analysis of the electrolyte composition, it was confirmed that the dialkyl-2,5-dioxahexane carboxylate was produced in the electrolyte after initial charging. This suggests the occurrence of trans-esterification.

  16. Sonochemical degradation of diclofenac: byproduct assessment, reaction mechanisms and environmental considerations.

    PubMed

    Ziylan, Asu; Dogan, Sifa; Agopcan, Sesil; Kidak, Rana; Aviyente, Viktorya; Ince, Nilsun H

    2014-05-01

    The study covers a thorough assessment of the overall degradation of diclofenac-Na (DCF) by high-frequency ultrasound, focusing particularly on identification, interpretation, and characterization of the oxidation byproducts and their reaction mechanisms. It was found that sonication of 5 mg L(-1) DCF at near neutral pH rendered complete conversion of the compound, 45 % carbon, 30 % chlorine, and 25 % nitrogen mineralization. Density functional theory (DFT) calculations confirmed the experimentally detected major byproduct 2,6-dichloroaniline, the formation of which was explained by OH• addition to the ipso-position of the amino group. The stability of UV absorption at around 276-280 nm throughout reaction was in agreement with the detected byproduct structures, i.e., the presence of amino/amine groups and phenolic, aniline, benzene, and quinine-type derivatives, which all absorbed at around the same band. Microtox toxicity of the reactor aliquots at early reaction showed that initially the reaction products, specifically 1-(2,6-dichlorophenyl)-2-indoline-one, were very toxic; subsequently toxicity exhibited a fluctuating pattern, and a steady declination towards the "non-toxic" level was observed only after 90 min. Oxygen uptake analysis also revealed the formation of harmful products at early reaction, but the reactor was totally biodegradable upon 1-h sonication. PMID:24453014

  17. Mechanism of chlorite degradation to chloride and dioxygen by the enzyme chlorite dismutase.

    PubMed

    Schaffner, Irene; Hofbauer, Stefan; Krutzler, Michael; Pirker, Katharina F; Furtmüller, Paul G; Obinger, Christian

    2015-05-15

    Heme b containing chlorite dismutase (Cld) catalyses the conversion of chlorite to chloride and dioxygen which includes an unusual OO bond formation. This review summarizes our knowledge about the interaction of chlorite with heme enzymes and introduces the biological role, phylogeny and structure of functional chlorite dismutases with differences in overall structure and subunit architecture. The paper sums up the available experimental and computational studies on chlorite degradation by water soluble porphyrin complexes as well as a model based on the active site of Cld. Finally, it reports the available biochemical and biophysical data of Clds from different organisms which allow the presentation of a general reaction mechanism. It includes binding of chlorite to ferric Cld followed by subsequent heterolytic OCl bond cleavage leading to the formation of Compound I and hypochlorite, which finally recombine for production of chloride and O2. The role of the Cld-typical distal arginine in catalysis is discussed together with the pH dependence of the reaction and the role of transiently produced hypochlorite in irreversible inactivation of the enzyme. PMID:25748001

  18. Influence of the intramedullary nail preparation method on nail's mechanical properties and degradation rate.

    PubMed

    Morawska-Chochół, Anna; Chłopek, Jan; Szaraniec, Barbara; Domalik-Pyzik, Patrycja; Balacha, Ewa; Boguń, Maciej; Kucharski, Rafael

    2015-06-01

    When it comes to the treatment of long bone fractures, scientists are still investigating new materials for intramedullary nails and different manufacturing methods. Some of the most promising materials used in the field are resorbable polymers and their composites, especially since there is a wide range of potential manufacturing and processing methods. The aim of this work was to select the best manufacturing method and technological parameters to obtain multiphase, and multifunctional, biodegradable intramedullary nails. All composites were based on a poly(l-lactide) matrix. Either magnesium alloy wires or carbon and alginate fibres were introduced in order to reinforce the nails. The polylactide matrix was also modified with tricalcium phosphate and gentamicin sulfate. The composite nails were manufactured using three different methods: forming from solution, injection moulding and hot pressing. The effect of each method of manufacturing on mechanical properties and degradation rate of the nails was evaluated. The study showed that injection moulding provides higher uniformity and homogeneity of the particle-modified polylactide matrix, whereas hot pressing favours applying higher volume fractions of fibres and their better impregnation with the polymer matrix. Thus, it was concluded that the fabrication method should be individually selected dependently on the nail's desired phase composition. PMID:25842113

  19. Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Ahlborg, Nadia L.; Zhu, Dongming

    2013-01-01

    The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

  20. Degradation mechanism of monosaccharides and xylan under pyrolytic conditions with theoretic modeling on the energy profiles.

    PubMed

    Wang, Shurong; Ru, Bin; Lin, Haizhou; Luo, Zhongyang

    2013-09-01

    Xylan and three monosaccharides (mannose, galactose, and arabinose) were selected as model compounds to investigate the mechanism of hemicellulose pyrolysis. The evolution of several typical pyrolysis products were observed by thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. Monosaccharides underwent similar pyrolysis routes involving ring opening and secondary decomposition. Breakage of the O-acetyl groups and 4-O-methylglucuronic acid units in xylan branches resulted in its different pyrolysis behavior for the formation of acetic acid, CO2, and CO. The detailed reaction pathways of the monosaccharides were studied using density functional theory calculations. Furfural formation was more favorable than the formation of 1-hydroxy-2-propanone and 4-hydroxydihydrofuran-2(3H)-one during xylose degradation. However, in the pyrolysis of mannose and galactose, formation of 5-hydroxymethyl-2-furaldehyde was preferred because of the high energy barrier of the dissociation of the hydroxymethyl group. Meanwhile, the breakage of O-acetyl groups leading to acetic acid formation easily occurred because of its lower energy barrier. PMID:23819973

  1. Molecular mechanism of lysosomal sialidase deficiency in galactosialidosis involves its rapid degradation.

    PubMed Central

    Vinogradova, M V; Michaud, L; Mezentsev, A V; Lukong, K E; El-Alfy, M; Morales, C R; Potier, M; Pshezhetsky, A V

    1998-01-01

    Galactosialidosis is an inherited lysosomal storage disease caused by the combined deficiency of lysosomal sialidase and beta-galactosidase secondary to the deficiency of cathepsin A/protective protein, which is associated with sialidase and beta-galactosidase in a high-molecular weight (1.27MDa) complex. Clinical phenotypes of patients as well as the composition of compounds which are stored in patient's tissues implicate sialidase deficiency as the underlying pathogenic defect. The recent cloning and sequencing of lysosomal sialidase [Pshezhetsky, Richard, Michaud, Igdoura, Wang, Elsliger, Qu, Leclerc, Gravel, Dallaire and Potier (1997), Nature Genet. 15, 316-320] allowed us to study the molecular mechanism of sialidase deficiency in galactosialidosis. By Western blotting, using antibodies against the recombinant human enzyme, and by NH2-terminal sequencing, we showed that sialidase is synthesized as a 45.5 kDa precursor and after the cleavage of the 47-amino acid signal peptide and glycosylation becomes a 48.3 kDa mature active enzyme present in the 1.27 kDa complex. Transgenic expression of sialidase in cultured skin fibroblasts from normal controls and from galactosialidosis patients, followed by immunofluorescent and immunoelectron microscopy showed that in both normal and affected cells the expressed sialidase was localized on lysosomal and plasma membranes, but the amount of sialidase found in galactosialidosis cells was approximately 5-fold reduced. Metabolic labelling studies demonstrated that the 48.3 kDa mature active form of sialidase was stable in normal fibroblasts (half-life approximately 2.7 h), whereas in galactosialidosis fibroblasts the enzyme was rapidly converted (half-life approximately 30 min) into 38.7 and 24 kDa catalytically inactive forms. Altogether our data provide evidence that the molecular mechanism of sialidase deficiency in galactosialidosis is associated with abnormal proteolytic cleavage and fast degradation. PMID:9480870

  2. Carnosine and Homocarnosine Degradation Mechanisms by the Human Carnosinase Enzyme CN1: Insights from Multiscale Simulations.

    PubMed

    Pavlin, Matic; Rossetti, Giulia; De Vivo, Marco; Carloni, Paolo

    2016-05-17

    The endogenous dipeptide l-carnosine, and its derivative homocarnosine, prevent and reduce several pathologies like amytrophic lateral sclerosis (ALS), Alzheimer's disease, and Parkinson's disease. Their beneficial action is severely hampered because of the hydrolysis by carnosinase enzymes, in particular the human carnosinase, hCN1. This belongs to the metallopeptidase M20 family, where a cocatalytic active site is formed by two Zn(2+) ions, bridged by a hydroxide anion. The protein may exist as a monomer and as a dimer in vivo. Here we used hybrid quantum mechanics/molecular mechanics simulations based on the dimeric apoenzyme's structural information to predict the Michaelis complexes with l-carnosine and its derivative homocarnosine. On the basis of our calculations, we suggest that (i) l-carnosine degradation occurs through a nucleophilic attack of a Zn(2+)-coordinated bridging moiety for both monomer and dimer. This mechanistic hypothesis for hCN1 catalysis differs from previous proposals, while it is in agreement with available experimental data. (ii) The experimentally measured higher affinity of homocarnosine for the enzyme relative to l-carnosine might be explained, at least in part, by more extensive interactions inside the monomeric and dimeric hCN1's active site. (iii) Hydrogen bonds at the binding site, present in the dimer but absent in the monomer, might play a role in the experimentally observed higher activity of the dimeric form. Investigations of the enzymatic reaction are required to establish or disprove this hypothesis. Our results may serve as a basis for the design of potent hCN1 inhibitors. PMID:27105448

  3. Thermo-mechanical processing of austenitic steel to mitigate surface related degradation

    NASA Astrophysics Data System (ADS)

    Idell, Yaakov Jonathan

    Thermo-mechanical processing plays an important role in materials property optimization through microstructure modification, required by demanding modern materials applications. Due to the critical role of austenitic stainless steels, such as 316L, as structural components in harsh environments, e.g. in nuclear power plants, improved degradation resistance is desirable. A novel two-dimensional plane strain machining process has shown promise achieving significant grain size refinement through severe plastic deformation (SPD) and imparting large strains in the surface and subsurface regions of the substrate in various metals and alloys. The deformation process creates a heavily deformed 20 -- 30 micron thick nanocrystalline surface layer with increased hardness and minimal martensite formation. Post-deformation processing annealing treatments have been applied to assess stability of the refined scale microstructures and the potential for obtaining grain boundary engineered microstructures with increased fraction of low-energy grain boundaries and altered grain boundary network structure. Varying the deformation and heat treatment process parameters, allows for development of a full understanding of the nanocrystalline layer and cross-section of the surface substrate created. Micro-characterization was performed using hardness measurements, magnetometry, x-ray diffraction, scanning and transmission electron microscopy to assess property and microstructural changes. This study provides a fundamental understanding of two-dimensional plane strain machining as a thermo-mechanical processing technique, which may in the future deliver capabilities for creating grain boundary engineered surface modified components, typified by a combination of grain refinement with improved grain boundary network interconnectivity attributes suitable for use in harsh environments, such as those in commercial nuclear power plants where improved resistance to irradiation stress corrosion

  4. Degradation of abamectin by newly isolated Stenotrophomonas maltophilia ZJB-14120 and characterization of its abamectin-tolerance mechanism.

    PubMed

    Wang, Yuan-Shan; Zheng, Xing-Chang; Hu, Qi-Wei; Zheng, Yu-Guo

    2015-06-01

    An abamectin (ABM)-degrading bacterium, Stenotrophomonas maltophilia ZJB-14120, was isolated and identified. This strain is capable of degrading 84.82% of ABM at an initial concentration of 200 mg/L over a 48 h incubation period. This strain showed efficient biodegradation ability (7.81 mg/L/h) to ABM and high tolerance (1000 mg/L) to all macrolides tested. In addition to ABM, emamectin, erythromycin and spiramycin can also be degraded by this strain. Modifications involving either reduction of the double bond between C22-C23 or replacement of the C25-group of ABM with a cyclohexyl group can completely inhibit biodegradation of ABM. The ABM-degrading capability of strain ZJB-14120 is likely to be intrinsic to its metabolism and could be inhibited by incubating with erythromycin, azithromycin, spiramycin or rifampicin. A new and successive degradation pathway was proposed based on metabolite analysis. Although there is evidence for metabolite inhibition, this strain has high ABM degradation activity and reusability. Further investigation showed that activated macrolide efflux pump(s) and an undetermined mechanism for regulating the intracellular ABM concentration are responsible for normal uptake of essential metabolites while pumping out excess harmful compounds. Strain ZJB-14120 may provide efficient treatment of water and soil contaminated by toxic levels of abamectin and emamectin. PMID:25957243

  5. A Multi-Layered Computational Model of Coupled Elastin Degradation, Vasoactive Dysfunction, and Collagenous Stiffening in Aortic Aging

    PubMed Central

    Valentín, A.; Humphrey, J.D.; Holzapfel, G.A.

    2011-01-01

    Arterial responses to diverse pathologies and insults likely occur via similar mechanisms. For example, many studies suggest that the natural process of aging and isolated systolic hypertension share many characteristics in arteries, including loss of functional elastin, decreased smooth muscle tone, and altered rates of deposition and/or cross-linking of fibrillar collagen. Our aim is to show computationally how these coupled effects can impact evolving aortic geometry and mechanical behavior. Employing a thick-walled, multi-layered constrained mixture model, we suggest that a coupled loss of elastin and vasoactive function are fundamental mechanisms by which aortic aging occurs. Moreover, it is suggested that collagenous stiffening, although itself generally an undesirable process, can play a key role in attenuating excessive dilatation, perhaps including the enlargement of abdominal aortic aneurysms. PMID:21380570

  6. Kinetics and mechanism of the degradation of methyl parathion in aqueous hydrogen sulfide solution: investigation of natural organic matter effects.

    PubMed

    Guo, Xiaofen; Jans, Urs

    2006-02-01

    The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment. PMID:16509335

  7. Effects of material thickness and processing method on poly(lactic-co-glycolic acid) degradation and mechanical performance.

    PubMed

    Shirazi, Reyhaneh Neghabat; Aldabbagh, Fawaz; Ronan, William; Erxleben, Andrea; Rochev, Yury; McHugh, Peter

    2016-10-01

    In this study, the effects of material thickness and processing method on the degradation rate and the changes in the mechanical properties of poly(lactic-co-glycolic acid) material during simulated physiological degradation were investigated. Two types of poly(lactic-co-glycolic acid) materials were considered: 0.12 mm solvent-cast films and 1 mm compression-moulded plates. The experimental results presented in this study were compared to the experimental results of Shirazi et al. (Acta Biomaterialia 10(11):4695-703, 2014) for 0.25 mm solvent-cast films. These experimental observations were used to validate the computational modelling predictions of Shirazi et al. (J Mech Behav Biomed Mater 54: 48-59, 2016) on critical diffusion length scale and also to refine the model parameters. The specific material processing methods considered here did not have a significant effect on the degradation rate and the changes in mechanical properties during degradation; however, they influenced the initial molecular weight and they determined the stiffness and hardness of the poly(lactic-co-glycolic acid) material. The experimental observations strongly supported the computational modelling predictions that showed no significant difference in the degradation rate and the changes in the elastic modulus of poly(lactic-co-glycolic acid) films for thicknesses larger than 100 μm. PMID:27590824

  8. Degradation mechanisms in high-power multi-mode InGaAs-AlGaAs strained quantum well lasers for high-reliability applications

    NASA Astrophysics Data System (ADS)

    Sin, Yongkun; Presser, Nathan; Brodie, Miles; Lingley, Zachary; Foran, Brendan; Moss, Steven C.

    2015-03-01

    Laser diode manufacturers perform accelerated multi-cell lifetests to estimate lifetimes of lasers using an empirical model. Since state-of-the-art laser diodes typically require a long period of latency before they degrade, significant amount of stress is applied to the lasers to generate failures in relatively short test durations. A drawback of this approach is the lack of mean-time-to-failure data under intermediate and low stress conditions, leading to uncertainty in model parameters (especially optical power and current exponent) and potential overestimation of lifetimes at usage conditions. This approach is a concern especially for satellite communication systems where high reliability is required of lasers for long-term duration in the space environment. A number of groups have studied reliability and degradation processes in GaAs-based lasers, but none of these studies have yielded a reliability model based on the physics of failure. The lack of such a model is also a concern for space applications where complete understanding of degradation mechanisms is necessary. Our present study addresses the aforementioned issues by performing long-term lifetests under low stress conditions followed by failure mode analysis (FMA) and physics of failure investigation. We performed low-stress lifetests on both MBE- and MOCVD-grown broad-area InGaAs- AlGaAs strained QW lasers under ACC (automatic current control) mode to study low-stress degradation mechanisms. Our lifetests have accumulated over 36,000 test hours and FMA is performed on failures using our angle polishing technique followed by EL. This technique allows us to identify failure types by observing dark line defects through a window introduced in backside metal contacts. We also investigated degradation mechanisms in MOCVD-grown broad-area InGaAs-AlGaAs strained QW lasers using various FMA techniques. Since it is a challenge to control defect densities during the growth of laser structures, we chose to

  9. Aging.

    PubMed

    Park, Dong Choon; Yeo, Seung Geun

    2013-09-01

    Aging is initiated based on genetic and environmental factors that operate from the time of birth of organisms. Aging induces physiological phenomena such as reduction of cell counts, deterioration of tissue proteins, tissue atrophy, a decrease of the metabolic rate, reduction of body fluids, and calcium metabolism abnormalities, with final progression onto pathological aging. Despite the efforts from many researchers, the progression and the mechanisms of aging are not clearly understood yet. Therefore, the authors would like to introduce several theories which have gained attentions among the published theories up to date; genetic program theory, wear-and-tear theory, telomere theory, endocrine theory, DNA damage hypothesis, error catastrophe theory, the rate of living theory, mitochondrial theory, and free radical theory. Although there have been many studies that have tried to prevent aging and prolong life, here we introduce a couple of theories which have been proven more or less; food, exercise, and diet restriction. PMID:24653904

  10. Aging

    PubMed Central

    Park, Dong Choon

    2013-01-01

    Aging is initiated based on genetic and environmental factors that operate from the time of birth of organisms. Aging induces physiological phenomena such as reduction of cell counts, deterioration of tissue proteins, tissue atrophy, a decrease of the metabolic rate, reduction of body fluids, and calcium metabolism abnormalities, with final progression onto pathological aging. Despite the efforts from many researchers, the progression and the mechanisms of aging are not clearly understood yet. Therefore, the authors would like to introduce several theories which have gained attentions among the published theories up to date; genetic program theory, wear-and-tear theory, telomere theory, endocrine theory, DNA damage hypothesis, error catastrophe theory, the rate of living theory, mitochondrial theory, and free radical theory. Although there have been many studies that have tried to prevent aging and prolong life, here we introduce a couple of theories which have been proven more or less; food, exercise, and diet restriction. PMID:24653904

  11. Accelerated Testing Of Photothermal Degradation Of Polymers

    NASA Technical Reports Server (NTRS)

    Kim, Soon Sam; Liang, Ranty Hing; Tsay, Fun-Dow

    1989-01-01

    Electron-spin-resonance (ESR) spectroscopy and Arrhenius plots used to determine maximum safe temperature for accelerated testing of photothermal degradation of polymers. Aging accelerated by increasing illumination, temperature, or both. Results of aging tests at temperatures higher than those encountered in normal use valid as long as mechanism of degradation same throughout range of temperatures. Transition between different mechanisms at some temperature identified via transition between activation energies, manifesting itself as change in slope of Arrhenius plot at that temperature.

  12. Long-term ageing and materials degradation of hybrid mica compressive seals for solid oxide fuel cells

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.

    2009-06-15

    Hybrid phlogopite mica seals with silver interlayers were evaluated in long term isothermal ageing tests in a dual environment consisting of dilute hydrogen vs. air at 800 degrees C. High-temperature leak tests with helium showed very stable leakage of 0.01-0.02 sccm/cm for 28366 hrs under a low applied compressive stress of 82 kPa (12 psi). Post-mortem SEM and EDS analyses of the mica showed minimum degradation in terms of changes in microstructure and chemical composition, although there appeared to be some Ag migration and segregation at interstices between mica flakes. Fluorine was also found to be released from mica. Overall, the low, constant leakage through the hybrid mica/Ag seals clearly demonstrated a very promising candidate for SOFC sealing.

  13. MECHANICAL DEGRADATION OF EMPLACEMENT DRIFTS AT YUCCA MOUNTAIN - A CASE STUDY IN ROCK MECHANICS, PART 1: NONLITHOPHYSAL ROCK, PART 2: LITHOPHYSAL ROCK

    SciTech Connect

    M. Lin, D. Kicker, B. Damjanac, M. Board, and M. Karakouzian

    2006-02-27

    This paper outlines rock mechanics investigations associated with mechanical degradation of planned emplacement drifts at Yucca Mountain, which is the designated site for a US high-level nuclear waste repository. The factors leading to drift degradation include stresses from the overburden, stresses induced by the heat released from the emplaced waste, stresses due to seismically related ground motions, and time-dependent strength degradation. The welded tuff emplacement horizon consists of two groups of rock with distinct engineering properties: nonlithophysal units and lithophysal units, based on the relative proportion of lithophysal cavities. Part I of the paper concentrates on the generally hard, strong, and fractured nonlithophysal rock. The degradation behavior of the tunnels in the nonlithophysal rock is controlled by the occurrence of keyblocks. A statistically equivalent fracture model was generated based on extensive underground fracture mapping data from the Exploratory Studies Facility at Yucca Mountain. Three-dimensional distinct block analyses, generated with the fracture patterns randomly selected from the fracture model, were developed with the consideration of in situ, thermal, seismic loads. In this study, field data, laboratory data, and numerical analyses are well integrated to provide a solution for the unique problem of modeling drift degradation throughout the regulatory period for repository performance.

  14. Low-Temperature Aging of Delta-Ferrite in 316L SS Welds; Changes in Mechanical Properties and Etching Properties

    NASA Astrophysics Data System (ADS)

    Abe, Hiroshi; Shimizu, Keita; Watanabe, Yutaka

    Thermal aging embrittlement of LWR components made of stainless cast (e.g. CF-8 and CF-8M) is a potential degradation issue, and careful attention has been paid on it. Although welds of austenitic stainless steels (SSs) have γ-δ duplex microstructure, which is similar to that of the stainless cast, examination on thermal aging characteristics of the SS welds is very limited. In order to evaluate thermal aging behavior of weld metal of austenitic stainless steel, the 316L SS weld metal has been prepared and changes in mechanical properties and in etching properties at isothermal aging at 335°C have been investigated. The hardness of the ferrite phase has increased with aging, while the hardness of austenite phase has stayed same. It has been suggested that spinodal decomposition has occurred in δ-ferrite by the 335°C aging. The etching rates of δ-ferrite at immersion test in 5wt% hydrochloric acid solution have been also investigated using an AFM technique. The etching rate of ferrite phase has decreased consistently with the increase in hardness of ferrite phase. It has been thought that this characteristic is also caused by spinodal decomposition of ferrite into chromium-rich (α') and iron-rich (α).

  15. Effects of aging on the structural, mechanical, and thermal properties of the silicone rubber current transformer insulation bushing for a 500 kV substation.

    PubMed

    Wang, Zhigao; Zhang, Xinghai; Wang, Fangqiang; Lan, Xinsheng; Zhou, Yiqian

    2016-01-01

    In order to analyze the cracking and aging reason of the silicone rubber current transformer (CT) insulation bushing used for 8 years from a 500 kV alternating current substation, characteristics including Fourier transform infrared (FTIR) spectroscopy, mechanical properties analysis, hardness, and thermo gravimetric analysis have been carried out. The FTIR results indicated that the external surface of the silicone rubber CT insulation bushing suffered from more serious aging than the internal part, fracture of side chain Si-C bond was much more than the backbone. Mechanical properties and thermal stability results illustrated that the main aging reasons were the breakage of side chain Si-C bond and the excessive cross-linking reaction of the backbone. This study can provide valuable basis for evaluating degradation mechanism and aging state of the silicone rubber insulation bushing in electric power field. PMID:27390631

  16. Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

    SciTech Connect

    Mumm, Daniel

    2013-08-31

    The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leading to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive

  17. Discover the network mechanisms underlying the connections between aging and age-related diseases

    PubMed Central

    Yang, Jialiang; Huang, Tao; Song, Won-min; Petralia, Francesca; Mobbs, Charles V.; Zhang, Bin; Zhao, Yong; Schadt, Eric E.; Zhu, Jun; Tu, Zhidong

    2016-01-01

    Although our knowledge of aging has greatly expanded in the past decades, it remains elusive why and how aging contributes to the development of age-related diseases (ARDs). In particular, a global mechanistic understanding of the connections between aging and ARDs is yet to be established. We rely on a network modelling named “GeroNet” to study the connections between aging and more than a hundred diseases. By evaluating topological connections between aging genes and disease genes in over three thousand subnetworks corresponding to various biological processes, we show that aging has stronger connections with ARD genes compared to non-ARD genes in subnetworks corresponding to “response to decreased oxygen levels”, “insulin signalling pathway”, “cell cycle”, etc. Based on subnetwork connectivity, we can correctly “predict” if a disease is age-related and prioritize the biological processes that are involved in connecting to multiple ARDs. Using Alzheimer’s disease (AD) as an example, GeroNet identifies meaningful genes that may play key roles in connecting aging and ARDs. The top modules identified by GeroNet in AD significantly overlap with modules identified from a large scale AD brain gene expression experiment, supporting that GeroNet indeed reveals the underlying biological processes involved in the disease. PMID:27582315

  18. Discover the network mechanisms underlying the connections between aging and age-related diseases.

    PubMed

    Yang, Jialiang; Huang, Tao; Song, Won-Min; Petralia, Francesca; Mobbs, Charles V; Zhang, Bin; Zhao, Yong; Schadt, Eric E; Zhu, Jun; Tu, Zhidong

    2016-01-01

    Although our knowledge of aging has greatly expanded in the past decades, it remains elusive why and how aging contributes to the development of age-related diseases (ARDs). In particular, a global mechanistic understanding of the connections between aging and ARDs is yet to be established. We rely on a network modelling named "GeroNet" to study the connections between aging and more than a hundred diseases. By evaluating topological connections between aging genes and disease genes in over three thousand subnetworks corresponding to various biological processes, we show that aging has stronger connections with ARD genes compared to non-ARD genes in subnetworks corresponding to "response to decreased oxygen levels", "insulin signalling pathway", "cell cycle", etc. Based on subnetwork connectivity, we can correctly "predict" if a disease is age-related and prioritize the biological processes that are involved in connecting to multiple ARDs. Using Alzheimer's disease (AD) as an example, GeroNet identifies meaningful genes that may play key roles in connecting aging and ARDs. The top modules identified by GeroNet in AD significantly overlap with modules identified from a large scale AD brain gene expression experiment, supporting that GeroNet indeed reveals the underlying biological processes involved in the disease. PMID:27582315

  19. Mechanisms of aging in senescence-accelerated mice

    PubMed Central

    Carter, Todd A; Greenhall, Jennifer A; Yoshida, Shigeo; Fuchs, Sebastian; Helton, Robert; Swaroop, Anand; Lockhart, David J; Barlow, Carrolee

    2005-01-01

    Background Progressive neurological dysfunction is a key aspect of human aging. Because of underlying differences in the aging of mice and humans, useful mouse models have been difficult to obtain and study. We have used gene-expression analysis and polymorphism screening to study molecular senescence of the retina and hippocampus in two rare inbred mouse models of accelerated neurological senescence (SAMP8 and SAMP10) that closely mimic human neurological aging, and in a related normal strain (SAMR1) and an unrelated normal strain (C57BL/6J). Results The majority of age-related gene expression changes were strain-specific, with only a few common pathways found for normal and accelerated neurological aging. Polymorphism screening led to the identification of mutations that could have a direct impact on important disease processes, including a mutation in a fibroblast growth factor gene, Fgf1, and a mutation in and ectopic expression of the gene for the chemokine CCL19, which is involved in the inflammatory response. Conclusion We show that combining the study of inbred mouse strains with interesting traits and gene-expression profiling can lead to the discovery of genes important for complex phenotypes. Furthermore, full-genome polymorphism detection, sequencing and gene-expression profiling of inbred mouse strains with interesting phenotypic differences may provide unique insights into the molecular genetics of late-manifesting complex diseases. PMID:15960800

  20. Aging mechanisms in amorphous phase-change materials

    NASA Astrophysics Data System (ADS)

    Raty, Jean Yves; Zhang, Wei; Luckas, Jennifer; Chen, Chao; Mazzarello, Riccardo; Bichara, Christophe; Wuttig, Matthias

    2015-06-01

    Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

  1. Age coarsening of colloidal gels: a micro-mechanical study

    NASA Astrophysics Data System (ADS)

    Zia, Roseanna; Landrum, Benjamin; Russel, William

    2013-11-01

    We study the evolving structure and time-dependent rheological properties of an aging colloidal gel, with a focus on understanding the non-equilibrium forces that drive late-age coarsening. The gel is formed from a dispersion of Brownian hard spheres that interact via a hard-sphere repulsion and short-range attraction. The O(kT) strength of attractions lead to an arrested phase separation, and the resulting structure is a bi-continuous, space-spanning network that exhibits elastic and viscous behaviors: the gel may sustain its weight under gravity, or flow under shear. With weak attractions the bonds are reversible, giving rise to a continuous breakage / formation process as the gel ages. This balance favors coarsening over time, accompanied by an increase in feature size and elastic strength. We show here that anisotropic surface migration leads to heterogeneous coarsening, and that this migration is driven by gradients in particle-phase stress.

  2. Improvement of physico-mechanical, thermomechanical, thermal and degradation properties of PCL/gelatin biocomposites: Effect of gamma radiation

    NASA Astrophysics Data System (ADS)

    Zaman, Haydar U.; Beg, M. D. H.

    2015-04-01

    This research was to study the effects of gelatin content variation and gamma radiation after the 2-ethylhexyl acrylate (EHA) pre-treatment on the foundamental properties of gelatin film laminated polycaprolactone (PCL) biocomposites. PCL/gelatin film (PCL/GF) composites were fabricated by compression molding and their properties were studied by physico-mechanical, thermomechanical, thermal and degradation properties. The results from mechanical properties such as tensile modulus and impact strength of the composites increased with increasing of gelatin content up to 10 wt% and then decreased while the tensile strength and elongation at break decreased. EHA monomer (2-8 wt%) was added to the gelatin solution and films were prepared by casting and found to increase the mechanical properties of the PCL/EHA blended gelatin film (PCL/EGF) composites. Treatment of the gelatin film with gamma radiation after the EHA pre-treatment showed the best mechanical properties of the resulting composites. Dynamic mechanical thermal analysis results showed that the storage modulus of the PCL/EGF and PCL/EHA blended gelatin film with gamma radiation (PCL/GEGF) composites was increased significantly. The degradation properties in water and soil were determined for the non-irradiated and irradiated composites. It was observed that the non-irradiated composite degrades more than that of the irradiated composites.

  3. Impact of aging mechanism on model simulated carbonaceous aerosols

    NASA Astrophysics Data System (ADS)

    Huang, Y.; Wu, S.; Dubey, M. K.; French, N. H. F.

    2013-07-01

    Carbonaceous aerosols including organic carbon and black carbon have significant implications for both climate and air quality. In the current global climate or chemical transport models, a fixed hydrophobic-to-hydrophilic conversion lifetime for carbonaceous aerosol (τ) is generally assumed, which is usually around one day. We have implemented a new detailed aging scheme for carbonaceous aerosols in a chemical transport model (GEOS-Chem) to account for both the chemical oxidation and the physical condensation-coagulation effects, where τ is affected by local atmospheric environment including atmospheric concentrations of water vapor, ozone, hydroxyl radical and sulfuric acid. The updated τ exhibits large spatial and temporal variations with the global average (up to 11 km altitude) calculated to be 2.6 days. The chemical aging effects are found to be strongest over the tropical regions driven by the low ozone concentrations and high humidity there. The τ resulted from chemical aging generally decreases with altitude due to increases in ozone concentration and decreases in humidity. The condensation-coagulation effects are found to be most important for the high-latitude areas, in particular the polar regions, where the τ values are calculated to be up to 15 days. When both the chemical aging and condensation-coagulation effects are considered, the total atmospheric burdens and global average lifetimes of BC, black carbon, (OC, organic carbon) are calculated to increase by 9% (3%) compared to the control simulation, with considerable enhancements of BC and OC concentrations in the Southern Hemisphere. Model evaluations against data from multiple datasets show that the updated aging scheme improves model simulations of carbonaceous aerosols for some regions, especially for the remote areas in the Northern Hemisphere. The improvement helps explain the persistent low model bias for carbonaceous aerosols in the Northern Hemisphere reported in literature. Further

  4. Age differences in the brain mechanisms of good taste.

    PubMed

    Rolls, Edmund T; Kellerhals, Michele B; Nichols, Thomas E

    2015-06-01

    There is strong evidence demonstrating age-related differences in the acceptability of foods and beverages. To examine the neural foundations underlying these age-related differences in the acceptability of different flavors and foods, we performed an fMRI study to investigate brain and hedonic responses to orange juice, orange soda, and vegetable juice in three different age groups: Young (22), Middle (40) and Elderly (60 years). Orange juice and orange soda were found to be liked by all age groups, while vegetable juice was disliked by the Young, but liked by the Elderly. In the insular primary taste cortex, the activations to these stimuli were similar in the 3 age groups, indicating that the differences in liking for these stimuli between the 3 groups were not represented in this first stage of cortical taste processing. In the agranular insula (anterior to the insular primary taste cortex) where flavor is represented, the activations to the stimuli were similar in the Elderly, but in the Young the activations were larger to the vegetable juice than to the orange drinks; and the activations here were correlated with the unpleasantness of the stimuli. In the anterior midcingulate cortex, investigated as a site where the activations were correlated with the unpleasantness of the stimuli, there was again a greater activation to the vegetable than to the orange stimuli in the Young but not in the Elderly. In the amygdala (and orbitofrontal cortex), investigated as sites where the activations were correlated with the pleasantness of the stimuli, there was a smaller activation to the vegetable than to the orange stimuli in the Young but not in the Elderly. The Middle group was intermediate with respect to the separation of their activations to the stimuli in the brain areas that represent the pleasantness or unpleasantness of flavors. Thus age differences in the activations to different flavors can in some brain areas be related to, and probably cause, the

  5. Modelling ecogeomorphic feedbacks: investigating mechanisms of land degradation in semi-arid grassland and shrubland

    NASA Astrophysics Data System (ADS)

    Turnbull, Laura; Mueller, Eva; Tietjen, Britta; Wainwright, John

    2014-05-01

    Across vast areas of the world's drylands, land degradation is exacerbated by ecohydrological processes, which alter the structure, function and connectivity of dryland hillslopes. These processes are often interlinked through feedback mechanisms in such a way that a trigger may result in a re-organization of the affected landscape. Here, we present a spatially explicit process-based ecogeomorphic model, MAHLERAN-EcoHyD to enhance our understanding of complex linkages between abiotic and biotic drivers and processes of degradation in drylands. This ecogeomorphic modelling approach is innovative in two main ways: it couples biotic and abiotic processes, and simulates intra and inter-event dynamics, thus overcoming a key limitation of previous modelling approaches in terms of their temporal scaling, by simulating key ecogeomorphic processes at process-relevant time steps. Redistribution of water, sediment and nutrients during high-intensity rainstorms is simulated at 1-sec time steps, soil moisture and transpiration dynamics at daily time steps, and vegetation dynamics (establishment, growth, mortality) at 14-day time steps, over a high-resolution 1x1 m grid. We use this innovative modelling approach to investigate soil-vegetation feedback mechanisms within a grassland-shrubland transition zone at the Sevilleta Long Term Ecological Research site in the south-western United States. Results from three modelling experiments are presented: the first modelling experiment investigates the impact of annual variations in individual high-intensity storms to assess long-term variations in runoff, soil-moisture conditions and sediment and nutrient fluxes over two decades; the second modelling experiment assesses the impact of vegetation composition on spatial changes in surface soil texture due to soil erosion by water; and the third modelling experiment investigates how long-term changes in vegetation alter feedbacks between biotic and abiotic processes using scenarios for

  6. Thermal degradation mechanism of triangular Ag@SiO2 nanoparticles.

    PubMed

    Gangishetty, Mahesh K; Scott, Robert W J; Kelly, Timothy L

    2016-06-14

    Triangular silver nanoparticles are promising materials for light harvesting applications because of their strong plasmon bands; these absorption bands are highly tunable, and can be varied over the entire visible range based on the particle size. A general concern with these materials is that they are unstable at elevated temperatures. When thermally annealed, they suffer from changes to the particle morphology, which in turn affects their optical properties. Because of this stability issue, these materials cannot be used in applications requiring elevated temperatures. In order to address this problem, it is important to first understand the degradation mechanism. Here, we measure the changes in particle morphology, oxidation state, and coordination environment of Ag@SiO2 nanotriangles caused by thermal annealing. UV-vis spectroscopy and TEM reveal that upon annealing the Ag@SiO2 nanotriangles in air, the triangular cores are truncated and smaller nanoparticles are formed. Ag K-edge X-ray absorption spectroscopy (XANES and EXAFS) shows that the small particles consist of Ag(0), and that there is a decrease in the Ag-Ag coordination number with an increase in the annealing temperature. We hypothesize that upon annealing Ag in air, it is first oxidized to AgxO, after which it subsequently decomposes back to well-dispersed Ag(0) nanoparticles. In contrast, when the Ag@SiO2 nanotriangles are annealed in N2, since there is no possibility of oxidation, no small particles are formed. Instead, the triangular core rearranges to form a disc-like shape. PMID:26875498

  7. Inhibition of endogenous NGF degradation induces mechanical allodynia and thermal hyperalgesia in rats

    PubMed Central

    2013-01-01

    Background We have previously shown a sprouting of sympathetic fibers into the upper dermis of the skin following subcutaneous injection of complete Freund’s adjuvant (CFA) into the hindpaw. This sprouting correlated with an increase in pain-related sensitivity. We hypothesized that this sprouting and pain-related behavior were caused by an increase in nerve growth factor (NGF) levels. In this study, we investigated whether the inhibition of mature NGF degradation, using a matrix metalloproteinase 2 and 9 (MMP-2/9) inhibitor, was sufficient to reproduce a similar phenotype. Results Behavioral tests performed on male Sprague–Dawley rats at 1, 3, 7 and 14 days after intra-plantar MMP-2/9 inhibitor administration demonstrated that acute and chronic injections of the MMP-2/9 inhibitor induced sensitization, in a dose dependent manner, to mechanical, hot and cold stimuli as measured by von Frey filaments, Hargreaves and acetone tests, respectively. Moreover, the protein levels of mature NGF (mNGF) were increased, whereas the levels and enzymatic activity of matrix metalloproteinase 9 were reduced in the glabrous skin of the hind paw. MMP-2/9 inhibition also led to a robust sprouting of sympathetic fibers into the upper dermis but there were no changes in the density of peptidergic nociceptive afferents. Conclusions These findings indicate that localized MMP-2/9 inhibition provokes a pattern of sensitization and fiber sprouting comparable to that previously obtained following CFA injection. Accordingly, the modulation of endogenous NGF levels should be considered as a potential therapeutic target for the management of inflammatory pain associated with arthritis. PMID:23889761

  8. Catalytic degradation of gaseous benzene by using TiO2/goethite immobilized on palygorskite: Preparation, characterization and mechanism

    NASA Astrophysics Data System (ADS)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Liu, Haibo; Huang, Li; Chen, Tianhu; Chen, Dong

    2015-11-01

    The nano-TiO2/goethite/palygorskite catalysts were prepared by sol-gel method. The morphology and structure of the catalysts were analyzed by X-ray diffraction (XRD), UV-Vis reflection spectrometer, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and N2 adsorption-desorption measurement. The results indicated that the self-made catalysts had excellent catalytic performance on gaseous benzene degradation. In the case of benzene concentration at 30 mg/m3, the degradation efficiency, over TiO2/goethite/palygorskite composite with mass ratio of 10:5:5, reached 70.4% after 180 min 254 nm UV irradiation. The reaction mechanism and kinetics study showed that palygorskite/goethite/TiO2 composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron-holes and oxygen synergy effect.

  9. Harboring oil-degrading bacteria: a potential mechanism of adaptation and survival in corals inhabiting oil-contaminated reefs.

    PubMed

    Al-Dahash, Lulwa M; Mahmoud, Huda M

    2013-07-30

    Certain coral reef systems north of the Arabian Gulf are characterized by corals with a unique ability to thrive and flourish despite the presence of crude oil continuously seeping from natural cracks in the seabed. Harboring oil-degrading bacteria as a part of the holobiont has been investigated as a potential mechanism of adaptation and survival for corals in such systems. The use of conventional and molecular techniques verified a predominance of bacteria affiliated with Gammaproteobacteria, Actinobacteria and Firmicutes in the mucus and tissues of Acropora clathrata and Porites compressa. These bacteria were capable of degrading a wide range of aliphatic (C9-C28) aromatic hydrocarbons (Phenanthrene, Biphenyl, Naphthalene) and crude oil. In addition, microcosms supplied with coral samples and various concentrations of crude oil shifted their bacterial population toward the more advantageous types of oil degraders as oil concentrations increased. PMID:23014479

  10. Cellular senescence in aging and age-related disease: from mechanisms to therapy

    PubMed Central

    Childs, Bennett G; Durik, Matej; Baker, Darren J; van Deursen, Jan M

    2016-01-01

    Cellular senescence, a process that imposes permanent proliferative arrest on cells in response to various stressors, has emerged as a potentially important contributor to aging and age-related disease, and it is an attractive target for therapeutic exploitation. A wealth of information about senescence in cultured cells has been acquired over the past half century; however, senescence in living organisms is poorly understood, largely because of technical limitations relating to the identification and characterization of senescent cells in tissues and organs. Furthermore, newly recognized beneficial signaling functions of senescence suggest that indiscriminately targeting senescent cells or modulating their secretome for anti-aging therapy may have negative consequences. Here we discuss current progress and challenges in understanding the stressors that induce senescence in vivo, the cell types that are prone to senesce, and the autocrine and paracrine properties of senescent cells in the contexts of aging and age-related diseases as well as disease therapy. PMID:26646499

  11. Mechanism driven structural elucidation of forced degradation products from hydrocortisone in solution.

    PubMed

    Zhang, Fa; Zhou, Jay; Shi, Yiqun; Tavlarakis, Panagiotis; Karaisz, Kenneth

    2016-09-01

    Hydrocortisone degradation products 1, 2, 3, and 4 along with hemiacetal derivatives 5, 6, 7, and 8 were observed through stressed hydrocortisone in solution. Their structures were identified based on HPLC-UV, HPLC-MS, and HPLC-HRMS (high resolution/high accuracy mass spectrometry) analyses as well as reaction mechanistic investigation and synthesis for structural confirmation. 1 and 2 are a pair of E/Z isomers and they were generated through acid catalyzed tautomerization/dehydration of hydrocortisone. Incorporation of water to 1 and 2 resulted in the formation of 3. We also discovered new degradation product 4 which was converted from 3 by oxidation. The degradation products were synthesized by stressing hydrocortisone under the optimized conditions and their structures were characterized by NMR ((1)H/(13)C, COSY, HMBC, HSQC, NOESY) and HRMS analyses. The degradation pathway of hydrocortisone is postulated. PMID:27328360

  12. Atmospheric degradation mechanism of CF{sub 3}OCH{sub 3}

    SciTech Connect

    Christensen, L.K.; Wallington, T.J.; Guschin, A.; Hurley, M.D.

    1999-05-27

    Recognition of the adverse effect of chlorofluorocarbon (CFC) release into the atmosphere has led to an international effort to replace CFCs with environmentally acceptable alternatives. Hydrofluoroethers (HFEs) are a class of compounds which have been developed to replace CFCs in applications such as the cleaning of electronic equipment, heat transfer agents in refrigeration systems, and carrier fluids for lubricant deposition. HFEs are volatile compounds and are released into the atmosphere when used. CF{sub 3}OCH{sub 3} has not been used commercially but is one of the simplest fluoroethers and serves as a model compound for the group of fluorinated ethers. A smog chamber/FTIR technique was used to study the Cl atom initiated oxidation of CF{sub 3}OCH{sub 3} in 700 Torr of N{sub 2}/O{sub 2} at 296 K. Using relative rate techniques it was determined that {kappa}(Cl + CF{sub 3}OCH{sub 3}) = (1.4 {+-} 0.2) {times} 10{sup {minus}13} and {kappa}(Cl + CF{sub 3}OC(O)H) = (9.8 {+-} 1.2) {times} 10{sup {minus}15} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. At 700 Torr of N{sub 2}/O{sub 2} diluent at 296 K reaction with O{sub 2} is the only loss mechanism of the CF{sub 3}OCH{sub 2}O{sup {sm_bullet}} radical. The infrared spectra of the peroxy nitrates CF{sub 3}OCH{sub 2}O{sub 2}NO{sub 2} and CF{sub 3}OC(O)O{sub 2}NO{sub 2} were recorded and compared to the nonfluorinated analogues CH{sub 3}OCH{sub 2}O{sub 2}NO{sub 2} and CH{sub 3}OC(O)O{sub 2}NO{sub 2}. The thermal decomposition rate of CF{sub 3}OC(O)NO{sub 2} is (2.3 {+-} 0.1) {times} 10{sup {minus}4} s{sup {minus}1} in 700 Torr of N{sub 2} at 295.8 K. The reaction of CF{sub 3}OC(O)O{sub 2} radicals with HO{sub 2} radicals gives CF{sub 3}OC(O)H in a yield of (80 {+-} 11)%. The results are discussed with respect to the atmospheric degradation mechanism of CF{sub 3}OCH{sub 3} and other ethers.

  13. Kinetic analysis of acid orange 7 degradation by pulsed discharge plasma combined with activated carbon and the synergistic mechanism exploration.

    PubMed

    Guo, He; Wang, Huijuan; Wu, Qiangshun; Zhou, Guangshun; Yi, Chengwu

    2016-09-01

    The synergistic technique of pulsed discharge plasma (PDP) and activated carbon (AC) was built to investigate the kinetics of acid orange 7 (AO7) degradation under different conditions of AC addition, electrode gap, initial pH value of solution, gas variety and gas flow rate. Emission spectra of OH and O, UV-vis absorption spectra of the AO7 solution and TOC removal were measured to illustrate the synergistic mechanism of the PDP and the AC. The obtained results indicated that the kinetic constant of AO7 degradation increased from 0.00947 min(-1) to 0.01419 min(-1) when 4 g AC was added into the PDP system; AO7 degradation was higher in the case of alkaline solution when oxygen was used as the flow gas in the PDP/AC system, 2 L/min oxygen flow was more favorable for the degradation. Results of the relative emission intensities of OH and O indicated the catalytic effect of the AC on the active species formation as well as the important role of the two radicals for the AO7 degradation. There was no new peaks appeared by the UV-vis analysis of the AO7 solution after 60 min treatment. The highest TOC removal in the PDP/AC system was 30.3%, which was achieved under the condition of 4 L/min air flow rate and 3 initial pH value. PMID:27295438

  14. Impact of aging mechanism on model simulated carbonaceous aerosols

    PubMed Central

    Huang, Y.; Wu, S.; Dubey, M.K.; French, N. H. F.

    2013-01-01

    Carbonaceous aerosols including organic carbon and black carbon have significant implications for both climate and air quality. In the current global climate or chemical transport models, a fixed hydrophobic-to-hydrophilic conversion lifetime for carbonaceous aerosol (τ) is generally assumed, which is usually around one day. We have implemented a new detailed aging scheme for carbonaceous aerosols in a chemical transport model (GEOS-Chem) to account for both the chemical oxidation and the physical condensation-coagulation effects, where τ is affected by local atmospheric environment including atmospheric concentrations of water vapor, ozone, hydroxyl radical and sulfuric acid. The updated τ exhibits large spatial and temporal variations with the global average (up to 11 km altitude) calculated to be 2.6 days. The chemical aging effects are found to be strongest over the tropical regions driven by the low ozone concentrations and high humidity there. The τ resulted from chemical aging generally decreases with altitude due to increases in ozone concentration and decreases in humidity. The condensation-coagulation effects are found to be most important for the high-latitude areas, in particular the polar regions, where the τ values are calculated to be up to 15 days. When both the chemical aging and condensation-coagulation effects are considered, the total atmospheric burdens and global average lifetimes of BC, black carbon, (OC, organic carbon) are calculated to increase by 9% (3%) compared to the control simulation, with considerable enhancements of BC and OC concentrations in the Southern Hemisphere. Model evaluations against data from multiple datasets show that the updated aging scheme improves model simulations of carbonaceous aerosols for some regions, especially for the remote areas in the Northern Hemisphere. The improvement helps explain the persistent low model bias for carbonaceous aerosols in the Northern Hemisphere reported in literature. Further

  15. In vitro degradation and mechanical integrity of calcium-containing magnesium alloys in modified-simulated body fluid.

    PubMed

    Kannan, M Bobby; Raman, R K Singh

    2008-05-01

    The successful applications of magnesium-based alloys as degradable orthopaedic implants are mainly inhibited due to their high degradation rates in physiological environment and consequent loss in the mechanical integrity. This study examines the degradation behaviour and the mechanical integrity of calcium-containing magnesium alloys using electrochemical techniques and slow strain rate test (SSRT) method, respectively, in modified-simulated body fluid (m-SBF). Potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) results showed that calcium addition enhances the general and pitting corrosion resistances of magnesium alloys significantly. The corrosion current was significantly lower in AZ91Ca alloy than that in AZ91 alloy. Furthermore, AZ91Ca alloy exhibited a five-fold increase in the surface film resistance than AZ91 alloy. The SSRT results showed that the ultimate tensile strength and elongation to fracture of AZ91Ca alloy in m-SBF decreased only marginally (approximately 15% and 20%, respectively) in comparison with these properties in air. The fracture morphologies of the failed samples are discussed in the paper. The in vitro study suggests that calcium-containing magnesium alloys to be a promising candidate for their applications in degradable orthopaedic implants, and it is worthwhile to further investigate the in vivo corrosion behaviour of these alloys. PMID:18313746

  16. Microwave-assisted rapid photocatalytic degradation of malachite green in TiO2 suspensions: mechanism and pathways.

    PubMed

    Ju, Yongming; Yang, Shaogui; Ding, Youchao; Sun, Cheng; Zhang, Aiqian; Wang, Lianhong

    2008-11-01

    Microwave-assisted photocatalytic (MPC) degradation of malachite green (MG) in aqueous TiO2 suspensions was investigated. A 20 mg/L sample of MG was rapidly and completely decomposed in 3 min with the corresponding TOC removal efficiency of about 85%. To gain insight into the degradation mechanism, both GC-MS and LC-ESI-MS/MS techniques were employed to identify the major intermediates of MG degradation, including N-demethylation intermediates [(p-dimethylaminophenyl)(p-methylaminophenyl)phenylmethylium (DM-PM), (p-methylaminophenyl)(p-methylaminophenyl)phenylmethylium (MM-PM), (p-methylaminophenyl)(p-aminophenyl)phenylmethylium (M-PM)]; a decomposition compound of the conjugated structure (4-dimethylaminobenzophenone (DLBP)); products resulting from the adduct reaction of hydroxyl radical; products of benzene removal; and other open-ring intermediates such as phenol, terephthalic acid, adipic acid, benzoic acid, etc. The possible degradation mechanism of MG included five processes: the N-demethylation process, adduct products of the hydroxyl radical, the breakdown of chromophores such as destruction of the conjugated structure intermediate, removal of benzene, and an open-ring reaction. To the best of our knowledge, it is the first time the whole MG photodegradation processes have been reported. PMID:18841945

  17. Effect of low-temperature aging on the mechanical behavior of ground Y-TZP.

    PubMed

    Pereira, Gkr; Amaral, M; Cesar, P F; Bottino, M C; Kleverlaan, C J; Valandro, L F

    2015-05-01

    This study evaluated the effects of low-temperature aging on the surface topography, phase transformation, biaxial flexural strength, and structural reliability of a ground Y-TZP ceramic. Disc-shaped specimens were manufactured and divided according to two factors: "grinding" - without grinding (as-sintered, Ctrl), grinding with an extra-fine diamond bur (25 µm Xfine) and coarse diamond bur (181 µm Coarse); and "low-temperature-aging" (absence or presence). Grinding was performed using a contra-angle handpiece under water-cooling. Aging was performed in an autoclave at 134 °C, under 2 bar, over a period of 20 h. Surface topography analysis showed an increase in roughness based on grit-size (Coarse>Xfine>Ctrl), and aging promoted different effects on roughness (Ctrl AgCoarse). Grinding and aging promoted an increase in the amount of m-phase, although different susceptibilities to degradation were observed. Weibull analysis showed an increase in characteristic strength after grinding (Coarse=Xfine>Ctrl); however, distinct effects were observed for aging (CtrlCoarse Ag). Weibull moduli were statistically similar. Grinding promoted an increase in characteristic strength as a result of an increase in m-phase content; when the Y-TZP surface was ground by coarse diamond burs followed by aging, characteristic strength was reduced, meaning the low-temperature degradation appeared to intensify for rougher Y-TZP surfaces. PMID:25746851

  18. Discrimination of degradation processes in lithium-ion cells based on the sensitivity of aging indicators towards capacity loss

    NASA Astrophysics Data System (ADS)

    Bauer, Marius; Guenther, Clemens; Kasper, Michael; Petzl, Mathias; Danzer, Michael A.

    2015-06-01

    In typical applications of lithium-ion batteries, the cells are monitored in order to guarantee a safe and stable performance during operation. Therefore, methods to characterize aging processes in a non-destructive way are desired. In this work, internal resistance and power capability calculated from time domain measurements are investigated. Test cells (NMC/graphite) are cycled at the lowest temperature in the operational range (T = 0 °C) as well as under high temperature conditions (T = 50 °C) in order to characterize the aging behavior for extreme temperatures. For both internal resistance and power capability, an analysis of their sensitivities towards capacity loss induced by high or low temperature cycling is carried out. It is demonstrated how discrepancies in sensitivity can be used for the diagnostic purpose of discriminating between low and high temperature aging effects during cycling. A baseline diagnostic approach for constant operating conditions and an extended algorithm for varying conditions are presented. The extended approach is based on the evaluation of cell trajectories in a state space with capacity loss and polarization parameters. It provides measures which characterize the aging behavior and allow to identify the dominant aging mechanism.

  19. Comparison of Quantifiler(®) Trio and InnoQuant™ human DNA quantification kits for detection of DNA degradation in developed and aged fingerprints.

    PubMed

    Goecker, Zachary C; Swiontek, Stephen E; Lakhtakia, Akhlesh; Roy, Reena

    2016-06-01

    The development techniques employed to visualize fingerprints collected from crime scenes as well as post-development ageing may result in the degradation of the DNA present in low quantities in such evidence samples. Amplification of the DNA samples with short tandem repeat (STR) amplification kits may result in partial DNA profiles. A comparative study of two commercially available quantification kits, Quantifiler(®) Trio and InnoQuant™, was performed on latent fingerprint samples that were either (i) developed using one of three different techniques and then aged in ambient conditions or (ii) undeveloped and then aged in ambient conditions. The three fingerprint development techniques used were: cyanoacrylate fuming, dusting with black powder, and the columnar-thin-film (CTF) technique. In order to determine the differences between the expected quantities and actual quantities of DNA, manually degraded samples generated by controlled exposure of DNA standards to ultraviolet radiation were also analyzed. A total of 144 fingerprint and 42 manually degraded DNA samples were processed in this study. The results indicate that the InnoQuant™ kit is capable of producing higher degradation ratios compared to the Quantifiler(®) Trio kit. This was an expected result since the degradation ratio is a relative value specific for a kit based on the length and extent of amplification of the two amplicons that vary from one kit to the other. Additionally, samples with lower concentrations of DNA yielded non-linear relationships of degradation ratio with the duration of aging, whereas samples with higher concentrations of DNA yielded quasi-linear relationships. None of the three development techniques produced a noticeably different degradation pattern when compared to undeveloped fingerprints, and therefore do not impede downstream DNA analysis. PMID:27107968

  20. Effects of mechanical and chemical processes on the degradation of plastic beach debris on the island of Kauai, Hawaii.

    PubMed

    Cooper, David A; Corcoran, Patricia L

    2010-05-01

    Plastic debris is accumulating on the beaches of Kauai at an alarming rate, averaging 484 pieces/day in one locality. Particles sampled were analyzed to determine the effects of mechanical and chemical processes on the breakdown of polymers in a subtropical setting. Scanning electron microscopy (SEM) indicates that plastic surfaces contain fractures, horizontal notches, flakes, pits, grooves, and vermiculate textures. The mechanically produced textures provide ideal loci for chemical weathering to occur which further weakens the polymer surface leading to embrittlement. Fourier transform infrared spectroscopy (FTIR) results show that some particles have highly oxidized surfaces as indicated by intense peaks in the lower wavenumber region of the spectra. Our textural analyses suggest that polyethylene has the potential to degrade more readily than polypropylene. Further evaluation of plastic degradation in the natural environment may lead to a shift away from the production and use of plastic materials with longer residence times. PMID:20106491

  1. Differential clearance mechanisms, neutrophil extracellular trap degradation and phagocytosis, are operative in systemic lupus erythematosus patients with distinct autoantibody specificities.

    PubMed

    Chauhan, Sudhir Kumar; Rai, Richa; Singh, Vikas Vikram; Rai, Madhukar; Rai, Geeta

    2015-12-01

    Systemic lupus erythematosus (SLE) patients are generally presented with autoantibodies against either dsDNA or RNA-associated antigens (also known as extractable nuclear antigens, ENA) or both. However, the mechanisms and processes that lead to this distinctive autoantibody profile are not well understood. Defects in clearance mechanism i.e. phagocytosis may lead to enhanced microbial and cellular debris of immunogenic potential. In addition to defective phagocytosis, impaired neutrophil extracellular trap (NET) degradation has been recently reported in SLE patients. However, the extent to which both these clearance processes (NET-degradation and phagocytosis) are operative in serologically distinguished subsets of SLE patients is not established. Therefore, in this report, we evaluated NET-degradation and phagocytosis efficiency among SLE patients with different autoantibody specificities. SLE patients were classified into three subsets based on their autoantibody profile (anti-dsDNA, anti-ENA or both) as determined by ELISA. NET-degradation by SLE and control sera was assessed by sytox orange-based fluorescence assay. Neutrophil-mediated phagocytosis in the presence of SLE and control sera was determined by flowcytometry. The segregation of SLE patients revealed significant differences in NET-degradation and phagocytosis in SLE patients with autoantibodies against dsDNA and ENA. We report that NET-degradation efficiency was significantly impaired in SLE patients with anti-dsDNA autoantibodies and not in those with anti-ENA autoantibodies. In contrast to NET-degradation, neutrophil-mediated phagocytosis was impaired in all three subsets independent of autoantibody specificity. These observations suggest that varying clearance mechanisms are operative in SLE subsets with anti-dsDNA or anti-ENA autoantibodies. The results outlined in this manuscript also suggest that sub-grouping of SLE patients could be useful in delineating the molecular and pathological

  2. Co-regulation proteomics reveals substrates and mechanisms of APC/C-dependent degradation

    PubMed Central

    Singh, Sasha A; Winter, Dominic; Kirchner, Marc; Chauhan, Ruchi; Ahmed, Saima; Ozlu, Nurhan; Tzur, Amit; Steen, Judith A; Steen, Hanno

    2014-01-01

    Using multiplexed quantitative proteomics, we analyzed cell cycle-dependent changes of the human proteome. We identified >4,400 proteins, each with a six-point abundance profile across the cell cycle. Hypothesizing that proteins with similar abundance profiles are co-regulated, we clustered the proteins with abundance profiles most similar to known Anaphase-Promoting Complex/Cyclosome (APC/C) substrates to identify additional putative APC/C substrates. This protein profile similarity screening (PPSS) analysis resulted in a shortlist enriched in kinases and kinesins. Biochemical studies on the kinesins confirmed KIFC1, KIF18A, KIF2C, and KIF4A as APC/C substrates. Furthermore, we showed that the APC/CCDH1-dependent degradation of KIFC1 regulates the bipolar spindle formation and proper cell division. A targeted quantitative proteomics experiment showed that KIFC1 degradation is modulated by a stabilizing CDK1-dependent phosphorylation site within the degradation motif of KIFC1. The regulation of KIFC1 (de-)phosphorylation and degradation provides insights into the fidelity and proper ordering of substrate degradation by the APC/C during mitosis. PMID:24510915

  3. Plutonium: Aging mechanisms and weapon pit lifetime assessment

    NASA Astrophysics Data System (ADS)

    Martz, Joseph C.; Schwartz, Adam J.

    2003-09-01

    Planning for future refurbishment and manufacturing needs of the U.S. nuclear weapons complex critically depends on credible estimates for component lifetimes. One of the most important of these components is the pit, that portion of the weapon that contains the fissile element plutonium. The U.S. government has proposed construction of a new Modern Pit Facility, and a key variable in planning both the size and schedule for this facility is the minimum estimated lifetime for stockpile pits. This article describes the current understanding of aging effects in plutonium, provides a lifetime estimate range, and outlines in some detail methodology that will improve this estimate over the next few years.

  4. The Paleozoic origin of enzymatic mechanisms for lignin degradation reconstructed using 31 fungal genomes

    SciTech Connect

    Floudas, Dimitrios; Binder, Manfred; Riley, Robert; Barry, Kerrie; Blanchette, Robert A; Henrissat, Bernard; Martinez, Angel T.; Otillar, Robert; Spatafora, Joseph W.; Yadav, Jagit S.; Aerts, Andrea; Benoit, Isabelle; Boyd, Alex; Carlson, Alexis; Copeland, Alex; Coutinho, Pedro M.; de Vries, Ronald P.; Ferreira, Patricia; Findley, Keisha; Foster, Brian; Gaskell, Jill; Glotzer, Dylan; Gorecki, Pawel; Heitman, Joseph; Hesse, Cedar; Hori, Chiaki; Igarashi, Kiyohiko; Jurgens, Joel A.; Kallen, Nathan; Kersten, Phil; Kohler, Annegret; Kues, Ursula; Kumar, T. K. Arun; Kuo, Alan; LaButti, Kurt; Larrondo, Luis F.; Lindquist, Erika; Ling, Albee; Lombard, Vincent; Lucas, Susan; Lundell, Taina; Martin, Rachael; McLaughlin, David J.; Morgenstern, Ingo; Morin, Emanuelle; Murat, Claude; Nagy, Laszlo G.; Nolan, Matt; Ohm, Robin A.; Patyshakuliyeva, Aleksandrina; Rokas, Antonis; Ruiz-Duenas, Francisco J.; Sabat, Grzegorz; Salamov, Asaf; Samejima, Masahiro; Schmutz, Jeremy; Slot, Jason C.; John, Franz; Stenlid, Jan; Sun, Hui; Sun, Sheng; Syed, Khajamohiddin; Tsang, Adrian; Wiebenga, Ad; Young, Darcy; Pisabarro, Antonio; Eastwood, Daniel C.; Martin, Francis; Cullen, Dan; Grigoriev, Igor V.; Hibbett, David S.

    2012-03-12

    Wood is a major pool of organic carbon that is highly resistant to decay, owing largely to the presence of lignin. The only organisms capable of substantial lignin decay are white rot fungi in the Agaricomycetes, which also contains non?lignin-degrading brown rot and ectomycorrhizal species. Comparative analyses of 31 fungal genomes (12 generated for this study) suggest that lignin-degrading peroxidases expanded in the lineage leading to the ancestor of the Agaricomycetes, which is reconstructed as a white rot species, and then contracted in parallel lineages leading to brown rot and mycorrhizal species. Molecular clock analyses suggest that the origin of lignin degradation might have coincided with the sharp decrease in the rate of organic carbon burial around the end of the Carboniferous period.

  5. Degradation mechanisms of selected hydrochlorofluorocarbons in the atmosphere: An assessment of the current knowledge

    NASA Technical Reports Server (NTRS)

    Cox, Richard A.; Lesclaux, Robert

    1990-01-01

    Volatile organic compounds are mainly degraded in the troposphere by attack of OH with abstraction of H atoms or addition to unsaturated linkages. The chlorofluorocarbons (CFC's) do not contain these reactive sites and consequently cannot be degraded in this way in the lower atmosphere. This results in pollution of the stratosphere by these molecules and attendant problems for ozone. The proposed replacements for CFC's, the hydrochlorofluorocarbons (HCFC's), and hydrofluorocarbons (HFC's), contain at least one hydrogen atom in the molecule, which confers on these compounds a greater sensitivity toward oxidation by OH in the troposphere and in the lower stratosphere, resulting in much shorter atmospheric lifetimes than the CFC's. Consequently, the Ozone Depletion Potential and the Atmospheric Warming Potential are reduced substantially compared to the CFC's. All the possible degradation processes of the HCFC's and HFC's proposed to replace the CFC's are examined with the principal aim of identifying chlorine- and fluorine-containing products which are stable under tropospheric conditions.

  6. The mechanism of sonochemical degradation of a cationic surfactant in aqueous solution.

    PubMed

    Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

    2011-03-01

    The sonochemical degradation of the cationic surfactant, laurylpyridinium chloride (LPC), in water was studied at concentrations of 0.1-0.6 mM, all below its critical micelle concentration (15 mM). It has been found that the initial step in the degradation of LPC occurs primarily by a pyrolysis pathway. Chemical analysis of sonicated solutions by gas chromatography, electrospray mass spectrometry, and high performance liquid chromatography reveals that a broad range of decomposition products, hydrocarbon gases and water-soluble species, are produced. Propionamide and acetamide were identified as two of the degradation intermediates and probably formed as the result of the opening of the pyridinium ring following OH radical addition. Most of the LPC is eventually converted into carboxylic acids. The complete mineralization of these carboxylic acids by sonolysis is however a comparatively slow process due to the hydrophilic nature of these low molecular weight products. PMID:21041108

  7. GRIZZLY Model of Multi-Reactive Species Diffusion, Moisture/Heat Transfer and Alkali-Silica Reaction for Simulating Concrete Aging and Degradation

    SciTech Connect

    Huang, Hai; Spencer, Benjamin W.; Cai, Guowei

    2015-09-01

    Concrete is widely used in the construction of nuclear facilities because of its structural strength and its ability to shield radiation. The use of concrete in nuclear power plants for containment and shielding of radiation and radioactive materials has made its performance crucial for the safe operation of the facility. As such, when life extension is considered for nuclear power plants, it is critical to have accurate and reliable predictive tools to address concerns related to various aging processes of concrete structures and the capacity of structures subjected to age-related degradation. The goal of this report is to document the progress of the development and implementation of a fully coupled thermo-hydro-mechanical-chemical model in GRIZZLY code with the ultimate goal to reliably simulate and predict long-term performance and response of aged NPP concrete structures subjected to a number of aging mechanisms including external chemical attacks and volume-changing chemical reactions within concrete structures induced by alkali-silica reactions and long-term exposure to irradiation. Based on a number of survey reports of concrete aging mechanisms relevant to nuclear power plants and recommendations from researchers in concrete community, we’ve implemented three modules during FY15 in GRIZZLY code, (1) multi-species reactive diffusion model within cement materials; (2) coupled moisture and heat transfer model in concrete; and (3) anisotropic, stress-dependent, alkali-silica reaction induced swelling model. The multi-species reactive diffusion model was implemented with the objective to model aging of concrete structures subjected to aggressive external chemical attacks (e.g., chloride attack, sulfate attack, etc.). It considers multiple processes relevant to external chemical attacks such as diffusion of ions in aqueous phase within pore spaces, equilibrium chemical speciation reactions and kinetic mineral dissolution/precipitation. The moisture

  8. Multi-criteria analysis of the mechanism of degradation of Portland cement based mortars exposed to external sulphate attack

    SciTech Connect

    El-Hachem, R.; Roziere, E.; Grondin, F.; Loukili, A.

    2012-10-15

    This work aims to contribute to the design of durable concrete structures exposed to external sulphate attacks (ESA). Following a preliminary study aimed at designing a representative test, the present paper suggests a study on the effect of the water-to-cement (w/c) ratio and the cement composition in order to understand the degradation mechanisms. Length and mass measurements were registered continuously, leached calcium and hydroxide ions were also quantified. In parallel, scanning electron microscopy observations as well as X-ray microtomography were realised at different times to identify the formed products and the crack morphology. Test results provide information on the basic aspects of the degradation mechanism, such as the main role of leaching and diffusion in the sulphate attack process. The mortar composition with a low w/c ratio leads to a better resistance to sulphate attack because the microstructure is less permeable. Reducing the C{sub 3}A content results in a macro-cracking decrease but it does not prevent expansion, which suggests the contribution of other expansive products, such as gypsum, in damage due to ESA. The observation of the cracks network in the microstructure helps to understand the micro-mechanisms of the degradation process.

  9. A preliminary mechanical property and stress corrosion evaluation of VIM-VAR work strengthened and direct aged Inconel 718 bar material

    NASA Technical Reports Server (NTRS)

    Montano, J. W.

    1987-01-01

    This report presents a preliminary mechanical property and stress corrosion evaluation of double melted (vacuum induction melted (VIM), and vacuum arc remelted (VAR)), solution treated, work strengthened and direct aged Inconel 718 alloy bar (5.50 in. (13.97 cm) diameter). Two sets of tensile specimens, one direct single aged and the other direct double aged, were tested at ambient temperature in both the longitudinal and transverse directions. Longitudinal tensile and yield strengths in excess of 200 ksi (1378.96 MPa) and 168 ksi (1158.33 MPa), respectively, were realized at ambient temperature, for the direct double aged specimen. No failures occurred in the single or double edged longitudinal and transverse tensile specimens stressed to 75 and 100 percent of their respective yield strengths and exposed to a salt fog environment for 180 days. Tensile tests performed after the stress corrosion test showed no mechanical property degradation.

  10. Modern evolutionary mechanics theories and resolving the programmed/non-programmed aging controversy.

    PubMed

    Goldsmith, Theodore C

    2014-10-01

    Modern programmed (adaptive) theories of biological aging contend that organisms including mammals have generally evolved mechanisms that purposely limit their lifespans in order to obtain an evolutionary benefit. Modern non-programmed theories contend that mammal aging generally results from natural deteriorative processes, and that lifespan differences between species are explained by differences in the degree to which they resist those processes. Originally proposed in the 19th century, programmed aging in mammals has historically been widely summarily rejected as obviously incompatible with the mechanics of the evolution process. However, relatively recent and continuing developments described here have dramatically changed this situation, and programmed mammal aging now has a better evolutionary basis than non-programmed aging. Resolution of this issue is critically important to medical research because the two theories predict that very different biological mechanisms are ultimately responsible for age-related diseases and conditions. PMID:25519063

  11. Resin Systems and Chemistry-Degradation Mechanisms and Durability in Long-Term Durability of Polymeric Matrix Composites. Chapter 1

    NASA Technical Reports Server (NTRS)

    Hinkley, Jeffrey A.; Connell, John W.

    2012-01-01

    In choosing a polymer-matrix composite material for a particular application, a number of factors need to be weighed. Among these are mechanical requirements, fabrication method (e.g. press-molding, resin infusion, filament winding, tape layup), and use conditions. Primary among the environmental exposures encountered in aerospace structures are moisture and elevated temperatures, but certain applications may require resistance to other fluids and solvents, alkaline agents, thermal cycling, radiation, or rapid, localized heating (for example, lightning strike). In this chapter, the main classes of polymer resin systems found in aerospace composites will be discussed. Within each class, their responses to environmental factors and the associated degradation mechanisms will be reviewed.

  12. Electrochemical performance and capacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys

    NASA Astrophysics Data System (ADS)

    Liu, Jingjing; Li, Yuan; Han, Da; Yang, Shuqin; Chen, Xiaocui; Zhang, Lu; Han, Shumin

    2015-12-01

    La-Mg-Ni-based hydrogen storage alloys are a promising candidate for the negative electrode materials of nickel metal hydride batteries. However, their fast capacity degradation hinders them from more extensive application. In this study, the electrochemical performance and capacity degradation mechanism of single-phase La2MgNi9, La3MgNi14 and La4MgNi19 alloys are studied from the perspective of their constituent subunits. It is found that the rate capability and cycling stability of the alloy electrodes increase with higher [LaNi5]/[LaMgNi4] subunit ratio, while the discharge capacity shows a reverse trend. Degradation study shows that the inter-molecular strains in the alloys are the main reason that leads to the fast capacity degradation of La-Mg-Ni-based alloys. The strains are caused by the difference in the expansion/contraction properties between [LaNi5] and [LaMgNi4] subunits during charge/discharge which is mainly observed in the H-dissolved solid solution instead of hydride. It is also found that the strains can be relieved by adjusting [LaNi5]/[LaMgNi4] subunit ratio of the alloys, thus achieving less pulverization and oxidation, and better cycling stability. We expect our findings can inspire new thoughts on improving the electrochemical performance of La-Mg-Ni-based alloys by tuning their superlattice structures.

  13. Degradation mechanism of Methyl Orange by electrochemical process on RuO(x)-PdO/Ti electrode.

    PubMed

    Du, Lin; Wu, Jin; Qin, Song; Hu, Changwei

    2011-01-01

    The electrochemical degradation of Methyl Orange in 0.1 M NaCl solution over RuO(x)-PdO/Ti anode was investigated. Chemical oxygen demand (COD), ion chromatography (IC), Fourier Transform Infrared Spectroscopy (FTIR) and Gas chromatography-mass spectrometry (GC-MS) were employed to detect the intermediates formed during the electrochemical degradation. In the present reaction system, Methyl Orange could be effectively degraded. After 1 h treatment, the discoloration could reach 97.9% with COD removal of 57.6%. The results indicated that in the presence of chloride, the electrolysis was able to oxidise the dye with partial mineralisation of carbon, nitrogen and sulfur into CO(2), NO(-)(3) and SO(2-)(4), respectively. After 8 h electrolysis, 62% of sulfur contained in Methyl Orange was transformed to SO(4)(2-), and 17.6% of nitrogen changed to NO(3)(-). The intermediates during electroprocess were detected to be low molecular weight compounds, chlorinated compounds, derivatives of benzene and long chain alkanes. Based on these data, a possible degradation mechanism of Methyl Orange was proposed. PMID:21508562

  14. A dual function of V0-ATPase a1 provides an endolysosomal degradation mechanism in Drosophila melanogaster photoreceptors

    PubMed Central

    Williamson, W. Ryan; Wang, Dong; Haberman, Adam S.

    2010-01-01

    The vesicular adenosine triphosphatase (v-ATPase) is a proton pump that acidifies intracellular compartments. In addition, mutations in components of the membrane-bound v-ATPase V0 sector cause acidification-independent defects in yeast, worm, fly, zebrafish, and mouse. In this study, we present a dual function for the neuron-specific V0 subunit a1 orthologue v100 in Drosophila melanogaster. A v100 mutant that selectively disrupts proton translocation rescues a previously characterized synaptic vesicle fusion defect and vesicle fusion with early endosomes. Correspondingly, V100 selectively interacts with syntaxins on the respective target membranes, and neither synaptic vesicles nor early endosomes require v100 for their acidification. In contrast, V100 is required for acidification once endosomes mature into degradative compartments. As a consequence of the complete loss of this neuronal degradation mechanism, photoreceptors undergo slow neurodegeneration, whereas selective rescue of the acidification-independent function accelerates cell death by increasing accumulations in degradation-incompetent compartments. We propose that V100 exerts a temporally integrated dual function that increases neuronal degradative capacity. PMID:20513768

  15. Degradation of refractory dibutyl phthalate by peroxymonosulfate activated with novel catalysts cobalt metal-organic frameworks: Mechanism, performance, and stability.

    PubMed

    Li, Huanxuan; Wan, Jinquan; Ma, Yongwen; Wang, Yan; Chen, Xi; Guan, Zeyu

    2016-11-15

    In this work, a new effective and relatively stable heterogeneous catalyst of Metal-Organic Framework Co3(BTC)2·12H2O (Co-BTC) has been synthesized and tested to activate peroxymonosulfate (PMS) for removal of refractory dibutyl phthalate (DBP). Co-BTC(A) and Co-BTC(B) were synthesized by different methods, which resulted in different activity towards PMS. The results indicated that Co-BTC(A) showed better performance on DBP degradation. The highest degradation rate of 100% was obtained within 30min. The initial pH showed respective level on DBP degradation with a rank of 5.0>2.75>9.0>7.0>11.0 in PMS/Co-BTC(A) system. No remarkable reduction of DBP was observed in the catalytic activity of Co-BTC(A) at 2nd run as demonstrated by recycling. However, the DBP degradation efficiency decreased by 8.26%, 10.9% and 25.6% in the 3rd, 4th, and 5th runs, respectively. The loss of active catalytic sites of Co(II) from Co-BTC(A) is responsible for the activity decay. Sulfate radicals (SO4(-)) and hydroxyl radicals (OH) were found at pH 2.75. Here, we propose the possible mechanism for activation of PMS by Co-BTC(A), which is involved in homogeneous and heterogeneous reactions in the solutions and the surface of Co-BTC(A), respectively. PMID:27420387

  16. Mechanism and kinetics of organic matter degradation based on particle structure variation during pig manure aerobic composting.

    PubMed

    Ge, Jinyi; Huang, Guangqun; Huang, Jing; Zeng, Jianfei; Han, Lujia

    2015-07-15

    Characterization of the dynamic structure of composting particles may facilitate our understanding of the mechanisms of organic matter degradation during pig manure-wheat straw aerobic composting. In this study, changes in the size, shape, pores, chemical compositions, and crystal structures of pig manure particles during composting were investigated. The results showed that the median diameter (D50) decreased exponentially, while the particle aspect ratio and sphericity were unchanged, suggesting that particles were degraded uniformly along different radial directions. Pores had a mean diameter of 15-30 μm and were elliptical. The particle porosity increased linearly mainly because of hemicellulose degradation. Furthermore, the influence of particle structure variation on the first order rate constant (k) of organic matter degradation was corrected, which may facilitate the optimization of operation conditions. The k value was proportional to the reciprocal of D50 according to the specific surface area of particles, and it decreased with increased porosity due to the stabilized chemical compositions and crystal structures of particles. However, the applicability of these data to other composting materials should be verified. PMID:25781372

  17. Polymeric Endoaortic Paving (PEAP): Mechanical, Thermoforming, and Degradation Properties of Polycaprolactone/Polyurethane Blends for Cardiovascular Applications

    PubMed Central

    Ashton, John H.; Mertz, James A. M.; Harper, John L.; Slepian, Marvin J.; Mills, Joseph L.; McGrath, Dominic V.; Vande Geest, Jonathan P.

    2010-01-01

    Polymeric endoaortic paving (PEAP) is a process by which a polymer is endovascularly delivered and thermoformed to coat or “pave” the lumen of the aorta. This method may offer an improvement to conventional endoaortic therapy in allowing conformal graft application with reduced risk of endoleak and customization to complex patient geometries. Polycaprolactone (PCL)/polyurethane (PU) blends of various blend ratios were assessed as a potential material for PEAP by characterizing their mechanical, thermoforming, and degradation properties. Biaxial tension testing revealed that the blends' stiffness is similar to that of aortic tissue, is higher for blends with more PCL content, and may be affected by thermoforming and degradation. Tubes of blends were able to maintain a higher diameter increase after thermoforming at higher PCL content and higher heating temperatures; 50/50 blend tubes heated to 55°C were able to maintain 90% of the diameter increase applied. Delamination forces of the blends ranged from 41 to 235 N/m2. In a Pseudomonas lipase solution, the 50/50 blend had a 94% lower degradation rate than pure PCL, and the 10/90 blend exhibited no degradation. These results indicate that PEAP, consisting of a PCL/PU blend, may be useful in developing the next generation of endoaortic therapy. PMID:20832506

  18. An Understanding of the Photocatalytic Properties and Pollutant Degradation Mechanism of SrTiO3 Nanoparticles.

    PubMed

    da Silva, Luís F; Lopes, Osmando F; de Mendonça, Vagner R; Carvalho, Kele T G; Longo, Elson; Ribeiro, Caue; Mastelaro, Valmor R

    2016-05-01

    Strontium titanate nanoparticles have attracted much attention due to their physical and chemical properties, especially as photocatalysts under ultraviolet irradiation. In this paper, we analyze the effect of heating rate during the crystallization process of SrTiO3 nanoparticles in the degradation of organic pollutants. The relationship between structural, morphological and photocatalytic properties of the SrTiO3 nanoparticles was investigated using different techniques. Transmission electron microscopy and N2 adsorption results show that particle size and surface properties are tuned by the heating rate of the SrTiO3 crystallization process. The SrTiO3 nanoparticles showed good photoactivity for the degradation of methylene blue, rhodamine B and methyl orange dyes, driven by a nonselective process. The SrTiO3 sample with the largest particle size exhibited higher photoactivity per unit area, independent of the molecule to be degraded. The results pointed out that the photodegradation of methylene blue dye catalyzed by SrTiO3 is caused by the action of valence band holes (direct pathway), and the indirect mechanism has a negligible effect, i.e. degradation by O2 (-•) and (•) OH radicals attack. PMID:27010848

  19. Degradation mechanisms of materials for large space systems in low Earth orbit

    NASA Technical Reports Server (NTRS)

    Gordon, William L.; Hoffman, R. W.

    1987-01-01

    Degradation was explored of various materials used in aerospace vehicles after severe loss of polymeric material coatings (Kapton) was observed on an early shuttle flight in low Earth orbit. Since atomic oxygen is the major component of the atmosphere at 300 km, and the shuttle's orbital velocity produced relative motion corresponding to approx. 5 eV of oxygen energy, it was natural to attribute much of this degradation to oxygen interaction. This assumption was tested using large volume vacuum systems and ion beam sources, in an exploratory effort to produce atomic oxygen of the appropriate energy, and to observe mass loss from various samples as well as optical radiation. Several investigations were initiated and the results of these investigations are presented in four papers. These papers are summarized. They are entitled: (1) The Space Shuttle Glow; (2) Laboratory Degradation of Kapton in a Low Energy Oxygen Ion Beam; (3) The Energy Dependence and Surface Morphology of Kapton Degradation Under Atomic Oxygen Bombardment; and (4) Surface Analysis of STS 8 Samples.

  20. [Degradation Mechanism of 4-Chlorophenol on a Pd-Fe/graphene Multifunctional Catalytic Cathode].

    PubMed

    Qi, Wen-zhi; Wang, Fan; Wang, Hui; Shi, Qin; Pang, Lei; Bian, Zhao-yong

    2015-06-01

    A Pd-Fe/graphene multifunctional catalytic cathode was prepared to build a diaphragm electrolysis system with a Ti/IrO2/RuO2 anode and an organicterylene filter cloth. The degradation of organic wastewater containing 4-chlorophenol by combination of cathodic hydrogenation dechlorination and oxidation of anode and cathode was investigated. The degradation process was monitored and characterized in aid of TOC analysis, UV-Vis spectra, high performance liquid chromatogram, and ion chromatogram. The results showed that the degradation efficiencies of 4-chlorophenol in the present system with Pd-Fe/graphene catalytic cathode were 98.1% (in cathodic chamber), 95.1% (in anodic chamber) under the optimal conditions, which were higher than those of the Pd/graphene catalytic cathode system (93.3% in cathodic chamber, 91.4% in anodic chamber). The chloride ion removal rate was more than 95% in the Pd-Fe/graphene catalytic cathode system, which suggested that the bimetallic catalyst had stronger hydrogenation capacity. 4-chlorophenol could be completely removed within 120 min under the synergetic effect of anodic-cathodic electrochemical degradation. In the cathodic chamber, 4-chlorophenol was initially reduced to form phenol under electrocatalytic hydrolysis. With further oxidation in both cathodic and anodic chambers, phenol was converted into hydroquinone and benzoquinone, then low molecular weight organic acids, and finally CO2 and H2O. Moreover, a reaction pathway involving all these intermediates was proposed. PMID:26387322

  1. POLYPHENOLS AND MECHANICAL MACERATION SHIFT PROTEIN FRACTIONS IN LEGUME HAYS FROM RAPIDLY TO SLOWLY DEGRADED FORMS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rapid proteolysis of forage protein during rumen fermentation can impair protein use by dairy cattle. The severity of conditioning at harvest may influence protein degradability in forages, particularly if protein-binding polyphenols are present. In 2002 and 2003, first and second cuttings of alfalf...

  2. Molecular Mechanism of Nicotine Degradation by a Newly Isolated Strain, Ochrobactrum sp. Strain SJY1

    PubMed Central

    Yu, Hao; Zhu, Xiongyu; Li, Yangyang

    2014-01-01

    A newly isolated strain, SJY1, identified as Ochrobactrum sp., utilizes nicotine as a sole source of carbon, nitrogen, and energy. Strain SJY1 could efficiently degrade nicotine via a variant of the pyridine and pyrrolidine pathways (the VPP pathway), which highlights bacterial metabolic diversity in relation to nicotine degradation. A 97-kbp DNA fragment containing six nicotine degradation-related genes was obtained by gap closing from the genome sequence of strain SJY1. Three genes, designated vppB, vppD, and vppE, in the VPP pathway were cloned and heterologously expressed, and the related proteins were characterized. The vppB gene encodes a flavin-containing amine oxidase converting 6-hydroxynicotine to 6-hydroxy-N-methylmyosmine. Although VppB specifically catalyzes the dehydrogenation of 6-hydroxynicotine rather than nicotine, it shares higher amino acid sequence identity with nicotine oxidase (38%) from the pyrrolidine pathway than with its isoenzyme (6-hydroxy-l-nicotine oxidase, 24%) from the pyridine pathway. The vppD gene encodes an NADH-dependent flavin-containing monooxygenase, which catalyzes the hydroxylation of 6-hydroxy-3-succinoylpyridine to 2,5-dihydroxypyridine. VppD shows 62% amino acid sequence identity with the hydroxylase (HspB) from Pseudomonas putida strain S16, whereas the specific activity of VppD is ∼10-fold higher than that of HspB. VppE is responsible for the transformation of 2,5-dihydroxypyridine. Sequence alignment and phylogenetic analysis suggested that the VPP pathway, which evolved independently from nicotinic acid degradation, might have a closer relationship with the pyrrolidine pathway. The proteins and functional pathway identified here provide a sound basis for future studies aimed at a better understanding of molecular principles of nicotine degradation. PMID:25344232

  3. Molecular mechanism of nicotine degradation by a newly isolated strain, Ochrobactrum sp. strain SJY1.

    PubMed

    Yu, Hao; Tang, Hongzhi; Zhu, Xiongyu; Li, Yangyang; Xu, Ping

    2015-01-01

    A newly isolated strain, SJY1, identified as Ochrobactrum sp., utilizes nicotine as a sole source of carbon, nitrogen, and energy. Strain SJY1 could efficiently degrade nicotine via a variant of the pyridine and pyrrolidine pathways (the VPP pathway), which highlights bacterial metabolic diversity in relation to nicotine degradation. A 97-kbp DNA fragment containing six nicotine degradation-related genes was obtained by gap closing from the genome sequence of strain SJY1. Three genes, designated vppB, vppD, and vppE, in the VPP pathway were cloned and heterologously expressed, and the related proteins were characterized. The vppB gene encodes a flavin-containing amine oxidase converting 6-hydroxynicotine to 6-hydroxy-N-methylmyosmine. Although VppB specifically catalyzes the dehydrogenation of 6-hydroxynicotine rather than nicotine, it shares higher amino acid sequence identity with nicotine oxidase (38%) from the pyrrolidine pathway than with its isoenzyme (6-hydroxy-l-nicotine oxidase, 24%) from the pyridine pathway. The vppD gene encodes an NADH-dependent flavin-containing monooxygenase, which catalyzes the hydroxylation of 6-hydroxy-3-succinoylpyridine to 2,5-dihydroxypyridine. VppD shows 62% amino acid sequence identity with the hydroxylase (HspB) from Pseudomonas putida strain S16, whereas the specific activity of VppD is ∼10-fold higher than that of HspB. VppE is responsible for the transformation of 2,5-dihydroxypyridine. Sequence alignment and phylogenetic analysis suggested that the VPP pathway, which evolved independently from nicotinic acid degradation, might have a closer relationship with the pyrrolidine pathway. The proteins and functional pathway identified here provide a sound basis for future studies aimed at a better understanding of molecular principles of nicotine degradation. PMID:25344232

  4. The Mechanisms and Physiological Relevance of Glycocalyx Degradation in Hepatic Ischemia/Reperfusion Injury

    PubMed Central

    van Golen, Rowan F.; Reiniers, Megan J.; Vrisekoop, Nienke; Zuurbier, Coert J.; Olthof, Pim B.; van Rheenen, Jacco; van Gulik, Thomas M.; Parsons, Barry J.

    2014-01-01

    Abstract Significance: Hepatic ischemia/reperfusion (I/R) injury is an inevitable side effect of major liver surgery that can culminate in liver failure. The bulk of I/R-induced liver injury results from an overproduction of reactive oxygen and nitrogen species (ROS/RNS), which inflict both parenchymal and microcirculatory damage. A structure that is particularly prone to oxidative attack and modification is the glycocalyx (GCX), a meshwork of proteoglycans and glycosaminoglycans (GAGs) that covers the lumenal endothelial surface and safeguards microvascular homeostasis. ROS/RNS-mediated degradation of the GCX may exacerbate I/R injury by, for example, inducing vasoconstriction, facilitating leukocyte adherence, and directly activating innate immune cells. Recent Advances: Preliminary experiments revealed that hepatic sinusoids contain a functional GCX that is damaged during murine hepatic I/R and major liver surgery in patients. There are three ROS that mediate GCX degradation: hydroxyl radicals, carbonate radical anions, and hypochlorous acid (HOCl). HOCl converts GAGs in the GCX to GAG chloramides that become site-specific targets for oxidizing and reducing species and are more efficiently fragmented than the parent molecules. In addition to ROS/RNS, the GAG-degrading enzyme heparanase acts at the endothelial surface to shed the GCX. Critical Issues: The GCX seems to be degraded during major liver surgery, but the underlying cause remains ill-defined. Future Directions: The relative contribution of the different ROS and RNS intermediates to GCX degradation in vivo, the immunogenic potential of the shed GCX fragments, and the role of heparanase in liver I/R injury all warrant further investigation. Antioxid. Redox Signal. 21, 1098–1118. PMID:24313895

  5. Detailed modeling of the atmospheric degradation mechanism of very-short lived brominated species

    NASA Astrophysics Data System (ADS)

    Krysztofiak, G.; Catoire, V.; Poulet, G.; Marécal, V.; Pirre, M.; Louis, F.; Canneaux, S.; Josse, B.

    2012-11-01

    Detailed chemical reaction schemes for the atmospheric degradations of the very short-lived species (VSLS) bromoform (CHBr3) and dibromomethane (CH2Br2) have been established. These degradation schemes have been implemented in the meteorological/tracer transport model CATT-BRAMS used in the present case as pseudo one-dimensional model with chemistry of CH4, CO, HOx, NOx, NOy and Ox. They include the main possible reactions of the intermediate brominated peroxy radicals RO2 (with R = CH2Br, CHBr2 and CBr3) for which the most likely reaction pathways with HO2 have been found using ab initio computational calculations. The full degradation schemes have been run for two well-defined realistic scenarios, “clean” atmosphere and “moderately” NOy-polluted atmosphere, as representative of a tropical coastal region where these VSLS natural emissions are expected to be important. The Henry's law constants of the brominated organics products have been estimated by using the Bond Contribution Method (BCM; Meylan and Howard, 1991) or the Molecular Connectivity Index (MCI; Nirmalakhandan and Speece, 1988). Using these constants, the least soluble species formed from the VSLS degradation are found to be CBr2O, CHBrO, CBr3O2NO2, CHBr2O2NO2, BrO, BrONO2 and HOBr, which leads those to be potentially transported into the tropical tropopause layer (TTL) in case of deep convection and contribute to stratospheric bromine additionally to the original substances. For bromoform and dibromomethane degradation, the moderate NOy pollution increases the production of the least soluble species and thus approximately doubles the bromine quantity potentially able to reach the TTL (from 22.5% to 43% for CHBr3 and from 8.8% to 20.2% for CH2Br2). The influence of the reactions of the RO2 radicals with HO2, CH3O2 and NO2 on the nature and abundance of the stable intermediate and end-products has been tested for CHBr3 degradation. As a result, the reactions of the RO2 radicals with NO2 have no

  6. Mechanical Degradation of Aggregate by the Los Angeles-, the Micro-Deval- and the Nordic Test Methods

    NASA Astrophysics Data System (ADS)

    Erichsen, E.; Ulvik, A.; Sævik, K.

    2011-05-01

    The quality of aggregate used as buildings materials is defined by European Standard test methods. According to the agreement within the European Economic Area, each individual country decides test methods of current interest. Among the Nordic countries, the Los Angeles-, micro-Deval- and the Nordic test are the most common methods used to decide the mechanical properties of the aggregate. The three test methods are all drum test where the degradation of the material occur by rotation between the test material and steel balls together with, or without water. The mechanical test methods are empirical and are believed to express either resistance to fragmentation or wearing. The results of this study show that analysing the particle size distribution of a material after the drum testing give indication of which type and degree of degradation the test material is exposed to. Knowledge of the type of degradation for the test methods is important compared to the understanding of the real breakdown of the aggregate for instance used in road construction.

  7. SELECTIVE AND NON-SELECTIVE METALLOPROTEINASE INHIBITORS REDUCE IL-1-INDUCED CARTILAGE DEGRADATION AND LOSS OF MECHANICAL PROPERTIES

    PubMed Central

    Wilson, Christopher G.; Palmer, Ashley W.; Zuo, Fengrong; Eugui, Elsie; Wilson, Stacy; Mackenzie, Rebecca; Sandy, John D.; Levenston, Marc E.

    2015-01-01

    Articular cartilage undergoes matrix degradation and loss of mechanical properties when stimulated with proinflammatory cytokines such as interleukin-1 (IL-1). Aggrecanases and matrix metalloproteinases (MMPs) are thought to be principal downstream effectors of cytokine-induced matrix catabolism, and aggrecanase- or MMP-selective inhibitors reduce or block matrix destruction in several model systems. The objective of this study was to use metalloproteinase inhibitors to perturb IL-1-induced matrix catabolism in bovine cartilage explants and examine their effects on changes in tissue compression and shear properties. Explanted tissue was stimulated with IL-1 for up to 24 days in the absence or presence of inhibitors which were aggrecanase-selective, MMP-selective, or non-selective. Analysis of conditioned media and explant digests revealed that aggrecanase-mediated aggrecanolysis was delayed to varying extents with all inhibitor treatments, but that aggrecan release persisted. Collagen degradation was abrogated by MMP- and non-selective inhibitors and reduced by the aggrecanase inhibitor. The inhibitors delayed but did not reduce loss of the equilibrium compression modulus, whereas the loss of dynamic compression and shear moduli was delayed and reduced. The data suggest that non-metalloproteinase mechanisms participate in IL-1-induced matrix degradation and loss of tissue material properties. PMID:17174540

  8. Genome sequencing reveals mechanisms for heavy metal resistance and polycyclic aromatic hydrocarbon degradation in Delftia lacustris strain LZ-C.

    PubMed

    Wu, Wenyang; Huang, Haiying; Ling, Zhenmin; Yu, Zhengsheng; Jiang, Yiming; Liu, Pu; Li, Xiangkai

    2016-01-01

    Strain LZ-C, isolated from a petrochemical wastewater discharge site, was found to be resistant to heavy metals and to degrade various aromatic compounds, including naphenol, naphthalene, 2-methylnaphthalene and toluene. Data obtained from 16S rRNA gene sequencing showed that this strain was closely related to Delftia lacustris. The 5,889,360 bp genome of strain LZ-C was assembled into 239 contigs and 197 scaffolds containing 5855 predicted open reading frames (ORFs). Among these predicted ORFs, 464 were different from the type strain of Delftia. The minimal inhibitory concentrations were 4 mM, 30 µM, 2 mM and 1 mM for Cr(VI), Hg(II), Cd(II) and Pb(II), respectively. Both genome sequencing and quantitative real-time PCR data revealed that genes related to Chr, Czc and Mer family genes play important roles in heavy metal resistance in strain LZ-C. In addition, the Na(+)/H(+) antiporter NhaA is important for adaptation to high salinity resistance (2.5 M NaCl). The complete pathways of benzene and benzoate degradation were identified through KEGG analysis. Interestingly, strain LZ-C also degrades naphthalene but lacks the key naphthalene degradation gene NahA. Thus, we propose that strain LZ-C exhibits a novel protein with a function similar to NahA. This study is the first to reveal the mechanisms of heavy metal resistance and salinity tolerance in D. lacustris and to identify a potential 2-methylnaphthalene degradation protein in this strain. Through whole-genome sequencing analysis, strain LZ-C might be a good candidate for the bioremediation of heavy metals and polycyclic aromatic hydrocarbons. PMID:26589947

  9. MDM2-Mediated Degradation of p14ARF: A Novel Mechanism to Control ARF Levels in Cancer Cells

    PubMed Central

    Vivo, Maria; Matarese, Maria; Sepe, Maria; Di Martino, Rosaria; Festa, Luisa; Calabrò, Viola; Mantia, Girolama La; Pollice, Alessandra

    2015-01-01

    We here show a new relationship between the human p14ARF oncosuppressor and the MDM2 oncoprotein. MDM2 overexpression in various cancer cell lines causes p14ARF reduction inducing its degradation through the proteasome. The effect does not require the ubiquitin ligase activity of MDM2 and preferentially occurs in the cytoplasm. Interestingly, treatment with inhibitors of the PKC (Protein Kinase C) pathway and use of p14ARF phosphorylation mutants indicate that ARF phosphorylation could play a role in MDM2 mediated ARF degradation reinforcing our previous observations that ARF phosphorylation influences its stability and biological activity. Our study uncovers a new potentially important mechanism through which ARF and MDM2 can counterbalance each other during the tumorigenic process. PMID:25723571

  10. Thermoelectric generator testing and RTG degradation mechanisms evaluation. Progress report No. 35

    SciTech Connect

    Lockwood, A.; Shields, V.

    1980-05-01

    The n-type selenide legs after 14,000 hours continue to show reasonable agreement with the 3M Co. published data. In the ingradient testing after 14,700 hours the n-legs show serious degradation in power to load. Weight loss measurements on the first samples of material produced by G.E. match the results previously obtained on R.C.A. material from the MHW program. The remaining MHW generator on test Q1-A has accumulated 22,519 hours and performance remains stable. The 18 couple modules S/N-1 and -3 previously tested at RCA show no significant change in operation during the current JPL testing. No changes in the trends of degradation of LES 8 and 9 and the Voyager RTGs have been observed.

  11. Mechanical degradation of porous titanium with entangled structure filled with biodegradable magnesium in Hanks' solution.

    PubMed

    Li, Qiuyan; Jiang, Guofeng; Wang, Cunlong; Dong, Jie; He, Guo

    2015-12-01

    The degradation behavior of the porous titanium with entangled structure filled with biodegradable magnesium (p-Ti/Mg) in Hanks' solution was investigated. It was found that the p-Ti/Mg composite had higher strength than pure magnesium and porous titanium with entangled structure (p-Ti). Although the magnesium in p-Ti/Mg was completely dissolved in Hanks' solution after immersion for 104 h, the rest of the sample still maintained strength of about 86 MPa. Moreover, the produced porousness (due to magnesium-degradation) could provide channels for the ingrowth and transportation of bone cells. However, the high corrosion rate of p-Ti/Mg is still a problem when used as a candidate biomedical material, which needs further improvement. PMID:26354275

  12. Investigation of accelerated stress factors and failure/degradation mechanisms in terrestrial solar cells

    NASA Technical Reports Server (NTRS)

    Lathrop, J. W.

    1984-01-01

    Research on the reliability of terrestrial solar cells was performed to identify failure/degradation modes affecting solar cells and to relate these to basic physical, chemical, and metallurgical phenomena. Particular concerns addressed were the reliability attributes of individual single crystalline, polycrystalline, and amorphous thin film silicon cells. Results of subjecting different types of crystalline cells to the Clemson accelerated test schedule are given. Preliminary step stress results on one type of thin film amorphous silicon (a:Si) cell indicated that extraneous degradation modes were introduced above 140 C. Also described is development of measurement procedures which are applicable to the reliability testing of a:Si solar cells as well as an approach to achieving the necessary repeatability of fabricating a simulated a:Si reference cell from crystalline silicon photodiodes.

  13. Reaction pathways and mechanisms of the electrochemical degradation of phenol on different electrodes.

    PubMed

    Li, Xiao-Yan; Cui, Yu-Hong; Feng, Yu-Jie; Xie, Zhao-Ming; Gu, Ji-Dong

    2005-05-01

    Laboratory experiments were carried out on the kinetics and pathways of the electrochemical (EC) degradation of phenol at three different types of anodes, Ti/SnO2-Sb, Ti/RuO2, and Pt. Although phenol was oxidised by all of the anodes at a current density of 20 mA/cm2 or a cell voltage of 4.6 V, there was a considerable difference between the three anode types in the effectiveness and performance of EC organic degradation. Phenol was readily mineralized at the Ti/SnO2-Sb anode, but its degradation was much slower at the Ti/RuO2 and Pt anodes. The analytical results of high-performance liquid chromatography (HPLC) and gas chromatography coupled with mass spectrometry (GC/MS) indicated that the intermediate products of EC phenol degradation, including benzoquinone and organic acids, were subsequently oxidised rapidly by the Ti/SnO2-Sb anode, but accumulated in the cells of Ti/RuO2 and Pt. There was also a formation of dark-coloured polymeric compounds and precipitates in the solutions electrolyzed by the Ti/RuO2 and Pt anodes, which was not observed for the Ti/SnO2-Sb cells. It is argued that anodic property not only affects the reaction kinetics of various steps of EC organic oxidation, but also alters the pathway of phenol electrolysis. Favourable surface treatment, such as the SnO2-Sb coating, provides the anode with an apparent catalytic function for rapid organic oxidation that is probably brought about by hydroxyl radicals generated from anodic water electrolysis. PMID:15882890

  14. Age-related changes of myocardial ATP supply and demand mechanisms

    PubMed Central

    Yaniv, Yael; Juhaszova, Magdalena; Sollott, Steven J.

    2013-01-01

    In advanced age, the resting myocardial oxygen consumption (M V̇O2) and cardiac work (CW) in the rat remain intact. However, M V̇O2, CW and cardiac efficiency achieved at high demand are decreased with age, compared to maximal values in the young. Whether this deterioration is due to decrease in myocardial ATP demand, ATP supply, or the control mechanisms that match them, remains controversial. Here we discuss evolving perspectives of age-related changes of myocardial ATP supply and demand mechanisms, and critique experimental models used to investigate aging. Specifically, we evaluate experimental data collected at the level of isolated mitochondria, tissue, or organism, and discuss how mitochondrial energetic mechanisms change in advanced age, both at basal and high energy demand levels. PMID:23845538

  15. INHIBITION OF CDK9 PREVENTS MECHANICAL INJURY-INDUCED INFLAMMATION, APOPTOSIS AND MATRIX DEGRADATION IN CARTILAGE EXPLANTS

    PubMed Central

    Hu, Z.; Yik, J.H.N.; Cissell, D.D.; Michelier, P.V.; Athanasiou, K.A.; Haudenschild, D.R.

    2016-01-01

    Joint injury often leads to post-traumatic osteoarthritis (PTOA). Acute injury responses to trauma induce production of pro-inflammatory cytokines and catabolic enzymes, which promote chondrocyte apoptosis and degrade cartilage to potentiate PTOA development. Recent studies show that the rate-limiting step for transcriptional activation of injury response genes is controlled by cyclin-dependent kinase 9 (CDK9), and thus it is an attractive target for limiting the injury response. Here, we determined the effects of CDK9 inhibition in suppressing the injury response in mechanically-injured cartilage explants. Bovine cartilage explants were injured by a single compressive load of 30 % strain at 100 %/s, and then treated with the CDK9 inhibitor Flavopiridol. To assess acute injury responses, we measured the mRNA expression of pro-inflammatory cytokines, catabolic enzymes, and apoptotic genes by RT-PCR, and chondrocyte viability and apoptosis by TUNEL staining. For long-term outcome, cartilage matrix degradation was assessed by soluble glycosaminoglycan release, and by determining the mechanical properties with instantaneous and relaxation moduli. Our data showed CDK9 inhibitor markedly reduced injury-induced inflammatory cytokine and catabolic gene expression. CDK9 inhibitor also attenuated chondrocyte apoptosis and reduced cartilage matrix degradation. Lastly, the mechanical properties of the injured explants were preserved by CDK9 inhibitor. Our results provide a temporal profile connecting the chain of events from mechanical impact, acute injury responses, to the subsequent induction of chondrocyte apoptosis and cartilage matrix deterioration. Thus, CDK9 is a potential disease-modifying agent for injury response after knee trauma to prevent or delay PTOA development. PMID:26859911

  16. An In Vitro Mechanism Study on the Proliferation and Pluripotency of Human Embryonic Stems Cells in Response to Magnesium Degradation

    PubMed Central

    Nguyen, Thanh Yen; Liew, Chee Gee; Liu, Huinan

    2013-01-01

    Magnesium (Mg) is a promising biodegradable metallic material for applications in cellular/tissue engineering and biomedical implants/devices. To advance clinical translation of Mg-based biomaterials, we investigated the effects and mechanisms of Mg degradation on the proliferation and pluripotency of human embryonic stem cells (hESCs). We used hESCs as the in vitro model system to study cellular responses to Mg degradation because they are sensitive to toxicants and capable of differentiating into any cell types of interest for regenerative medicine. In a previous study when hESCs were cultured in vitro with either polished metallic Mg (99.9% purity) or pre-degraded Mg, cell death was observed within the first 30 hours of culture. Excess Mg ions and hydroxide ions induced by Mg degradation may have been the causes for the observed cell death; hence, their respective effects on hESCs were investigated for the first time to reveal the potential mechanisms. For this purpose, the mTeSR®1 hESC culture media was either modified to an alkaline pH of 8.1 or supplemented with 0.4–40 mM of Mg ions. We showed that the initial increase of media pH to 8.1 had no adverse effect on hESC proliferation. At all tested Mg ion dosages, the hESCs grew to confluency and retained pluripotency as indicated by the expression of OCT4, SSEA3, and SOX2. When the supplemental Mg ion dosages increased to greater than 10 mM, however, hESC colony morphology changed and cell counts decreased. These results suggest that Mg-based implants or scaffolds are promising in combination with hESCs for regenerative medicine applications, providing their degradation rate is moderate. Additionally, the hESC culture system could serve as a standard model for cytocompatibility studies of Mg in vitro, and an identified 10 mM critical dosage of Mg ions could serve as a design guideline for safe degradation of Mg-based implants/scaffolds. PMID:24146887

  17. Irradiation of ultrasound to 5-methylbenzotriazole in aqueous phase: Degradation kinetics and mechanisms.

    PubMed

    Kim, Duk K; He, Yingxin; Jeon, Junho; O'Shea, Kevin E

    2016-07-01

    Ultrasonic irradiation (640kHz) leads to the effective degradation of 5-methyl-benzotriazole (5-MBT) in O2 saturated aqueous solution. Up to 97% of 5-MBT is eliminated within 2h of treatment. Upon extended treatment of 6h, UV absorbance of the n→π(∗) and π→π(∗) transitions associated with aromatic and conjugated systems are completely removed, indicating complete destruction of the aromatic system in 5-MBT. The decomposition of 5-MBT follows pseudo-first order kinetics and the observed decomposition rate dropped significantly in the presence of tertiary butyl alcohol. Detailed product studies were performed employing a negative mode ESI LC-MS. Twenty eight intermediate products were detected during ultrasonic mediated degradation of 5-MBT. Reaction pathways are proposed based on the structures of products assigned to observed 28 masses from LC-MS and commonly accepted degradation pathways observed by thermal and hydroxyl radical mediated pathways often associated with ultrasonic treatment. PMID:26964945

  18. Study of the thermal degradation mechanism of a composite propellant. [using electron microscopes

    NASA Technical Reports Server (NTRS)

    Schmidt, W. G.

    1975-01-01

    The current experimental program was designed to systematically investigate the role of the oxidizer in the thermal degradation process of composite propellants. The scanning electron microscope (SEM) was used to examine the failure sites in thermally degraded propellant samples. The formulation variables tested were oxidizer purity, oxidizer particle size, and oxidizer to binder bonding agent. The binder, a saturated hydrocarbon, was kept constant throughout the experiments. The oxidizers were: AP, chlorate-doped AP, arsenate-doped AP, and phosphate-doped AP. The oxidizer particle size distribution was 60% of the large fraction and 40% of the small fraction. The bonding agent, when present, was used at the 0.15% level. The data showed that both the oxidizer purity and particle size had an important affect on the thermal degradation process. The affect of the oxidizer particle size was more noticeable at the higher temperature and stress levels. An examination of the failure site, by SEM, of propellants subject to these latter conditions indicated that the fracturing of the large oxidizer particles led to the propellant cracking.

  19. Kinetics and mechanism of degradation of dichlorvos in aqueous solutions containing reduced sulfur species.

    PubMed

    Gan, Qiu; Singh, Raphael M; Wu, Tong; Jans, Urs

    2006-09-15

    Reactions of dichlorvos with five reduced sulfur species (hydrogen sulfide, bisulfide, thiosulfate, thiophenol, and thiophenolate) were examined in well-defined anoxic aqueous solutions to investigate their role in its degradation. Reactions were monitored at varying concentrations of reduced sulfur species over pH range to obtain the second-order reaction rate constants. Experiments at 25 degrees C demonstrated that degradation of dichlorvos promoted by bisufide, thiosulfate, and thiophenolate were of much greater importance than hydrolysis under the experimental conditions in our study. In contrast, hydrogen sulfide and thiophenol were not effective in the degradation of dichlorvos. The activation parameters of the reaction of dichlorvos with bisulfide, thiosulfate, and thiophenolate were also determined from the measured second-order rate constants over a temperature range of 12-50 degrees C. The relative reactivity of the reduced sulfur species decreases in the following order: PhS- > HS- approximately equal to S2O3(2-). When the second-order rate constants at 25 degrees C are multiplied by the environmentally relevant concentration of the reduced sulfur species, predicted half-lives of dichlorvos ranged from hours to days. The results indicated that reduced sulfur species could play a very important role in the chemical fate of dichlorvos in coastal marine environments. PMID:17007131

  20. The Role of Exercise in Cardiac Aging: From Physiology to Molecular Mechanisms.

    PubMed

    Roh, Jason; Rhee, James; Chaudhari, Vinita; Rosenzweig, Anthony

    2016-01-22

    Aging induces structural and functional changes in the heart that are associated with increased risk of cardiovascular disease and impaired functional capacity in the elderly. Exercise is a diagnostic and therapeutic tool, with the potential to provide insights into clinical diagnosis and prognosis, as well as the molecular mechanisms by which aging influences cardiac physiology and function. In this review, we first provide an overview of how aging impacts the cardiac response to exercise, and the implications this has for functional capacity in older adults. We then review the underlying molecular mechanisms by which cardiac aging contributes to exercise intolerance, and conversely how exercise training can potentially modulate aging phenotypes in the heart. Finally, we highlight the potential use of these exercise models to complement models of disease in efforts to uncover new therapeutic targets to prevent or treat heart disease in the aging population. PMID:26838314

  1. Multi-level femoral morphology and mechanical properties of rats of different ages.

    PubMed

    Zhang, Rui; Gong, He; Zhu, Dong; Ma, Renshi; Fang, Juan; Fan, Yobo

    2015-07-01

    A macro-micro-nano-multi-level study was conducted to explore age-related structural and mechanical properties of bone, as well as the effects of aging on bone properties. A total of 70 male Wistar rats were used, ranging in the ages of 1, 3, 5, 7, 9, 11, 14, 15, 16, and 17 months (n = 7/age group). After micro-computed tomography (CT) scanning, longitudinal cortical bone specimens with a length of 5mm were cut along the femoral shaft axis from left femur shafts for mechanical testing, and the cross-sectional areas were measured. The macro-mechanical properties obtained in mechanical testing and microarchitecture parameters measured by micro-CT were significantly correlated with the animal age (r(2) = 0.96, p < 0.001). Scanning electron microscopy was used for detecting the microarchitecture features of the fractured surfaces, which exhibited age-related plate-fibrous-mixed fibrous-plate texture, resulting in changes in macro-mechanical properties (r(2) > 0.90, p < 0.001). The mineral phase of the left femoral shaft and head was analyzed by atomic force microscopy. Longitudinal and transverse trabecular bone tissues, as well as longitudinal cortical bone tissue, were used for nanoindentation test, and the chemical composition was evaluated by quantitative chemical analyses. The correlations between mineral content and bone material properties (i.e., elastic properties of the bone tissue and size and roughness of bone mineral grains) were highly significant (r > 0.95, p < 0.001). Multi-level femur morphology, mechanical property, and mineral content were significantly correlated with the animal age. The correlations between bone mineral content and bone material morphological and mechanical properties may partly explain the increase in bone fragility with aging, which will provide a theoretical basis for the investigation of age-related bone properties in clinics. PMID:25857690

  2. Environmental aging in polycrystalline-Si photovoltaic modules: comparison of chamber-based accelerated degradation studies with field-test data

    NASA Astrophysics Data System (ADS)

    Lai, T.; Biggie, R.; Brooks, A.; Potter, B. G.; Simmons-Potter, K.

    2015-09-01

    Lifecycle degradation testing of photovoltaic (PV) modules in accelerated-degradation chambers can enable the prediction both of PV performance lifetimes and of return-on-investment for installations of PV systems. With degradation results strongly dependent on chamber test parameters, the validity of such studies relative to fielded, installed PV systems must be determined. In the present work, accelerated aging of a 250 W polycrystalline silicon module is compared to real-time performance degradation in a similar polycrystalline-silicon, fielded, PV technology that has been operating since October 2013. Investigation of environmental aging effects are performed in a full-scale, industrial-standard environmental chamber equipped with single-sun irradiance capability providing illumination uniformity of 98% over a 2 x 1.6 m area. Time-dependent, photovoltaic performance (J-V) is evaluated over a recurring, compressed night-day cycle providing representative local daily solar insolation for the southwestern United States, followed by dark (night) cycling. This cycle is synchronized with thermal and humidity environmental variations that are designed to mimic, as closely as possible, test-yard conditions specific to a 12 month weather profile for a fielded system in Tucson, AZ. Results confirm the impact of environmental conditions on the module long-term performance. While the effects of temperature de-rating can be clearly seen in the data, removal of these effects enables the clear interpretation of module efficiency degradation with time and environmental exposure. With the temperature-dependent effect removed, the normalized efficiency is computed and compared to performance results from another panel of similar technology that has previously experienced identical climate changes in the test yard. Analysis of relative PV module efficiency degradation for the chamber-tested system shows good comparison to the field-tested system with ~2.5% degradation following

  3. Energy-restricted diet benefits body composition but degrades bone integrity in middle-aged obese female rats.

    PubMed

    Shen, Chwan-Li; Zhu, Wenbin; Gao, Weimin; Wang, Shu; Chen, Lixia; Chyu, Ming-Chien

    2013-08-01

    This study investigates the effects of a restricted diet (RD) on body composition and musculoskeletal health along with endocrines and molecular mechanism in established mature obese rats. Twenty female rats were fed with a high-fat diet (HFD) ad libitum for 4 months and then assigned to either HFD or RD group for another 4 months. Another 10 rats were on a low-fat diet for 8 months. Outcome measures included body composition, bone mineral density, microarchitecrure, and strength; serum leptin, adiponectin, insulin-like growth factor I, and liver glutathione peroxidase activity; and protein expression and spleen tumor necrosis factor α messenger RNA expression. We hypothesized that mature obese rats on a 35% energy restriction diet for 4 months would improve body composition but degrade microstructural and mechanical properties of long bones, and such changes in musculoskeletal integrity are related to the modulation of obesity-related endocrines and proinflammation. Relative to HFD, RD benefited body composition (decreased body weight and %fat mass and increased %fat-free mass); decreased insulin-like growth factor I and leptin; elevated adiponectin, glutathione peroxidase activity and protein expression and tumor necrosis factor α messenger RNA expression; and suppressed bone formation and increased bone resorption, resulting in decreased trabecular and cortical bone volume, bone mineral density, and bone strength. Relative to low-fat diet, RD had a similar effect on body composition and serum markers but increased bone turnover rate and decreased bone mineral density and strength. Our data suggest that long-term RD has a negative impact on bone remodeling in obese female rats, probably through modification of endocrines and elevation of proinflammation. PMID:23890357

  4. Understanding aging mechanisms in lithium-ion battery packs: From cell capacity loss to pack capacity evolution

    NASA Astrophysics Data System (ADS)

    Zheng, Yuejiu; Ouyang, Minggao; Lu, Languang; Li, Jianqiu

    2015-03-01

    Battery cell capacity loss is extensively studied so as to extend battery life in varied applications from portable consumer electronics to energy storage devices. Battery packs are constructed especially in energy storage devices to provide sufficient voltage and capacity. However, engineering practice indicates that battery packs always fade more critically than cells. We investigate the evolution of battery pack capacity loss by analyzing cell aging mechanisms using the "Electric quantity - Capacity Scatter Diagram (ECSD)" from a system point of view. The results show that cell capacity loss is not the sole contributor to pack capacity loss. The loss of lithium inventory variation at anodes between cells plays a significant role in pack capacity evolution. Therefore, we suggest more attention could be paid to the loss of lithium inventory at anodes in order to mitigate pack capacity degradation.

  5. Mechanical behavior of a Y-TZP ceramic for monolithic restorations: effect of grinding and low-temperature aging.

    PubMed

    Pereira, G K R; Silvestri, T; Camargo, R; Rippe, M P; Amaral, M; Kleverlaan, C J; Valandro, L F

    2016-06-01

    This study aimed to investigate the effects of grinding with diamond burs and low-temperature aging on the mechanical behavior (biaxial flexural strength and structural reliability), surface topography, and phase transformation of a Y-TZP ceramic for monolithic dental restorations. Disc-shaped specimens (Zirlux FC, Ivoclar Vivadent) were manufactured according to ISO 6872 (2008) and divided in accordance with two factors: "grinding - 3 levels" and "LTD - 2 levels". Grinding was performed using a contra-angle handpiece under constant water-cooling with different grit-sizes (extra-fine and coarse diamond burs). LTD was simulated in an autoclave at 134°C, under a pressure of 2 bar, over a period of 20h. Surface topography analysis showed an increase in roughness based on surface treatment grit-size (Coarse>Xfine>Ctrl), LTD did not influence roughness values. Both grinding and LTD promoted an increase in the amount of m-phase, although different susceptibilities to degradation were observed. According to existing literature the increase of m-phase content is a direct indicative of Y-TZP degradation. Weibull analysis showed an increase in characteristic strength after grinding (Coarse=Xfine>Ctrl), while for LTD, distinct effects were observed (Ctrlaging in autoclave for 20h (LTD) and grinding showed not to be detrimental to the mechanical properties of Zirlux FC Y-TZP ceramic. PMID:27040197

  6. Design, Degradation Mechanism and Long-Term Cytotoxicity of Poly(L-lactide) and Poly(Lactide-co-ϵ-Caprolactone) Terpolymer Film and Air-Spun Nanofiber Scaffold.

    PubMed

    Sabbatier, Gad; Larrañaga, Aitor; Guay-Bégin, Andrée-Anne; Fernandez, Jorge; Diéval, Florence; Durand, Bernard; Sarasua, Jose-Ramon; Laroche, Gaétan

    2015-10-01

    Degradable nanofiber scaffold is known to provide a suitable, versatile and temporary structure for tissue regeneration. However, synthetic nanofiber scaffold must be properly designed to display appropriate tissue response during the degradation process. In this context, this publication focuses on the design of a finely-tuned poly(lactide-co-ϵ-caprolactone) terpolymer (PLCL) that may be appropriate for vascular biomaterials applications and its comparison with well-known semi-crystalline poly(l-lactide) (PLLA). The degradation mechanism of polymer film and nanofiber scaffold and endothelial cells behavior cultured with degradation products is elucidated. The results highlights benefits of using PLCL terpolymer as vascular biomaterial compared to PLLA. PMID:26058993

  7. Review of Recent Aging-Related Degradation Occurrences of Structures and Passive Components in U.S. Nuclear Power Plants

    SciTech Connect

    Nie,J.; Braverman, J.; Hofmayer, C.; Choun, Y.-S.; Kim, M.K.; Choi, I.-K.

    2009-04-02

    The Korea Atomic Energy Research Institute (KAERI) and Brookhaven National Laboratory (BNL) are collaborating to develop seismic capability evaluation technology for degraded structures and passive components (SPCs) under a multi-year research agreement. To better understand the status and characteristics of degradation of SPCs in nuclear power plants (NPPs), the first step in this multi-year research effort was to identify and evaluate degradation occurrences of SPCs in U.S. NPPs. This was performed by reviewing recent publicly available information sources to identify and evaluate the characteristics of degradation occurrences and then comparing the information to the observations in the past. Ten categories of SPCs that are applicable to Korean NPPs were identified, comprising of anchorage, concrete, containment, exchanger, filter, piping system, reactor pressure vessel, structural steel, tank, and vessel. Software tools were developed to expedite the review process. Results from this review effort were compared to previous data in the literature to characterize the overall degradation trends.

  8. Adaptive coupling between damage mechanics and peridynamics: A route for objective simulation of material degradation up to complete failure

    NASA Astrophysics Data System (ADS)

    Han, Fei; Lubineau, Gilles; Azdoud, Yan

    2016-09-01

    The objective (mesh-independent) simulation of evolving discontinuities, such as cracks, remains a challenge. Current techniques are highly complex or involve intractable computational costs, making simulations up to complete failure difficult. We propose a framework as a new route toward solving this problem that adaptively couples local-continuum damage mechanics with peridynamics to objectively simulate all the steps that lead to material failure: damage nucleation, crack formation and propagation. Local-continuum damage mechanics successfully describes the degradation related to dispersed microdefects before the formation of a macrocrack. However, when damage localizes, it suffers spurious mesh dependency, making the simulation of macrocracks challenging. On the other hand, the peridynamic theory is promising for the simulation of fractures, as it naturally allows discontinuities in the displacement field. Here, we present a hybrid local-continuum damage/peridynamic model. Local-continuum damage mechanics is used to describe "volume" damage before localization. Once localization is detected at a point, the remaining part of the energy is dissipated through an adaptive peridynamic model capable of the transition to a "surface" degradation, typically a crack. We believe that this framework, which actually mimics the real physical process of crack formation, is the first bridge between continuum damage theories and peridynamics. Two-dimensional numerical examples are used to illustrate that an objective simulation of material failure can be achieved by this method.

  9. Mechanisms Regulating the Degradation of Dentin Matrices by Endogenous Dentin Proteases and their Role in Dental Adhesion. A Review

    PubMed Central

    Sabatini, Camila; Pashley, David H.

    2015-01-01

    Purpose This systematic review provides an overview of the different mechanisms proposed to regulate the degradation of dentin matrices bye host-derived dentin proteases, particularly as it relates to their role in dental adhesion. Methods Significant developments have taken place over the last few years that have contributed to a better understanding of all the factors affecting the durability of adhesive resin restorations. The complexity of dentin-resin interfaces mandates a thorough understanding of all the mechanical, physical and biochemical aspects that play a role in the formation of hybrid layers. The ionic and hydrophilic nature of current dental adhesives yields permeable, unstable hybrid layers susceptible to water sorption, hydrolytic degradation and resin leaching. The hydrolytic activity of host-derived proteases also contributes to the degradation of the resin-dentin bonds. Preservation of the collagen matrix is critical to the improvement of resin-dentin bond durability. Approaches to regulate collagenolytic activity of dentin proteases have been the subject of extensive research in the last few years. A shift has occurred from the use of proteases inhibitors to the use of collagen cross-linking agents. Data provided by fifty-one studies published in peer-reviewed journals between January 1999 and December 2013 was compiled in this systematic review. Results Appraisal of the data provided by the studies included in the present review yielded a summary of the mechanisms which have already proven to be clinically successful and those which need further investigation before new clinical protocols can be adopted. PMID:25831604

  10. In-situ polymerisation of fully bioresorbable polycaprolactone/phosphate glass fibre composites: In vitro degradation and mechanical properties.

    PubMed

    Chen, Menghao; Parsons, Andrew J; Felfel, Reda M; Rudd, Christopher D; Irvine, Derek J; Ahmed, Ifty

    2016-06-01

    Fully bioresorbable composites have been investigated in order to replace metal implant plates used for hard tissue repair. Retention of the composite mechanical properties within a physiological environment has been shown to be significantly affected due to loss of the integrity of the fibre/matrix interface. This study investigated phosphate based glass fibre (PGF) reinforced polycaprolactone (PCL) composites with 20%, 35% and 50% fibre volume fractions (Vf) manufactured via an in-situ polymerisation (ISP) process and a conventional laminate stacking (LS) followed by compression moulding. Reinforcing efficiency between the LS and ISP manufacturing process was compared, and the ISP composites revealed significant improvements in mechanical properties when compared to LS composites. The degradation profiles and mechanical properties were monitored in phosphate buffered saline (PBS) at 37°C for 28 days. ISP composites revealed significantly less media uptake and mass loss (p<0.001) throughout the degradation period. The initial flexural properties of ISP composites were substantially higher (p<0.0001) than those of the LS composites, which showed that the ISP manufacturing process provided a significantly enhanced reinforcement effect than the LS process. During the degradation study, statistically higher flexural property retention profiles were also seen for the ISP composites compared to LS composites. SEM micrographs of fracture surfaces for the LS composites revealed dry fibre bundles and poor fibre dispersion with polymer rich zones, which indicated poor interfacial bonding, distribution and adhesion. In contrast, evenly distributed fibres without dry fibre bundles or polymer rich zones, were clearly observed for the ISP composite samples, which showed that a superior fibre/matrix interface was achieved with highly improved adhesion. PMID:26748261

  11. Mechanism of triphenylmethane Cresol Red degradation by Trichoderma harzianum M06.

    PubMed

    Nor, Nurafifah Mohd; Hadibarata, Tony; Zubir, Meor Mohd Fikri Ahmad; Lazim, Zainab Mat; Adnan, Liyana Amalina; Fulazzaky, Mohamad Ali

    2015-11-01

    Cresol Red belongs to the triphenylmethane (TPM) class of dyes which are potentially carcinogenic or mutagenic. However, very few studies on biodegradation of Cresol Red were investigated as compared to other type dyes such as azo and anthraquinone dye. The aim of this work is to evaluate triphenylmethane dye Cresol Red degradation by fungal strain isolated from the decayed wood in Johor Bahru, Malaysia. Detailed taxonomic studies identified the organisms as Trichoderma species and designated as strain Trichoderma harzianum M06. In this study, Cresol Red was decolorized up to 88% within 30 days under agitation condition by Trichoderma harzianum M06. Data analysis revealed that a pH value of 3 yielded a highest degradation rate among pH concentrations (73%), salinity concentrations of 100 g/L (73%), and a volume of 0.1 mL of Tween 80 (79%). Induction in the enzyme activities of manganese peroxidase, lignin peroxidase, laccase, 1,2- and 2,3-dioxygenase indicates their involvement in Cresol Red removal. Various analytical studies such as Thin-Layer Chromatography (TLC), UV-Vis spectrophotometer, and Gas chromatography mass spectrometry (GC-MS) confirmed the biotransformation of Cresol Red by the fungus. Two metabolites were identified in the treated medium: 2,4-dihydroxybenzoic acid (t R 7.3 min and m/z 355) and 2-hydroxybenzoic acid (t R 8.6 min and m/z 267). Based on these products, a probable pathway has been proposed for the degradation of Cresol Red by Trichoderma harzianum M06. PMID:26275435

  12. Kinetic and mechanism investigation on the gamma irradiation induced degradation of endosulfan sulfate.

    PubMed

    Shah, Noor S; Khan, Javed Ali; Nawaz, Shah; Ismail, M; Khan, Kifayatullah; Khan, Hasan M

    2015-02-01

    The gamma irradiation was investigated for potential removal of endosulfan sulfate, an emerging water pollutant and central nervous system disruptor. A removal efficiency of 99.5% of initially 1.30 μM endosulfan sulfate was observed at an absorbed dose of 1020 Gy. Aqueous electron (eaq(-)) was found to play primary role in the removal of endosulfan sulfate which was possibly due to greater reactivity of eaq(-) with endosulfan sulfate, considering the second-order rate constant of 8.1×10(9) and 3.4×10(10) M(-1) s(-1) for hydroxyl radical (·OH) and eaq(-), respectively, with endosulfan sulfate. The removal efficiency of endosulfan sulfate was affected by the pH of aqueous solution, with observed removal efficiency of 99.5%, 98.3% and 31.3% at pH 6.2, pH 10.0, and pH 2.6, respectively. The efficiency was also influenced by inorganic anions and humic acid in the order of nitrate>nitrite>bicarbonate>carbonate ≃ humic acid. The initial degradation rate increased while degradation constant decreased with increasing initial concentrations of endosulfan sulfate. The degradation pathways showed that oxidative pathway was initiated at the SO2 bond while reductive pathways at the chlorine attached to the ring of endosulfan sulfate. The mass balance showed removal of 98% chloride and 72% sulfate ions from endosulfan sulfate at an absorbed dose of 1020 Gy. The removal of endosulfan sulfate followed by subsequent loss of by-products under extended treatment showed that gamma irradiation is potential technique for the remediation of organic pollutants from a water environment. PMID:25466821

  13. Thermo-Mechanical Properties of Semi-Degradable Poly(β-amino ester)-co-Methyl Methacrylate Networks under Simulated Physiological Conditions

    PubMed Central

    Safranski, David L.; Crabtree, Jacob C.; Huq, Yameen R.; Gall, Ken

    2011-01-01

    Poly(β-amino ester) networks are being explored for biomedical applications, but they may lack the mechanical properties necessary for long term implantation. The objective of this study is to evaluate the effect of adding methyl methacrylate on networks' mechanical properties under simulated physiological conditions. The networks were synthesized in two parts: (1) a biodegradable crosslinker was formed from a diacrylate and amine, (2) and then varying concentrations of methyl methacrylate were added prior to photopolymerizing the network. Degradation rate, mechanical properties, and glass transition temperature were studied as a function of methyl methacrylate composition. The crosslinking density played a limited role on mechanical properties for these networks, but increasing methyl methacrylate concentration improved the toughness by several orders of magnitude. Under simulated physiological conditions, networks showed increasing toughness or sustained toughness as degradation occurred. This work establishes a method of creating degradable networks with tailorable toughness while undergoing partial degradation. PMID:21966028

  14. Degradation of sulfur mustard on KF/Al2O3 supports: insights into the products and the reactions mechanisms.

    PubMed

    Zafrani, Yossi; Goldvaser, Michael; Dagan, Shai; Feldberg, Liron; Mizrahi, Dana; Waysbort, Daniel; Gershonov, Eytan; Columbus, Ishay

    2009-11-01

    The degradation of the warfare agent sulfur mustard (HD) adsorbed onto KF/Al(2)O(3) sorbents is described. These processes were explored by MAS NMR, using (13)C-labeled sulfur mustard (HD*) and LC-MS techniques. Our study on the detoxification of this blister agent showed the formation of nontoxic substitution and less-toxic elimination products (t(1/2) = 3.5-355 h). Interestingly, the reaction rates were found to be affected by MAS conditions, i.e., by a centrifugation effect. The products and the mechanisms of these processes are discussed. PMID:19817399

  15. Insight on RDX degradation mechanism by Rhodococcus strains using 13C and 15N kinetic isotope effects.

    PubMed

    Bernstein, Anat; Ronen, Zeev; Gelman, Faina

    2013-01-01

    The explosive Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is known to be degraded aerobically by various isolates of the Rhodococcus species, with denitration being the key step, mediated by Cytochrome P450. Our study aimed at gaining insight into the RDX degradation mechanism by Rhodococcus species and comparing isotope effects associated with RDX degradation by distinct Rhodococcus strains. For these purposes, enrichment in (13)C and (15)N isotopes throughout RDX denitration was studied for three distinct Rhodococcus strains, isolated from soil and groundwater in an RDX-contaminated site. The observable (15)N enrichment throughout the reaction, together with minor (13)C enrichment, suggests that N-N bond cleavage is likely to be the key rate-limiting step in the reaction. The similarity in the kinetic (15)N isotope effect between the three tested strains suggests that either isotope-masking effects are negligible, or are of a similar extent for all tested strains. The lack of variability in the kinetic (15)N isotope effect allows the interpretation of environmental studies with greater confidence. PMID:23215036

  16. Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

    PubMed

    Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

    2015-11-01

    Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation. PMID:26455367

  17. Mechanism and kinetic properties of OH-initiated atmospheric oxidation degradation of methamidophos in the presence of O2/NO

    NASA Astrophysics Data System (ADS)

    Shi, Xiangli; Zhang, Ruiming; Zhang, Qingzhu; Wang, Wenxing

    2016-05-01

    Methamidophos is a member of the organophosphorus insecticides. In the present work, the mechanism of the OH radical-initiated atmospheric oxidation degradation of methamidophos and the possible degradation products were investigated with the aid of quantum chemical calculations. The geometrical parameters and vibrational frequencies were calculated at the MPWB1K/6-31+G(d,p) level. The energies of all the stationary points were carried out at the MPWB1K/6-311+G(3df,2p) level of theory. The rate constants of key elementary steps involved in the OH radical-initiated atmospheric degradation of methamidophos were calculated by meaning of the canonical variation transition-state (CVT) theory with the small curvature tunneling (SCT) correction over the possible atmospheric temperature range of 273-333 K. The rate-temperature formulas were fitted for the first time. The pre-exponential factor and the activation energy were obtained. Studies show that the OH additions from the trans-positions of the NH2 and OCH3 groups, the H abstractions from the SCH3 and OCH3 groups as well as the substitution reaction resulting in the products of CH3OP(O)OHNH2 and SCH3 are thermodynamically favorable reaction pathways for the reaction of methamidophos with OH radicals due to the low barrier and strong exothermicity.

  18. Degradation of oligosaccharides in nonenzymatic browning by formation of alpha-dicarbonyl compounds via a "peeling off" mechanism.

    PubMed

    Hollnagel, A; Kroh, L W

    2000-12-01

    The formation of alpha-dicarbonyl-containing substances and Amadori rearrangement products was studied in the glycine-catalyzed (Maillard reaction) and uncatalyzed thermal degradation of glucose, maltose, and maltotriose using o-phenylenediamine as trapping agent. Various degradation products, especially alpha-dicarbonyl compounds, are formed from carbohydrates with differing degrees of polymerization during nonenzymatic browning. The different Amadori rearrangement products, isomerization products, and alpha-dicarbonyls produced by the used carbohydrates were quantified throughout the observed reaction time, and the relevance of the different degradation pathways is discussed. In the Maillard reaction (MR) the amino-catalyzed rearrangement with subsequent elimination of water predominated, giving rise to hexosuloses with alpha-dicarbonyl structure, whereas under caramelization conditions more sugar fragments with an alpha-dicarbonyl moiety were formed. For the MR of oligosaccharides a mechanism is proposed in which 1,4-dideoxyosone is formed as the predominating alpha-dicarbonyl in the quasi-water-free thermolysis of di- and trisaccharides in the presence of glycine. PMID:11312795

  19. Enhanced UV-visible response of bismuth subcarbonate nanowires for degradation of xanthate and photocatalytic reaction mechanism.

    PubMed

    Cui, Kuixin; He, Yuehui; Jin, Shengming

    2016-04-01

    (BiO)2CO3 nanowires were prepared by simple hydrothermal treatment of commercial Bi2O3 powders and characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of (BiO)2CO3 nanowires was studied through degradation of sodium isopropyl xanthate. Photocatalytic experimental results indicated that the as-prepared (BiO)2CO3 nanowires show high photocatalytic efficiency. Photocatalytic activity increased after two cycles. Time-dependent UV-vis spectra demonstrated that the final degradation products included isopropyl alcohol and carbon disulfide. UV-vis diffuse reflection spectra showed that the band gap of the as-prepared (BiO)2CO3 nanowires and recycled (BiO)2CO3 nanowires were 2.75 eV and 1.15 eV, respectively. XPS results indicated that formation of Bi2S3@(BiO)2CO3 core-shell nanowires occurred after recycled photodegradation of isopropyl xanthate owing to existence of two types of Bi configurations in the recycled (BiO)2CO3 nanowires. A probable degradation mechanism of isopropyl xanthate was also proposed. PMID:26866962

  20. Quantifying the effects of sterilization and aging on the oxidative degradation and wear of crosslinked and conventional polyethylene used in total joint replacement

    NASA Astrophysics Data System (ADS)

    Willie, Bettina Maria

    2005-07-01

    Nearly 500,000 total knee and hip replacements are performed annually in the United States. The generation of ultra-high molecular weight polyethylene (PE) particulate wear debris and associated osteolysis has increasingly become the predominant cause of revision operation. Research has shown that radiation sterilization in air results in increased oxidative degradation and accelerated wear of PE components. The overall goal of this work was to better understand the effect of sterilization, radiation crosslinking, and aging on the oxidative degradation and wear performance of PE components in order to improve clinical outcomes in total joint replacement. The data indicated that after four years of real-time shelf aging, PE that was radiation sterilized in air or nitrogen had significantly greater oxidative degradation compared to PE that was sterilized with either gas plasma or ethylene oxide. After two years of real-time shelf aging, negligible oxidation occurred with minimal changes in density and percent crystallinity, indicating that oxidative degradation was not an issue in the highly crosslinked and conventional polyethylene components examined. The differences measured between time zero and two years shelf aging may be likely explained by instrumentation error or variation within polyethylene manufacturing lots. Data suggest that current manufacturing and packaging technologies have successfully avoided oxidative degradation during shelf aging. Shelf aging may not be a concern in highly crosslinked or conventional polyethylene with current packaging technologies. Conventional PE tibial components had significantly greater percent area of premelt total surface damage compared to crosslinked PE tibial components. However, conventional PE tibial components did not have a significantly different percent area of postmelt total surface damage compared to crosslinked PE tibial components. Data indicated that in vivo duration was a significant predictor of premelt

  1. In vitro degradation and mechanical properties of PLA-PCL copolymer unit cell scaffolds generated by two-photon polymerization.

    PubMed

    Felfel, R M; Poocza, Leander; Gimeno-Fabra, Miquel; Milde, Tobias; Hildebrand, Gerhard; Ahmed, Ifty; Scotchford, Colin; Sottile, Virginie; Grant, David M; Liefeith, Klaus

    2016-02-01

    The manufacture of 3D scaffolds with specific controlled porous architecture, defined microstructure and an adjustable degradation profile was achieved using two-photon polymerization (TPP) with a size of 2  ×  4  ×  2 mm(3). Scaffolds made from poly(D,L-lactide-co-ɛ-caprolactone) copolymer with varying lactic acid (LA) and ɛ -caprolactone (CL) ratios (LC16:4, 18:2 and 9:1) were generated via ring-opening-polymerization and photoactivation. The reactivity was quantified using photo-DSC, yielding a double bond conversion ranging from 70% to 90%. The pore sizes for all LC scaffolds were see 300 μm and throat sizes varied from 152 to 177 μm. In vitro degradation was conducted at different temperatures; 37, 50 and 65 °C. Change in compressive properties immersed at 37 °C over time was also measured. Variations in thermal, degradation and mechanical properties of the LC scaffolds were related to the LA/CL ratio. Scaffold LC16:4 showed significantly lower glass transition temperature (T g) (4.8 °C) in comparison with the LC 18:2 and 9:1 (see 32 °C). Rates of mass loss for the LC16:4 scaffolds at all temperatures were significantly lower than that for LC18:2 and 9:1. The degradation activation energies for scaffold materials ranged from 82.7 to 94.9 kJ mol(-1). A prediction for degradation time was applied through a correlation between long-term degradation studies at 37 °C and short-term studies at elevated temperatures (50 and 65 °C) using the half-life of mass loss (Time (M1/2)) parameter. However, the initial compressive moduli for LC18:2 and 9:1 scaffolds were 7 to 14 times higher than LC16:4 (see 0.27) which was suggested to be due to its higher CL content (20%). All scaffolds showed a gradual loss in their compressive strength and modulus over time as a result of progressive mass loss over time. The manufacturing process utilized and the scaffolds produced have potential for use in tissue engineering and regenerative medicine

  2. 77 FR 41457 - Aging Management Associated With Wall Thinning Due to Erosion Mechanisms

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-13

    ... Register on June 22, 2010 (75 FR 35510). The NRC staff has developed draft LR-ISG-2012-01 to: (a) Revise... COMMISSION Aging Management Associated With Wall Thinning Due to Erosion Mechanisms AGENCY: Nuclear... Interim Staff Guidance (LR-ISG), LR-ISG-2012-01, ``Wall Thinning Due to Erosion Mechanisms.'' The draft...

  3. Thermoelectric generator testing and RTG degradation mechanisms evaluation. Progress report No. 37

    SciTech Connect

    Lockwood, A.; Shields, V.

    1980-09-01

    The n-type selenide legs after 16,500 hours continue to show reasonable agreement with the 3M Co. published thermal conductivity data. In the ingradient testing after 17,000 hours the 3 surviving n-legs (out of 5) show serious degradation in power to load. Small scale ratcheting has been observed on the four p-legs but no large scale effects. Weight loss for both coated and uncoated material produced by G.E. are reported. No significant discrepancies with the results previously obtained on R.C.A. material from the MHW program have been found. Thermal conductivity measurements are also in agreement. The remaining MHW generator on test, Q1-A, has accumulated 25,600 hours and performance remains stable. The 18 couple modules S/N-1 and -3 previously tested at RCA show no significant change in operation during the current JPL testing. No changes in the trends of degradation of LES 8 and 9 and the Voyager RTGs have been observed.

  4. Thermoelectric generator testing and RTG degradation mechanisms evaluation. Progress report No. 36

    SciTech Connect

    Lockwood, A.; Shields, V.

    1980-07-01

    The n-type selenide legs after 15,000 hours continue to show reasonable agreement with the 3M Co. published thermal conductivity data. In the ingradient testing after 16,500 hours the 3 surviving n-legs (out of 5) show serious degradation in power to load. Weight loss and thermoelectricity property measurements on the first samples of material produced by G.E. continue to correspond to the results previously obtained on R.C.A. material from the MHW program. The remaining MHW generator on test, Q1-A, has accumulated 23,679 hours and performance remains stable. The 18 couple modules S/N-1 and -3 previously tested at RCA show no significant change in operation during the current JPL testing. A comparison of LES 8/9 RTG's with an improved version of DEGRA is shown. No changes in the trends of degradation of LES 8 and 9 and the Voyager RTGs have been observed.

  5. Visualization of TlBr ionic transport mechanism by the Accelerated Device Degradation technique

    NASA Astrophysics Data System (ADS)

    Datta, Amlan; Becla, Piotr; Motakef, Shariar

    2015-06-01

    Thallium Bromide (TlBr) is a promising gamma radiation semiconductor detector material. However, it is an ionic semiconductor and suffers from polarization. As a result, TlBr devices degrade rapidly at room temperature. Polarization is associated with the flow of ionic current in the crystal under electrical bias, leading to the accumulation of charged ions at the device's electrical contacts. We report a fast and reliable direct characterization technique to identify the effects of various growth and post-growth process modifications on the polarization process. The Accelerated Device Degradation (ADD) characterization technique allows direct observation of nucleation and propagation of ionic transport channels within the TlBr crystals under applied bias. These channels are observed to be initiated both directly under the electrode as well as away from it. The propagation direction is always towards the anode indicating that Br- is the mobile diffusing species within the defect channels. The effective migration energy of the Br- ions was calculated to be 0.33±0.03 eV, which is consistent with other theoretical and experimental results.

  6. Photooxidative degradation mechanism of model compounds of poly( p-phenylenevinylenes) [PPVs

    NASA Astrophysics Data System (ADS)

    Ma, Lichuan; Wang, Xuesong; Wang, Bojie; Chen, Jingrong; Wang, Jianhua; Huang, Kai; Zhang, Baowen; Cao, Yi; Han, Zhenhui; Qian, Suping; Yao, Side

    2002-12-01

    Seven model compounds of poly( p-phenylenevinylenes) [M-PPVs] were designed to perform the photooxidative degradation experiments. The degradation rates of M-PPVs depend on the nature, number, and position of substituents. The transient species including singlet oxygen, superoxide radical anion, M-PPV triplet state, M-PPV radical cation and anion in M-PPV photodegradation were observed and characterized systematically with ESR spin trapping, pulse radiolysis, and laser flash photolysis techniques. By using rose bengal, methylene blue, fullerene, tetraphenyl porphyrin, 9,10-dicyanoanthracene, or biacetyl as sensitizer in dye-sensitized M-PPV photodegradation experiments, we found that singlet oxygen does not play the principal role as previous reported. Results of triplet-triplet energy transfer from biacetyl to M-PPVs and M-PPV triplet state quenching by 1,4-diazabicyclo[2.2.2] octane (DABCO) suggested that the reaction between M-PPV triplet state and oxygen is really the key step in the processes of photodegradation of the conjugated structure.

  7. A comparative study of commercial lithium ion battery cycle life in electrical vehicle: Aging mechanism identification

    NASA Astrophysics Data System (ADS)

    Han, Xuebing; Ouyang, Minggao; Lu, Languang; Li, Jianqiu; Zheng, Yuejiu; Li, Zhe

    2014-04-01

    When lithium-ion batteries age with cycling, the battery capacity decreases and the resistance increases. The aging mechanism of different types of lithium-ion batteries differs. The loss of lithium inventory, loss of active material, and the increase in resistance may result in battery aging. Generally, analysis of the battery aging mechanism requires dismantling of batteries and using methods such as X-ray diffraction and scanning electron microscopy. These methods may permanently damage the battery. Therefore, the methods are inappropriate for the battery management system (BMS) in an electric vehicle. The constant current charging curves while charging the battery could be used to get the incremental capacity and differential voltage curves for identifying the aging mechanism; the battery state-of-health can then be estimated. This method can be potentially used in the BMS for online diagnostic and prognostic services. The genetic algorithm could be used to quantitatively analyze the battery aging offline. And the membership function could be used for onboard aging mechanism identification.

  8. Cardiac Aging: From Molecular Mechanisms to Significance in Human Health and Disease

    PubMed Central

    Dai, Dao-Fu; Chen, Tony; Johnson, Simon C.; Szeto, Hazel

    2012-01-01

    Abstract Cardiovascular diseases (CVDs) are the major causes of death in the western world. The incidence of cardiovascular disease as well as the rate of cardiovascular mortality and morbidity increase exponentially in the elderly population, suggesting that age per se is a major risk factor of CVDs. The physiologic changes of human cardiac aging mainly include left ventricular hypertrophy, diastolic dysfunction, valvular degeneration, increased cardiac fibrosis, increased prevalence of atrial fibrillation, and decreased maximal exercise capacity. Many of these changes are closely recapitulated in animal models commonly used in an aging study, including rodents, flies, and monkeys. The application of genetically modified aged mice has provided direct evidence of several critical molecular mechanisms involved in cardiac aging, such as mitochondrial oxidative stress, insulin/insulin-like growth factor/PI3K pathway, adrenergic and renin angiotensin II signaling, and nutrient signaling pathways. This article also reviews the central role of mitochondrial oxidative stress in CVDs and the plausible mechanisms underlying the progression toward heart failure in the susceptible aging hearts. Finally, the understanding of the molecular mechanisms of cardiac aging may supp