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Sample records for aging degradation mechanisms

  1. Aging degradation of cast stainless steels: Effects on mechanical properties

    SciTech Connect

    Chopra, O.K.; Chung, H.M.

    1987-06-01

    A program is being conducted to investigate the significance of in-service embrittlement of cast duplex stainless steels under light-water operating conditions. Mechanical property data are presented from Charpy-impact, tensile, and J-R curve tests for several heats of cast stainless steel aged up to 10,000 h at 450, 400, 350, 320, and 290/sup 0/C. The results indicate that thermal aging increases the tensile strength and decreases the impact energy, J/sub IC/, and tearing modulus of the steels. Also, the ductile-to-brittle transition curve shifts to higher temperatures. The fracture toughness results are consistent with the Charpy-impact data, i.e., the relative reduction in J/sub IC/ is similar to the relative decrease in impact energy. The ferrite content and concentration of C in the steel have a strong effect on the overall process of low-temperature embrittlement. The low-carbon CF-3 steels are the most resistant and Mo-containing CF-8M steels are most susceptible to embrittlement. Weakening of the ferrite/austenite phase boundaries by carbide precipitates has a significant effect on the kinetics and extent of embrittlement of the high-carbon CF-8 and CF-8M steels, particularly after aging at temperatures greater than or equal to400/sup 0/C. The influence of N content and distribution of ferrite on loss of toughness are discussed. The data also indicate that existing correlations do not accurately represent the embrittlement behavior over the temperature range 280 to 450/sup 0/C, i.e., extrapolation of high-temperature data to reactor temperatures may not be valid for some compositions of cast stainless steel.

  2. Correlation between mechanical and chemical degradation after outdoor and accelerated laboratory aging for multilayer photovoltaic backsheets

    NASA Astrophysics Data System (ADS)

    Lin, Chiao-Chi; Lyu, Yadong; Yu, Li-Chieh; Gu, Xiaohong

    2016-09-01

    Channel cracking fragmentation testing and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy were utilized to study mechanical and chemical degradation of a multilayered backsheet after outdoor and accelerated laboratory aging. A model sample of commercial PPE backsheet, namely polyethylene terephthalate/polyethylene terephthalate/ethylene vinyl acetate (PET/PET/EVA) was investigated. Outdoor aging was performed in Gaithersburg, Maryland, USA for up to 510 days, and complementary accelerated laboratory aging was conducted on the NIST (National Institute of Standards and Technology) SPHERE (Simulated Photodegradation via High Energy Radiant Exposure). Fracture energy, mode I stress intensity factor and film strength were analyzed using an analytical model based on channel cracking fragmentation testing results. The correlation between mechanical and chemical degradation was discussed for both outdoor and accelerated laboratory aging. The results of this work provide preliminary understanding on failure mechanism of backsheets after weathering, laying the groundwork for linking outdoor and indoor accelerated laboratory testing for multilayer photovoltaic backsheets.

  3. Restricting the ageing degradation of the mechanical properties of gamma irradiated UHMWPE using MWCNTs.

    PubMed

    Rama Sreekanth, P S; Kanagaraj, S

    2013-05-01

    Property degradation of the medical grade polymers after gamma irradiation is the primary concern that limits longevity of them. Though the conventional antioxidant material helps to reduce the degradation but it limits the degree of crosslinking of the polymer. The objective of the present work is to study the influence of multi walled carbon nanotubes (MWCNTs) on restricting the degradation of mechanical properties of medical grade ultra high molecular weight polyethylene (UHMWPE) after its irradiation. UHMWPE was reinforced by chemically treated MWCNTs at different concentrations such as 0.5, 1.0, 1.5, and 2.0 wt%. The test samples were then subjected to Co⁶⁰ gamma irradiation with an integral dose of 25, 50, 75 and 100 kGy in air. The mechanical properties of irradiated samples were evaluated within 10 days, 60 and 120 days after irradiation. It was observed that the mechanical properties of virgin UHMWPE and nanocomposites were enhanced immediately after irradiation but they were found to be reduced at later stages. It was also observed that the presence of MWCNTs limited the ageing degradation of the mechanical properties of UHMWPE. Raman spectroscopic and TEM studies confirmed the formation of irradiation induced defects on the MWCNTs. Electron spin resonance studies showed that the relative radical intensity of virgin UHWMPE was reduced significantly with an increase of MWCNTs concentration confirming the radical scavenging ability of them. It is concluded that MWCNTs restricted the ageing degradation of irradiated UHMWPE.

  4. Changes in Structural-Mechanical Properties and Degradability of Collagen during Aging-associated Modifications*

    PubMed Central

    Panwar, Preety; Lamour, Guillaume; Mackenzie, Neil C. W.; Yang, Heejae; Ko, Frank; Li, Hongbin; Brömme, Dieter

    2015-01-01

    During aging, changes occur in the collagen network that contribute to various pathological phenotypes in the skeletal, vascular, and pulmonary systems. The aim of this study was to investigate the consequences of age-related modifications on the mechanical stability and in vitro proteolytic degradation of type I collagen. Analyzing mouse tail and bovine bone collagen, we found that collagen at both fibril and fiber levels varies in rigidity and Young's modulus due to different physiological changes, which correlate with changes in cathepsin K (CatK)-mediated degradation. A decreased susceptibility to CatK-mediated hydrolysis of fibrillar collagen was observed following mineralization and advanced glycation end product-associated modification. However, aging of bone increased CatK-mediated osteoclastic resorption by ∼27%, and negligible resorption was observed when osteoclasts were cultured on mineral-deficient bone. We observed significant differences in the excavations generated by osteoclasts and C-terminal telopeptide release during bone resorption under distinct conditions. Our data indicate that modification of collagen compromises its biomechanical integrity and affects CatK-mediated degradation both in bone and tissue, thus contributing to our understanding of extracellular matrix aging. PMID:26224630

  5. Degradation mechanisms of cable insulation materials during radiation-thermal ageing in radiation environment

    NASA Astrophysics Data System (ADS)

    Seguchi, Tadao; Tamura, Kiyotoshi; Ohshima, Takeshi; Shimada, Akihiko; Kudoh, Hisaaki

    2011-02-01

    Radiation and thermal degradation of ethylene-propylene rubber (EPR) and crosslinked polyethylene (XLPE) as cable insulation materials were investigated by evaluating tensile properties, gel-fraction, and swelling ratio, as well as by the infrared (FTIR) analysis. The activation energy of thermal oxidative degradation changed over the range 100-120 °C for both EPR and XLPE. This may be attributed to the fact that the content of an antioxidant used as the stabilizer for polymers decreases by evaporation during thermal ageing at high temperatures. The analysis of antioxidant content and oxidative products in XLPE as a model sample showed that a small amount of antioxidant significantly reduced the extent of thermal oxidation, but was not effective for radiation induced oxidation. The changes in mechanical properties were well reflected by the degree of oxidation. A new model of polymer degradation mechanisms was proposed where the degradation does not take place by chain reaction via peroxy radical and hydro-peroxide. The role of the antioxidant in the polymer is the reduction of free radical formation in the initiation step in thermal oxidation, and it could not stop radical reactions for either radiation or thermal oxidation.

  6. 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.

  7. 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.

  8. 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.

  9. DEA degradation mechanism

    SciTech Connect

    Meisen, A.; Kennard, M.L.

    1982-10-01

    Examines factors that increase diethanolamine (DEA) degradation, which reportedly depends on temperature, pressure, gas composition, amine concentration, pH of the amine solution and the presence of metal ions. Plant operators have tried to solve the problem by changing operating conditions and/or installing activated carbon filters. DEA degradation is frequently experienced in gas plants used for removing acidic gases such as carbon dioxide and hydrogen sulfide from light hydrocarbons. Experimental results reveal that degradation is governed by: solubility of CO/sub 2/ in the DEA solution; degree of dissociation of the DEA molecules in solution; interaction of DEA and CO/sub 2/ molecules and/or ionic complexes. Most, or all, these phenomena are affected by temperature, pressure, DEA concentration and pH. A series of tests to determine whether activated carbon is capable of removing impurities from partially degraded DEA solutions showed that this treatment did not remove any major degradation compounds from the solutions.

  10. 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.

  11. 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.

  12. 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.

  13. Age-related degradation of Westinghouse 480-volt circuit breakers

    SciTech Connect

    Subudhi, M.; Shier, W.; MacDougall, E. )

    1990-07-01

    An aging assessment of Westinghouse DS-series low-voltage air circuit breakers was performed as part of the Nuclear Plant Aging Research (NPAR) program. The objectives of this study are to characterize age-related degradation within the breaker assembly and to identify maintenance practices to mitigate their effect. Since this study has been promulgated by the failures of the reactor trip breakers at the McGuire Nuclear Station in July 1987, results relating to the welds in the breaker pole lever welds are also discussed. The design and operation of DS-206 and DS-416 breakers were reviewed. Failure data from various national data bases were analyzed to identify the predominant failure modes, causes, and mechanisms. Additional operating experiences from one nuclear station and two industrial breaker-service companies were obtained to develop aging trends of various subcomponents. The responses of the utilities to the NRC Bulletin 88-01, which discusses the center pole lever welds, were analyzed to assess the final resolution of failures of welds in the reactor trips. Maintenance recommendations, made by the manufacturer to mitigate age-related degradation were reviewed, and recommendations for improving the monitoring of age-related degradation are discussed. As described in Volume 2 of this NUREG, the results from a test program to assess degradation in breaker parts through mechanical cycling are also included. The testing has characterized the cracking of center-pole lever welds, identified monitoring techniques to determine aging in breakers, and provided information to augment existing maintenance programs. Recommendations to improve breaker reliability using effective maintenance, testing, and inspection programs are suggested. 13 refs., 21 figs., 8 tabs.

  14. Mechanisms of Military Coatings Degradation

    DTIC Science & Technology

    2003-08-01

    series of reactions this results in carboxylic acid and urethane group as the end products of the degradation. Both the destruction of the urethane... reaction that, ultimately, created poor adhesion and film properties. SEM micrographs and small spot XPS mapping showed the presence of intermetallic... reactions nucleating at these sites. The result was a complete loss of corrosion protection at certain locations of the substrate. The dynamics of

  15. 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.

  16. 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.

  17. 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].

  18. 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

  19. 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

  20. Degradation mechanisms in thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Shinde, S. L.; Olson, D. A.; Dejonghe, L. C.; Miller, R. A.

    1986-01-01

    The degradation mechanism in thermal barrier coating systems subjected to prolonged heating in air as well as to thermal cycling was studied. Bond coat oxidation was found to be the most important reason for degradation. The oxidation produced NiO as well as Al?O? in one set of samples, but the variation in initial coating structure made it difficult to resolve systematic differences between isothermally heated and thermally cycled samples. However, the contribution to degradation from changes in substrate composition seemed less in the cycled sample.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. [Seed aging and survival mechanisms].

    PubMed

    Grappin, Philippe; Bourdais, Gildas; Collet, Boris; Godin, Béatrice; Job, Dominique; Ogé, Laurent; Jullien, Marc; Rajjou, Loïc

    2008-01-01

    Aging and death are universal to living systems. In temperate climate latitudes the mature seeds of higher plants are exposed to aging and have developed resistance mechanisms allowing survival and plant propagation. In addition to the physicochemical properties of the seed that confer stress resistance, the protein metabolism contributes importantly to longevity mechanisms. Recently, genetic studies have demonstrated the occurrence of the Protein L-isoaspartyl methyltransferase repair enzyme in controlling age-related protein damages and seed survival. These protective mechanisms by protein repair are widespread in all kingdoms, so that the use of seeds as models to study these controlling processes offers the prospect of understanding longevity mechanisms better.

  6. Insight into thermal degradation mechanism of Sr2Si5N8:Eu2+ phosphor during high-temperature aging processes

    NASA Astrophysics Data System (ADS)

    Wang, Qiuyue; Dong, Yan; Shao, Qiyue; Teng, Xiaoming; Jiang, Jianqing; Hintzen, H. T. (Bert)

    2017-04-01

    The thermal degradation is considered as one the most common limitations of Sr2-xEuxSi5N8 nitride phosphors due to the elevated working temperatures in LED. In order to examine the origin of the thermal degradation, Sr2-xEuxSi5N8 was synthesized using high-temperature solid-state reaction. The nitride with activators and the nitride host lattice were studied separately. The diffuse reflectance spectra, the internal quantum efficiency, and optical absorption rate, as well as the element binding energy and element content before and after annealing at high temperature, were investigated. Also, the morphology and surface layers were observed using high-resolution transmission electron microscopy (HRTEM). The results suggested the formation of an amorphous layer on the grain surface, which decreased luminescence efficiency after the heat treatment. It was found that oxidation of both the europium and Sr2Si5N8 host lattice caused the formation of the amorphous layer.

  7. Effects of Age on Long Term Memory for Degraded Speech

    PubMed Central

    Thiel, Christiane M.; Özyurt, Jale; Nogueira, Waldo; Puschmann, Sebastian

    2016-01-01

    Prior research suggests that acoustical degradation impacts encoding of items into memory, especially in elderly subjects. We here aimed to investigate whether acoustically degraded items that are initially encoded into memory are more prone to forgetting as a function of age. Young and old participants were tested with a vocoded and unvocoded serial list learning task involving immediate and delayed free recall. We found that degraded auditory input increased forgetting of previously encoded items, especially in older participants. We further found that working memory capacity predicted forgetting of degraded information in young participants. In old participants, verbal IQ was the most important predictor for forgetting acoustically degraded information. Our data provide evidence that acoustically degraded information, even if encoded, is especially vulnerable to forgetting in old age. PMID:27708570

  8. 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.

  9. Aging degradation of cast stainless steel

    SciTech Connect

    Chopra, O.K.; Chung, H.M.

    1986-10-01

    A program is being conducted to investigate the significance of in-service embrittlement of cast duplex stainless steels under light-water reactor operating conditions. Microstructures of cast materials subjected to long-term aging either in reactor service or in the laboratory have been characterized by TEM, SANS, and APFIM techniques. Two precipitate phases, i.e., the Cr-rich ..cap alpha..' and Ni- and Si-rich G phase, have been identified in the ferrite matrix of the aged steels. The results indicate that the low-temperature embrittlement is primarily caused by ..cap alpha..' precipitates which form by spinodal decomposition. The relative contribution of G phase to loss of toughness is now known. Microstructural data also indicate that weakening of ferrite/austenite phase boundary by carbide precipitates has a significant effect on the onset and extent of embrittlement of the high-carbon CF-8 and CF-8M grades of stainless steels, particularly after aging at 400 or 450/sup 0/C. Data from Charpy-impact, tensile, and J-R curve tests for several heats of cast stainless steel aged up to 10,000 h at 350, 400, and 450/sup 0/C are presented and correlated with the microstructural results. Thermal aging of the steels results in an increase in tensile strength and a decrease in impact energy, J/sub IC/, and tearing modulus. The fracture toughness results show good agreement with the Charpy-impact data. The effects of compositional and metallurgical variables on loss of toughness are discussed.

  10. Degradation of toxaphene in aged and freshly contaminated soil.

    PubMed

    Lacayo-Romero, Martha; van Bavel, Bert; Mattiasson, Bo

    2006-04-01

    Degradation of toxaphene in soil from both newly contaminated (from Sweden) and aged spills (from Nicaragua) were studied. The newly contaminated soil contained approximately 11 mg kg(-1) toxaphene while the aged Nicaraguan soil contained approximately 100 mg kg(-1). Degradation was studied in anaerobic bioreactors, some of which were supplied with lactic acid and others with Triton X-114. In this study we found that the lower isomers Parlar 11, 12 were degraded while the concentration of isomer Parlar 15 increased. This supported an earlier evaluation which indicated that less chlorinated isomers are formed from more heavily isomers. Lactic acid when added to the soil, interfere with the degradation of toxaphene. Lactic acid was added; several isomers appeared to degrade rather slowly in newly contaminated Swedish soil. The Swedish soil, without any external carbon source, showed the slowest degradation rate of all the compounds studied. When Triton X-114 at 0.4 mM was added, the degradation rate of the compounds increased. This study illustrates that biodegradation of toxaphene is a complex process and several parameters have to be taken into consideration. Degradation of persistent pollutants in the environment using biotechnology is dependent on bioavailability, carbon sources and formation of metabolites.

  11. 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

  12. Aging degradation of cast stainless steel

    SciTech Connect

    Chopra, O.K.; Chung, H.M.

    1985-10-01

    A program is being conducted to investigate the significance of in-service embrittlement of cast-duplex stainless steels under light-water reactor operating conditions. Data from room-temperature Charpy-impact tests for several heats of cast stainless steel aged up to 10,000 h at 350, 400, and 450/sup 0/C are presented and compared with results from other studies. Microstructures of cast-duplex stainless steels subjected to long-term aging either in the laboratory or in reactor service have been characterized. The results indicate that at least two processes contribute to the low-temperature embrittleent of duplex stainless steels, viz., weakening of the ferrite/austenite phase boundary by carbide precipitation and embrittlement of ferrite matrix by the formation of additional phases such as G-phase, Type X, or the ..cap alpha..' phase. Carbide precipitation has a significant effect on the onset of embrittlement of CF-8 and -8M grades of stainless steels aged at 400 or 450/sup 0/C. The existing correlations do not accurately represent the embrittlement behavior over the temperature range 300 to 450/sup 0/C. 18 refs., 13 figs.

  13. Age Effects on Hypocotyl Mechanics

    PubMed Central

    Weichold, Susann; Reinecke, Antje; Lisec, Jan; Döring, Anett; Neumetzler, Lutz; Burgert, Ingo; Eder, Michaela

    2016-01-01

    Numerous studies deal with composition and molecular processes involved in primary cell wall formation and alteration in Arabidopsis. However, it still remains difficult to assess the relation between physiological properties and mechanical function at the cell wall level. The thin and fragile structure of primary cell walls and their large biological variability, partly related to structural changes during growth, make mechanical experiments challenging. Since, to the best of our knowledge, there is no reliable data in the literature about how the properties of the fully elongated zone of hypocotyls change with age. We studied in a series of experiments on two different seed batches the tensile properties the region below the growth zone of 4 to 7 day old etiolated Arabidopsis hypocotyls. Additionally, we analysed geometrical parameters, hypocotyl density and cellulose content as individual traits and their relation to tissue mechanics. No significant differences of the mechanical parameters of the non-growing region between 5–7 day old plants could be found whereas in 4 day old plants both tensile stiffness and ultimate tensile stress were significantly lower than in the older plants. Furthermore hypocotyl diameters and densities remain almost the same for 5, 6 and 7 day old seedlings. Naturally, hypocotyl lengths increase with age. The evaluation whether the choice–age or length—influences the mechanical properties showed that both are equally applicable sampling parameters. Additionally, our detailed study allows for the estimation of biological variability, connections between mechanics and hypocotyl age could be established and complement the knowledge on biochemistry and genetics affecting primary plant cell wall growth. The application of two different micromechanical devices for testing living Arabidopsis hypocotyls allows for emphasizing and discussing experimental limitations and for presenting a wide range of possibilities to address current and

  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. Multisensory integration mechanisms during aging.

    PubMed

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

    2013-12-13

    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.

  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. Ultrasound based AOP for emerging pollutants: from degradation to mechanism.

    PubMed

    Rayaroth, Manoj P; Aravind, Usha K; Aravindakumar, Charuvila T

    2016-04-14

    Ultrasound is known to degrade organic compounds by pyrolysis and by the reaction of free radicals. In this work, sonolytic degradation of an identified water pollutant, coomassie brilliant blue (CBB), has been carried out in pure water as well as in river water. In the case of pure water, 90 % degradation was obtained after 30 min of sonication (350 kHz frequency, 60 W power), whereas in river water, the same efficiency was achieved only after 90 min. The degradation was also performed in the presence of varying concentration of (10-100 mg L(-1)) inorganic ions such as chloride, sulfate, nitrate, bicarbonate, and carbonate ions which were detected in the river water sample. Higher concentration of chloride enhanced the degradation due to the salting out mechanism. The enhancement of degradation in the presence of nitrate is mainly due to the change in the surface potential at the interface of the cavitating bubble. Bicarbonate ion and carbonate ion enhanced the degradation due to the involvement of carbonate radicals. A possible degradation mechanism is proposed based on the product profile determined by LC-Q-ToF-MS. The low efficiency of degradation in river water compared to that in pure water is likely due to the increased rate of bubble dissolution or escape of bubbles (degassing effect), and the scavenging of (•)OH by the organic content (high chemical oxygen demand (COD)).

  19. Corrosion degradation mechanisms in coiled tubing

    SciTech Connect

    Kane, R.D.; Cayard, M.S.

    1994-12-31

    This paper reviews the historical aspects related to the development of coiled tubing for oilfield drilling, logging, workover and production operations. It focuses on the metallurgical and process variables of coiled tubing and their interrelationship with aspects of the downhole service environment and the resultant corrosion performance. Special emphasis is placed on (1) operating conditions that can lead to excessive corrosion and/or cracking damage and corrosion fatigue and (2) metallurgical and processing parameters which can be controlled to maximize coiled tubing resistance to corrosion degradation.

  20. Metabolism of AGEs – Bacterial AGEs Are Degraded by Metallo-Proteases

    PubMed Central

    Cohen-Or, Ifat; Katz, Chen; Ron, Eliora Z.

    2013-01-01

    Advanced Glycation End Products (AGEs) are the final products of non-enzymatic protein glycation that results in loss of protein structure and function. We have previously shown that in E. coli AGEs are continually formed as high-molecular weight protein complexes. Moreover, we showed that AGEs are removed from the cells by an active, ATP-dependent secretion and that these secreted molecules have low molecular weight. Taken together, these results indicate that E. coli contains a fraction of low molecular weight AGEs, in addition to the high-molecular weight AGEs. Here we show that the low-molecular weight AGEs originate from high-molecular weight AGEs by proteolytic degradation. Results of in-vitro and in vivo experiments indicated that this degradation is carried out not by the major ATP-dependent proteases that are responsible for the main part of bacterial protein quality control but by an alternative metal-dependent proteolysis. This proteolytic reaction is essential for the further secretion of AGEs from the cells. As the biochemical reactions involving AGEs are not yet understood, the implication of a metalloprotease in breakdown of high molecular weight AGEs and their secretion constitutes an important step in the understanding of AGEs metabolism. PMID:24130678

  1. Infection resistance of degradable versus non-degradable biomaterials: an assessment of the potential mechanisms.

    PubMed

    Daghighi, Seyedmojtaba; Sjollema, Jelmer; van der Mei, Henny C; Busscher, Henk J; Rochford, Edward T J

    2013-11-01

    Extended life expectancy and medical development has led to an increased reliance on biomaterial implants and devices to support or restore human anatomy and function. However, the presence of an implanted biomaterial results in an increased susceptibility to infection. Due to the severity of the potential outcomes of biomaterial-associated infection, different strategies have been employed to reduce the infection risk. Interestingly, degradable biological materials demonstrate increased resistance to bacterial infection compared to non-degradable synthetic biomaterials. Current knowledge about the specific mechanisms of how degradable biological materials are afforded increased resistance to infection is limited. Therefore, in this paper a number of hypotheses to explain the decreased infection risk associated with the use of degradable versus non-degradable biomaterials are evaluated and discussed with reference to the present state of knowledge.

  2. 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 nuclear power plants in the United States have initial operating licenses of 40 years, though most of 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 research on online monitoring of concrete structures conducted under the Advanced Instrumentation, Information, and Control Systems 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, 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 propose to develop a framework of research activities for the health monitoring of nuclear power plant concrete structures that includes the 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.

  3. Sonolytic degradation of dimethoate: kinetics, mechanisms and toxic intermediates controlling.

    PubMed

    Yao, Juan-Juan; Hoffmann, Michael R; Gao, Nai-Yun; Zhang, Zhi; Li, Lei

    2011-11-15

    The sonolytic degradation of aqueous solutions of dimethoate, O,O-dimethyl S-[2-(methylamino)-2-oxoethyl]dithiophosphate, was examined. Optimal degradation rates were obtained at 619 kHz for continuous sonolysis and 406 kHz for pulse sonolysis. The primary pathways for degradation include hydroxyl radical oxidation, hydrolysis and pyrolysis on collapsing cavitation bubble interfaces. Reaction mechanisms coupled with the corresponding kinetic models are proposed to reproduce the observed concentration versus time profiles for dimethoate, omethoate and N-(methyl) mercaptoacetamide during sonolysis. The oxidation and hydrolysis of dimethoate and omethoate occurred at the water-bubble interface was the rate-determining step for sonolytic overall degradation of dimethoate. More than 90% toxicity of dimethoate was reduced within 45 min ultrasonic irradiation. Ferrous ion at micro molar level can significantly enhance the sonolytic degradation of dimethoate and effectively reduce the yields of toxic intermediate omethoate.

  4. 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

  5. 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

  6. Effect of aging on catalytic properties in mechanochemical degradation of pentachlorophenol by birnessite.

    PubMed

    Pizzigallo, Maria D R; Leo, Paola Di; Ancona, Valeria; Spagnuolo, Matteo; Schingaro, Emanuela

    2011-01-01

    Mechanochemistry, a technique concerning with milling contaminated samples for prolonged times, induces massive degradation of pollutants by grinding them in ball mills with different soil components or additives. In the present study, laboratory experiments were conducted to evaluate the effect of aging on the mechanochemical efficiency of the Mn-oxide birnessite in degrading pentachlorophenol (PCP). A comparative study on an aged birnessite (KBiA), used after 3years from synthesis, and a fresh birnessite (KBiF), employed immediately after synthesis, was carried out. The differences between the two birnessites, evidenced by spectroscopic and diffractometric techniques, are mainly relative to reduction of the Mn(IV) centered at the MnO₆ octahedra layers from the birnessite structure, which represent the most reactive sites for PCP degradation. The long term air drying at room temperature, by favouring reduction of Mn(IV) to Mn(III), produces an inorganic substrate that offers paucity of the less reactive sites for PCP degradation, thus reducing the oxidative potential of the KBiA. Accordingly, the more reactive fresh birnessite was employed in the experiment with a polluted soil. Adding a small amount of KBiF to soil only induces a light increase in PCP removal, probably due to the mechanically induced PCP adsorption and transformation onto clay minerals present in the soil. Besides, adding a higher dose of birnessite causes a stronger degradation of PCP.

  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. DEGRADATION SUSCEPTIBILITY METRICS AS THE BASES FOR BAYESIAN RELIABILITY MODELS OF AGING PASSIVE COMPONENTS AND LONG-TERM REACTOR RISK

    SciTech Connect

    Unwin, Stephen D.; Lowry, Peter P.; Toyooka, Michael Y.; Ford, Benjamin E.

    2011-07-17

    Conventional probabilistic risk assessments (PRAs) are not well-suited to addressing long-term reactor operations. Since passive structures, systems and components are among those for which refurbishment or replacement can be least practical, they might be expected to contribute increasingly to risk in an aging plant. Yet, passives receive limited treatment in PRAs. Furthermore, PRAs produce only snapshots of risk based on the assumption of time-independent component failure rates. This assumption is unlikely to be valid in aging systems. The treatment of aging passive components in PRA does present challenges. First, service data required to quantify component reliability models are sparse, and this problem is exacerbated by the greater data demands of age-dependent reliability models. A compounding factor is that there can be numerous potential degradation mechanisms associated with the materials, design, and operating environment of a given component. This deepens the data problem since the risk-informed management of materials degradation and component aging will demand an understanding of the long-term risk significance of individual degradation mechanisms. In this paper we describe a Bayesian methodology that integrates the metrics of materials degradation susceptibility being developed under the Nuclear Regulatory Commission's Proactive Management of Materials of Degradation Program with available plant service data to estimate age-dependent passive component reliabilities. Integration of these models into conventional PRA will provide a basis for materials degradation management informed by the predicted long-term operational risk.

  9. Lysosomal cell death mechanisms in aging.

    PubMed

    Gómez-Sintes, Raquel; Ledesma, María Dolores; Boya, Patricia

    2016-12-01

    Lysosomes are degradative organelles essential for cell homeostasis that regulate a variety of processes, from calcium signaling and nutrient responses to autophagic degradation of intracellular components. Lysosomal cell death is mediated by the lethal effects of cathepsins, which are released into the cytoplasm following lysosomal damage. This process of lysosomal membrane permeabilization and cathepsin release is observed in several physiopathological conditions and plays a role in tissue remodeling, the immune response to intracellular pathogens and neurodegenerative diseases. Many evidences indicate that aging strongly influences lysosomal activity by altering the physical and chemical properties of these organelles, rendering them more sensitive to stress. In this review we focus on how aging alters lysosomal function and increases cell sensitivity to lysosomal membrane permeabilization and lysosomal cell death, both in physiological conditions and age-related pathologies.

  10. Multitasking During Degraded Speech Recognition in School-Age Children.

    PubMed

    Grieco-Calub, Tina M; Ward, Kristina M; Brehm, Laurel

    2017-01-01

    Multitasking requires individuals to allocate their cognitive resources across different tasks. The purpose of the current study was to assess school-age children's multitasking abilities during degraded speech recognition. Children (8 to 12 years old) completed a dual-task paradigm including a sentence recognition (primary) task containing speech that was either unprocessed or noise-band vocoded with 8, 6, or 4 spectral channels and a visual monitoring (secondary) task. Children's accuracy and reaction time on the visual monitoring task was quantified during the dual-task paradigm in each condition of the primary task and compared with single-task performance. Children experienced dual-task costs in the 6- and 4-channel conditions of the primary speech recognition task with decreased accuracy on the visual monitoring task relative to baseline performance. In all conditions, children's dual-task performance on the visual monitoring task was strongly predicted by their single-task (baseline) performance on the task. Results suggest that children's proficiency with the secondary task contributes to the magnitude of dual-task costs while multitasking during degraded speech recognition.

  11. Multitasking During Degraded Speech Recognition in School-Age Children

    PubMed Central

    Ward, Kristina M.; Brehm, Laurel

    2017-01-01

    Multitasking requires individuals to allocate their cognitive resources across different tasks. The purpose of the current study was to assess school-age children’s multitasking abilities during degraded speech recognition. Children (8 to 12 years old) completed a dual-task paradigm including a sentence recognition (primary) task containing speech that was either unprocessed or noise-band vocoded with 8, 6, or 4 spectral channels and a visual monitoring (secondary) task. Children’s accuracy and reaction time on the visual monitoring task was quantified during the dual-task paradigm in each condition of the primary task and compared with single-task performance. Children experienced dual-task costs in the 6- and 4-channel conditions of the primary speech recognition task with decreased accuracy on the visual monitoring task relative to baseline performance. In all conditions, children’s dual-task performance on the visual monitoring task was strongly predicted by their single-task (baseline) performance on the task. Results suggest that children’s proficiency with the secondary task contributes to the magnitude of dual-task costs while multitasking during degraded speech recognition. PMID:28105890

  12. 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.

  13. 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.

  14. 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.

  15. Modelling the molecular mechanisms of aging.

    PubMed

    Mc Auley, Mark T; Guimera, Alvaro Martinez; Hodgson, David; Mcdonald, Neil; Mooney, Kathleen M; Morgan, Amy E; Proctor, Carole J

    2017-02-28

    The aging process is driven at the cellular level by random molecular damage that slowly accumulates with age. Although cells possess mechanisms to repair or remove damage, they are not 100% efficient and their efficiency declines with age. There are many molecular mechanisms involved and exogenous factors such as stress also contribute to the aging process. The complexity of the aging process has stimulated the use of computational modelling in order to increase our understanding of the system, test hypotheses and make testable predictions. As many different mechanisms are involved, a wide range of models have been developed. This paper gives an overview of the types of models that have been developed, the range of tools used, modelling standards and discusses many specific examples of models that have been grouped according to the main mechanisms that they address. We conclude by discussing the opportunities and challenges for future modelling in this field.

  16. Modelling the molecular mechanisms of aging

    PubMed Central

    Mc Auley, Mark T.; Guimera, Alvaro Martinez; Hodgson, David; Mcdonald, Neil; Mooney, Kathleen M.; Morgan, Amy E.

    2017-01-01

    The aging process is driven at the cellular level by random molecular damage that slowly accumulates with age. Although cells possess mechanisms to repair or remove damage, they are not 100% efficient and their efficiency declines with age. There are many molecular mechanisms involved and exogenous factors such as stress also contribute to the aging process. The complexity of the aging process has stimulated the use of computational modelling in order to increase our understanding of the system, test hypotheses and make testable predictions. As many different mechanisms are involved, a wide range of models have been developed. This paper gives an overview of the types of models that have been developed, the range of tools used, modelling standards and discusses many specific examples of models that have been grouped according to the main mechanisms that they address. We conclude by discussing the opportunities and challenges for future modelling in this field. PMID:28096317

  17. 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.

  18. Mechanism and kinetics of COS-induced diethanolamine degradation

    SciTech Connect

    Dawodu, O.F.; Meisen, A. . Dept. of Chemical Engineering)

    1994-03-01

    The degradation of aqueous diethanolamine (DEA) solutions by carbonyl sulfide was examined by using a 600-mL well-stirred reactor operating under the following conditions: DEA concentration 20--40 wt %, temperature 120--180 C, COS partial pressure 0.3--1.17 MPa. The reaction products were identified by GC/MS, and reaction mechanisms are developed which conform with experimental observations. The reaction rate constants are determined, and a mathematical model for estimating DEA degradation by COS is presented.

  19. 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.

  20. Ageing mechanisms and associated lipid changes.

    PubMed

    Kolovou, Genovefa; Katsiki, Niki; Pavlidis, Antonis; Bilianou, Helen; Goumas, George; Mikhailidis, Dimitri P

    2014-01-01

    Ageing is related to slowdown/breakdown of the somatotropic axis (i.e. the somatopause) leading to many physiological changes. The somatopause is accompanied by DNA and other macromolecule damage, and is characterized by a progressive decline in vitality and tissue function. We still do not have a definitive understanding of the mechanism( s) of ageing. Several overlapping theories have been proposed such as: 1) The free radical theory, 2) Mitochondrial Ageing, 3) The Glycation Theory, 4) Protein Damage and Maintenance in Ageing, and, 5) DNA Damage and Repair. Furthermore, several models of ageing were introduced such as genetically programmed senescence, telomere shortening, genomic instability, heterochromatin loss, altered epigenetic patterns and long lived cells. There are certain lipid modifications associated with the somatopause, characterized mainly by an increase in total cholesterol and triglyceride levels in both genders. In this review we consider the mechanisms of ageing and the associated changes in lipid metabolism according to gender.

  1. Degradation mechanism of laser diodes for 880-nm band

    NASA Astrophysics Data System (ADS)

    DÄ browska, E.; Nakielska, M.; Kozłowska, A.; Teodorczyk, M.; KrzyŻak, K.; Sobczak, G.; Kalbarczyk, J.; MalÄ g, A.

    2013-01-01

    The laser diodes (LD) have numerous applications and promise to become key elements for next generation laser technologies. LD are usually operated under conditions of heavy thermal load. As a result, the devices are affected by aging processes leading to changes of the operation parameters, degradation and, eventually, complete failure. Degradation of high power semiconductor lasers remains a serious problem for practical application of these devices. We investigated the effect of mounting induced strain and defects on the performance of high power laser. In this paper measurements of the temperature distribution and the electroluminescence along the cavity of InGaAs quantum well lasers before and after accelerated aging processes are presented. The electro-optical parameters of the high output power laser diodes, such as emission wavelength, output power, threshold current, slope efficiency, and operating lifetime are presented too.

  2. 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.

  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. 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.

  5. Hybrid polyurea elastomers with enzymatic degradation and tunable mechanical properties.

    PubMed

    Sears, Nicholas A; Pena-Galea, Geraldine; Cereceres, Stacy N; Cosgriff-Hernandez, Elizabeth

    2016-01-01

    Herein, we report on the synthesis and characterization of enzymatically labile polyureas for use as a tissue-engineered ligament scaffold. Polyureas were selected due to their excellent tensile properties, fatigue resistance, and highly tunable nature. Incorporation of a collagenase-sensitive peptide into the backbone of the polyurea provided a means to confer cell-responsive degradation to the synthetic polymer. Chemical, morphological, and mechanical testing were used to confirm incorporation of the peptide and characterize polyurea films. Notably, the incorporation of the peptide resulted in an increase in modulus, elongation, and tensile strength. This was attributed to an increase in phase mixing and an increase in hydrogen bonding between the hard and soft segments. Candidate polyureas with varying levels of collagen-mimetic peptide (0%, 10%, 20%) were then subjected to degradation in collagenase media or buffer at 37°C over 4 weeks. Statistically significant decreases in strength and elongation were observed in polyureas with 20% peptide content after collagenase treatment, whereas specimens in phosphate-buffered saline showed no statistically significant difference. These observations confirmed that enzyme-specific degradation was conferred to the polyurea. Overall, these polyureas hold great promise as a material for ligament reconstruction due to the promising mechanical properties and potential for cell-mediated degradation.

  6. Hybrid polyurea elastomers with enzymatic degradation and tunable mechanical properties

    PubMed Central

    Sears, Nicholas A; Pena-Galea, Geraldine; Cereceres, Stacy N; Cosgriff-Hernandez, Elizabeth

    2016-01-01

    Herein, we report on the synthesis and characterization of enzymatically labile polyureas for use as a tissue-engineered ligament scaffold. Polyureas were selected due to their excellent tensile properties, fatigue resistance, and highly tunable nature. Incorporation of a collagenase-sensitive peptide into the backbone of the polyurea provided a means to confer cell-responsive degradation to the synthetic polymer. Chemical, morphological, and mechanical testing were used to confirm incorporation of the peptide and characterize polyurea films. Notably, the incorporation of the peptide resulted in an increase in modulus, elongation, and tensile strength. This was attributed to an increase in phase mixing and an increase in hydrogen bonding between the hard and soft segments. Candidate polyureas with varying levels of collagen-mimetic peptide (0%, 10%, 20%) were then subjected to degradation in collagenase media or buffer at 37°C over 4 weeks. Statistically significant decreases in strength and elongation were observed in polyureas with 20% peptide content after collagenase treatment, whereas specimens in phosphate-buffered saline showed no statistically significant difference. These observations confirmed that enzyme-specific degradation was conferred to the polyurea. Overall, these polyureas hold great promise as a material for ligament reconstruction due to the promising mechanical properties and potential for cell-mediated degradation. PMID:27994846

  7. 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.

  8. Fundamental study of mechanical and chemical degradation mechanisms of PEM fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Yoon, Wonseok

    One of the important factors determining the lifetime of polymer electrolyte membrane fuel cells (PEMFCs) is membrane degradation and failure. The lack of effective mitigation methods is largely due to the currently very limited understanding of the underlying mechanisms for mechanical and chemical degradations of fuel cell membranes. In order to understand degradation of membranes in fuel cells, two different experimental approaches were developed; one is fuel cell testing under open circuit voltage (OCV) with bi-layer configuration of the membrane electrode assemblies (MEAs) and the other is a modified gas phase Fenton's test. Accelerated degradation tests for polymer electrolyte membrane (PEM) fuel cells are frequently conducted under open circuit voltage (OCV) conditions at low relative humidity (RH) and high temperature. With the bi-layer MEA technique, it was found that membrane degradation is highly localized across thickness direction of the membrane and qualitatively correlated with location of platinum (Pt) band through mechanical testing, Infrared (IR) spectroscopy, fluoride emission, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive spectroscopy (EDS) measurement. One of the critical experimental observations is that mechanical behavior of membranes subjected to degradation via Fenton's reaction exhibit completely different behavior with that of membranes from the OCV testing. This result led us to believe that other critical factors such as mechanical stress may affect on membrane degradation and therefore, a modified gas phase Fenton's test setup was developed to test the hypothesis. Interestingly, the results showed that mechanical stress directly accelerates the degradation rate of ionomer membranes, implying that the rate constant for the degradation reaction is a function of mechanical stress in addition to commonly known factors such as temperature and humidity. Membrane degradation induced by

  9. 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

  10. High Temperature Degradation Mechanisms in Polymer Matrix Composites

    NASA Technical Reports Server (NTRS)

    Cunningham, Ronan A.; McManus, Hugh L.

    1997-01-01

    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 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 in

  11. 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

  12. 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).

  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

    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.

  15. Loss of adaptive mechanisms during aging.

    PubMed

    Adelman, R C

    1979-05-01

    Factors contributing to modifications in the capability for enzyme adaptation as an expression of aging are reviewed. Specific examples of altered enzyme adaptations during aging include the responses of hepatic glucokinase activity to glucose and hepatic tyrosine aminotransferase activity to starvation in Sprague-Dawley rats. These impaired enzyme adaptations apparently are not the consequence of alterations in hepatic function during aging. Instead, they reflect disturbances in extrahepatic hormonal regulatory mechanisms. Specific examples include modifications in the control of circulating levels of insulin glucagon, corticosteroids, and thyroid hormones. Age-dependent changes in the regulation of circulating levels of insulin probably originate within the impaired ability of pancreatic islets of Langerhans to secrete the hormone in response to glucose. The rationale for exploiting this experimental approach as a means to understand biological aging is discussed.

  16. 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

  17. COMPONENT DEGRADATION SUSCEPTIBILITIES AS THE BASES FOR MODELING REACTOR AGING RISK

    SciTech Connect

    Unwin, Stephen D.; Lowry, Peter P.; Toyooka, Michael Y.

    2010-07-18

    The extension of nuclear power plant operating licenses beyond 60 years in the United States will be necessary if we are to meet national energy needs while addressing the issues of carbon and climate. Characterizing the operating risks associated with aging reactors is problematic because the principal tool for risk-informed decision-making, Probabilistic Risk Assessment (PRA), is not ideally-suited to addressing aging systems. The components most likely to drive risk in an aging reactor - the passives - receive limited treatment in PRA, and furthermore, standard PRA methods are based on the assumption of stationary failure rates: a condition unlikely to be met in an aging system. A critical barrier to modeling passives aging on the wide scale required for a PRA is that there is seldom sufficient field data to populate parametric failure models, and nor is there the availability of practical physics models to predict out-year component reliability. The methodology described here circumvents some of these data and modeling needs by using materials degradation metrics, integrated with conventional PRA models, to produce risk importance measures for specific aging mechanisms and component types. We suggest that these measures have multiple applications, from the risk-screening of components to the prioritization of materials research.

  18. 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.

  19. Mechanical Tests For Monitoring Aging Of Composites

    NASA Technical Reports Server (NTRS)

    Bowles, Kenneth J.

    1994-01-01

    Experimental study addresses related topics of thermo-oxidative aging of PMR-15 (polyimide matrix/graphite-fiber composite materials) strengths of interfacial bonds, effects of various surface treatments, and relative merits of mechanical tests yielding measures of strengths of materials.

  20. 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.

  1. Longevity and aging. Mechanisms and perspectives.

    PubMed

    Labat-Robert, J; Robert, L

    2015-12-01

    Longevity can mostly be determined with relative accuracy from birth and death registers when available. Aging is a multifactorial process, much more difficult to quantitate. Every measurable physiological function declines with specific speeds over a wide range. The mechanisms involved are also different, genetic factors are of importance for longevity determinations. The best-known genes involved are the Sirtuins, active at the genetic and epigenetic level. Aging is multifactorial, not "coded" in the genome. There are, however, a number of well-studied physical and biological parameters involved in aging, which can be determined and quantitated. We shall try to identify parameters affecting longevity as well as aging and suggest some reasonable predictions for the future.

  2. Analysis of the degradation mechanisms in an impacted ceramic

    NASA Astrophysics Data System (ADS)

    Denoual, C.; Cottenot, C. E.; Hild, F.

    1998-07-01

    To analyze the degradation mechanisms in a natural sintered SiC (SSiC) ceramic during impact, three edge-on impact configurations are considered. First, the ceramic is confined by aluminum to allow a post-mortem analysis. In the second configuration, a polished surface of the ceramic is observed each micro-second by a high-speed camera to follow the damage generation and evolution. The third configuration uses a high-speed Moiré photography system to measure dynamic 2-D strain fields. Sequences of fringe patterns are analyzed.

  3. Electrolyte and Cathode Degradation Mechanisms in Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Tebbe, Jonathon

    Lithium ion battery technologies suffer from limitations in performance, such as capacity fading, due in part to degradation of the cathode and electrolyte materials. Quantum chemical simulations were employed to investigate the reactions leading to degradation of LiCoO2 cathodes and the electrolyte molecules. Formation of HF in the electrolyte resulting from reaction between PF5 and H2O impurities was first investigated. This research predicts HF is produced as a result of PF5 complexing with H2O, then reacting through ligand exchange to form HF and PF4OH with an activation barrier of 1.18 eV and reaction enthalpy of 0.15 eV. HF undergoes dissociative adsorption at that the (101¯4) surface of LiCoO2 without a barrier, leading to formation of LiF-Li+ precipitates and H 2O on the surface with a reaction energy of -2.41 eV. The formation of H2O is of particular concern because H2O drives further formation of HF in the electrolyte, resulting in an autocatalytic cycle of degradation. These findings indicate that HF initially occurs in low concentrations rapidly increases due to H2O generation upon HF attack. Reduction in capacity fading is observed in alumina ALD coated LiCoO2 cathodes and we have investigated a monolayer alumina coating on the LiCoO2 (101¯4) surface to identify the mechanism by which the alumina coating protects the cathode surface. We have found that HF will preferentially dissociate at the alumina coating with a reaction energy of -2.84 eV and without any resolvable barrier to dissociation. Additionally, our calculations predict that H2O does not form as a result of HF dissociation at the alumina monolayer; instead HF dissociation produces neighboring hydroxyl sites on the alumina surface. Consequently, the alumina coating prevents the autocatalytic degradation of the cathode by sequestering HF impurities in the alumina film. Finally, we found that Lewis acid-base complexation between ethylene carbonate (EC) electrolyte molecules and PF5 or the Li

  4. RELIABILITY MODELS OF AGING PASSIVE COMPONENTS INFORMED BY MATERIALS DEGRADATION METRICS TO SUPPORT LONG-TERM REACTOR OPERATIONS

    SciTech Connect

    Unwin, Stephen D.; Lowry, Peter P.; Toyooka, Michael Y.

    2012-05-01

    Paper describes a methodology for the synthesis of nuclear power plant service data with expert-elicited materials degradation information to estimate the future failure rates of passive components. This method should be an important resource to long-term plant operations and reactor life extension. Conventional probabilistic risk assessments (PRAs) are not well suited to addressing long-term reactor operations. Since passive structures and components are among those for which replacement can be least practical, they might be expected to contribute increasingly to risk in an aging plant; yet, passives receive limited treatment in PRAs. Furthermore, PRAs produce only snapshots of risk based on the assumption of time-independent component failure rates. This assumption is unlikely to be valid in aging systems. The treatment of aging passive components in PRA presents challenges. Service data to quantify component reliability models are sparse, and this is exacerbated by the greater data demands of age-dependent reliability models. Another factor is that there can be numerous potential degradation mechanisms associated with the materials and operating environment of a given component. This deepens the data problem since risk-informed management of component aging will demand an understanding of the long-term risk significance of individual degradation mechanisms. In this paper we describe a Bayesian methodology that integrates metrics of materials degradation susceptibility with available plant service data to estimate age-dependent passive component reliabilities. Integration of these models into conventional PRA will provide a basis for materials degradation management informed by predicted long-term operational risk.

  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. PEM fuel cell catalyst degradation mechanism and mathematical modeling

    NASA Astrophysics Data System (ADS)

    Bi, Wu

    The durability of carbon-supported platinum oxygen reduction electrocatalysts is one of the limiting factors for their commercial applications in PEM fuel cell cathodes. In this work, we applied both experimental and numerical tools to study Pt/C catalyst degradation mechanisms. An accelerated catalyst degradation protocol through cycling the cathode potential in a square-wave profile was applied to study cell performances, Pt/C catalyst ORR activity, and active surface area losses. Post-mortem analyses of cathode Pt particle size were conducted by X-ray diffraction. Changes of platinum distributions in CCMs were studied by SEM/EDS analyses with surface coated Au as the reference element. The mechanisms of platinum deposition in membrane were investigated. It was confirmed by the SEM/EDS Pt distribution analyses that the deposited Pt atoms originated from the cathode. It was hypothesized that dissolved Pt ions from the cathode diffused into the membrane and were reduced by the permeated hydrogen from the anode. These deposited Pt atoms catalyzed the combustion of permeated oxygen and hydrogen. Pt band was predicted and experimentally confirmed at the location where the permeated hydrogen and oxygen completely reacted with each other. An active research thrust for PEM fuel cells is the development of membranes for high temperature (above 80°C) and low humidity operations. However a large tradeoff the benefits running fuel cell at relatively high temperatures was observed due to the accelerated cathode degradation processes. And at low humidity conditions, the cathode degradation rate decreased due to the slow transport of soluble platinum ions in possible narrowed/limited water (or ionic) channel networks in polymer electrolytes. From the Pt dissolution experiments in 0.5 M HClO4 solution, large positive effects of holding potentials on dissolution rates and soluble Pt concentrations were observed. Without an external holding potential, Pt dissolution rate was

  7. [Attenuated Total Reflection Infrared Spectroscopy for Degradation Profile of High Density Polyethylene after Weathering Aging].

    PubMed

    Guo, Jun-jun; Yan, Hua; Bao, He-bin; Wang, Xue-mei; Hu, Zhi-de; Yang, Jian-jian

    2015-06-01

    High density polyethylene (HDPE) was widely used as rotational packaging case in the material reserve field. The chemical changes of HDPE, exposed to particular climatic conditions of tropic marine atmosphere for one year-long in Wanning Hainan, were elucidated by the attenuated total reflection infrared spectroscopy (ATR-FTIR). The structural changes were studied qualitatively, mainly from the polymeric chain breaking, branching and oxidation to distinguish the degradation profile. The variations of crystallinity & carbonyl index were also studied quantitatively according to the characteristic peaks intensity & area ratio. Finally, the relationships between structural changes and mechanical properties were investigated. The results showed that the polymeric chain breaking & branching play a leading role before 3 months in the aging progress. Then oxidation phenomena gradually takes place during 3-6 months. The chain branching & oxidation were predominant factors after 6 months. Nine months later, the oxidation was saturated gradually. Furthermore, the aging process is positively correlated to the temperature and irradiation. After 12 months aging, the carbonyl index increased by 112 times and crystallinity was 10% higher than before. The tensile/bending modulus deceased faster than tensile/bending strength of HDPE. The linear degree of tensile modulus and carbonyl index was 0.97. The degree of linearity of tensile strength and crystallinity calculated by feature bands (720-730 cm(-1)) was 0.96. It showed that the mechanical properties of HDPE can be speculated from the structural changes by ATR-FTIR.

  8. Mechanisms of age-related bone loss.

    PubMed

    Mosekilde, L

    2001-01-01

    The human skeleton is formed and modelled during childhood and youth through the influence of hormones and daily mechanical usage. Around the age of 20-25 years, the skeleton achieves its maximum mass and strength. Thereafter, and throughout adult life, bone is lost at an almost constant rate due to the dynamic bone turnover process: the remodelling process. During this process, small packets of bone are renewed by teams of bone cells coupled together in time and space. In an adult human skeleton there will be 1-2 million active remodelling sites at any time point. The vast number of turnover units combined with a slightly negative balance at the completion of each process leads to the age-related loss of bone mass mentioned above and, concomitantly, to loss of structural continuity and strength. The magnitude of this loss will be determined by hormonal factors, nutrition and mechanical usage. As a consequence of the remodelling process, the bone tissue of the skeleton will always be younger than the age of the individual. However, as a consequence of the remodelling process, osteopenia and osteoporotic fractures will also occur. In this article, the remodelling-induced changes in the human spine will be used as an example of ageing bone.

  9. 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.

  10. 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.

  11. Free-radical-induced oxidative and reductive degradation of fibrate pharmaceuticals: kinetic studies and degradation mechanisms.

    PubMed

    Razavi, Behnaz; Song, Weihua; Cooper, William J; Greaves, John; Jeong, Joonseon

    2009-02-19

    The presence of pharmaceutically active compounds (PhACs) in aquatic systems is an emerging environmental issue and poses a potential threat to ecosystems and human health. Unfortunately, current water treatment techniques do not efficiently remove all of the PhACs, which results in the occurrence of such compounds in surface and ground waters. Advanced oxidation/reduction processes (AO/RPs) which utilize free radical reactions to directly degrade chemical contaminants are alternatives to traditional water treatment methods. This study reports the absolute bimolecular reaction rate constants for three pharmaceutical compounds (fibrates), clofibric acid, bezafibrate, and gemfibrozil, with the hydroxyl radical (*OH) and hydrated electron (e(-)(aq)). The bimolecular reaction rate constants for *OH were (6.98 +/- 0.12) x 10(9), (8.00 +/- 0.22) x 10(9), and (10.0 +/- 0.6) x 10(9), and for e(-)(aq) were (6.59 +/- 0.43) x 10(8), (112 +/- 3) x 10(8), and (6.26 +/- 0.58) x 10(8), for clofibric acid, bezafibrate, and gemfibrozil, respectively. Transient spectra were obtained for the intermediate radicals produced by the hydroxyl radical reactions. In addition, preliminary degradation mechanisms and major products were elucidated using (137)Cs gamma-irradiation and LC-MS. These data are required for evaluating the potential use of AO/RPs for the destruction of these compounds in treating water for various purposes.

  12. Mechanisms of accelerated degradation in the front cells of PEMFC stacks and some mitigation strategies

    NASA Astrophysics Data System (ADS)

    Li, Pengcheng; Pei, Pucheng; He, Yongling; Yuan, Xing; Chao, Pengxiang; Wang, Xizhong

    2013-11-01

    The accelerated degradation in the front cells of a polymer electrolyte membrane fuel cell(PEMFC) stack seriously reduces the reliability and durability of the whole stack. Most researches only focus on the size and configuration of the gas intake manifold, which may lead to the maldistribution of flow and pressure. In order to find out the mechanisms of the accelerated degradation in the front cells, an extensive program of experimental and simulation work is initiated and the results are reported. It is found that after long-term lifetime tests the accelerated degradation in the front cells occurs in all three fuel cell stacks with different flow-fields under the U-type feed configuration. Compared with the rear cells of the stack, the voltage of the front cells is much lower at the same current densities and the membrane electrode assembly(MEA) has smaller active area, more catalyst particle agglomeration and higher ohmic impedance. For further investigation, a series of three dimensional isothermal numerical models are built to investigate the degradation mechanisms based on the experimental data. The simulation results reveal that the dry working condition of the membrane and the effect of high-speed gas scouring the MEA are the main causes of the accelerated degradation in the front cells of a PEM fuel cell stack under the U-type feed configuration. Several mitigation strategies that would mitigate these phenomena are presented: removing cells that have failed and replacing them with those of the same aging condition as the average of the stack; choosing a Z-type feed pattern instead of a U-type one; putting several air flow-field plates without MEA in the front of the stack; or exchanging the gas inlet and outlet alternately at a certain interval. This paper specifies the causes of the accelerated degradation in the front cells and provides the mitigation strategies.

  13. The effects of irradiation and EtO-treatment on ultrahigh molecular weight polyethylene acetabular cups following accelerated aging: Degradation of mechanical properties and morphology changes during hip simulator tests

    NASA Astrophysics Data System (ADS)

    Taddei, Paola; Affatato, Saverio; Rocchi, Mirko; Fagnano, Concezio; Viceconti, Marco

    2008-03-01

    The present study was aimed at investigating the effects of the sterilization method and accelerated aging on the wear and morphology of ultrahigh molecular weight polyethylene. In a first test, gamma- and EtO-sterilized acetabular cups were tested in a hip joint simulator for two million cycles. After the test, the cups underwent an accelerated aging treatment (80 °C, 4 weeks in air furnace) and were newly tested for another three million cycles. Wear was evaluated by gravimetric measurements, morphology by micro-Raman spectroscopy. During the first test, the EtO-sterilized cups underwent a significantly higher wear than the gamma-sterilized ones (62 and 30 mg/million cycles, respectively). No significant crystallinity changes were observed. Upon accelerated aging, the crystallinity increase of the gamma-sterilized cups was more pronounced than for the EtO-sterilized cups, due to chain scission and oxygen incorporation. In the second test, the wear rate of EtO-sterilized cups decreased to 38 mg/million cycles, while for gamma-irradiated cups it increased to 84 mg/million cycles. At the same time, the latter cups underwent significant increases in temperature and crystallinity, due to the higher friction. For the EtO-sterilized cups a significant decrease in crystallinity was observed, due to the occurrence of an orthorhombic → monoclinic phase transformation.

  14. Degradation mechanisms of current gain in NPN transistors

    NASA Astrophysics Data System (ADS)

    Li, Xing-Ji; Geng, Hong-Bin; Lan, Mu-Jie; Yang, De-Zhuang; He, Shi-Yu; Liu, Chao-Ming

    2010-06-01

    An investigation of ionization and displacement damage in silicon NPN bipolar junction transistors (BJTs) is presented. The transistors were irradiated separately with 90-keV electrons, 3-MeV protons and 40-MeV Br ions. Key parameters were measured in-situ and the change in current gain of the NPN BJTS was obtained at a fixed collector current (Ic = 1 mA). To characterise the radiation damage of NPN BJTs, the ionizing dose Di and displacement dose Dd as functions of chip depth in the NPN BJTs were calculated using the SRIM and Geant4 code for protons, electrons and Br ions, respectively. Based on the discussion of the radiation damage equation for current gain, it is clear that the current gain degradation of the NPN BJTs is sensitive to both ionization and displacement damage. The degradation mechanism of the current gain is related to the ratio of Dd/(Dd + Di) in the sensitive region given by charged particles. The irradiation particles leading to lower Dd/(Dd + Di) within the same chip depth at a given total dose would mainly produce ionization damage to the NPN BJTs. On the other hand, the charged particles causing larger Dd/(Dd + Di) at a given total dose would tend to generate displacement damage to the NPN BJTs. The Messenger-Spratt equation could be used to describe the experimental data for the latter case.

  15. Characterizing mechanical effects of aging damage

    SciTech Connect

    Sewell, T.D.; Chen, S.P.; Schoonover, J.R.; Trent, B.C.; Howe, P.M.; Hjelm, R.P.; Browning, R.V.

    1998-12-01

    This is the final report of a two-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal was to develop and apply several different experimental and theoretical/computational tools to better understand physical and chemical aging phenomena in plastic-bonded high explosives, and to develop a methodology for predicting the likely effects of aging on the mechanical properties of the composite based on input from these fundamental studies. Initial comparisons were done for spectra of fresh and aged Esane, as well as PBX-9501, and the authors found differences in the carbonyl region of the spectrum, which possibly reflect differences in hydrogen bonding due to aging phenomena. The micromechanical model of composites was extended to study various volume fractions of HMX with binders. The results showed that, as the binder fraction increases, there is a decrease in the maximum stress that can be supported but an increase in the percent strain at final fracture. A more realistic microstructural model was obtained through the use of a phase field model. Using this model, the authors have studied the microstructural evolution as a function of the grain boundary energy vs. misorientation relationship. The initial results indicate that there are some changes in the grain growth rate when the grain-boundary energy dependence on the angle is not constant. They also find that solute tends to segregate at the grain boundary and slows the grain growth kinetics.

  16. Thermal degradation of aqueous 2-aminoethylethanolamine in CO2 capture; identification of degradation products, reaction mechanisms and computational studies.

    PubMed

    Saeed, Idris Mohamed; Lee, Vannajan Sanghiran; Mazari, Shaukat Ali; Si Ali, B; Basirun, Wan Jeffrey; Asghar, Anam; Ghalib, Lubna; Jan, Badrul Mohamed

    2017-01-01

    Amine degradation is the main significant problems in amine-based post-combustion CO2 capture, causes foaming, increase in viscosity, corrosion, fouling as well as environmental issues. Therefore it is very important to develop the most efficient solvent with high thermal and chemical stability. This study investigated thermal degradation of aqueous 30% 2-aminoethylethanolamine (AEEA) using 316 stainless steel cylinders in the presence and absence of CO2 for 4 weeks. The degradation products were identified by gas chromatography mass spectrometry (GC/MS) and liquid chromatography-time-of-flight-mass spectrometry (LC-QTOF/MS). The results showed AEEA is stable in the absence of CO2, while in the presence of CO2 AEEA showed to be very unstable and numbers of degradation products were identified. 1-(2-Hydroxyethyl)-2-imidazolidinone (HEIA) was the most abundance degradation product. A possible mechanism for the thermal degradation of AEEA has been developed to explain the formation of degradation products. In addition, the reaction energy of formation of the most abundance degradation product HEIA was calculated using quantum mechanical calculation.

  17. Analysis of the degradation mechanisms in an impacted ceramic

    NASA Astrophysics Data System (ADS)

    Denoual, Christophe; Cottenot, Charles; Hild, Francois

    1997-07-01

    To analyze the degradation mechanism in a SiC ceramic during impact, three edge-on impact configurations are used with a steel blunt cylinder projectile fired at 330 m/s. First, the polished surface of the ceramic is recorded each 300 nano-second with a high speed camera that allows to follow the damage generation and evolution. The main damage mechanism is shown to be microcracking in mode I. The second configuration uses a high speed Moiré photography system which allows to measure dynamic 2-D strain fields. Sequences of fringe patterns are analyzed. An illustration of the history of strains and principal directions of a 32mm*32mm strain field is shown. In the third configuration, the ceramic is confined by aluminum to allow a post mortem analysis. The main result is that the macroscopic cracks are surrounded by many short cracks. This study can be used to validate damage evolution laws for impacted ceramics, as shown in a companion paper.

  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.

  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.

  1. A New Class of Risk-Importance Measures to Support Reactor Aging Management and the Prioritization of Materials Degradation Research

    SciTech Connect

    Unwin, Stephen D.; Lowry, Peter P.; Toyooka, Michael Y.

    2010-06-07

    As the US fleet of light water reactors ages, the risks of operation might be expected to increase. Although probabilistic risk assessment has proven a critical resource in risk-informed regulatory decision-making, limitations in current methods and models have constrained their prospective value in reactor aging management. These limitations stem principally from the use of static component failure rate models (which do not allow the impact of component aging on failure rates to be represented) and a very limited treatment of passive components (which would be expected to have an increasingly significant risk contribution in an aging system). Yet, a PRA captures a substantial knowledge base that could be of significant value in addressing plant aging. In this paper we will describe a methodology and a new class of risk importance measures that allow the use of an existing PRA model to support the management of plant aging, the prioritization of improvements to non-destructive examination and monitoring techniques, and the establishment of research emphases in materials science. This methodology makes use of data resources generated under the USNRC Proactive Management of Materials Degradation program which addresses the anticipated effects of numerous aging degradation mechanisms on a wide variety of component types.

  2. 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.

  3. 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.

  4. 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.

  5. Epigenetic Mechanisms of the Aging Human Retina.

    PubMed

    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.

  6. 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

  7. Analysis of degradation mechanisms in donor-acceptor copolymer based organic photovoltaic devices using impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Srivastava, S. B.; Sonar, P.; Singh, S. P.

    2016-09-01

    The stability of organic photovoltaic (OPV) devices in ambient conditions has been a serious issue which needs to be addressed and resolved timely. In order to probe the degradation mechanism in a donor-acceptor polymer PDPP-TNT: PC71BM bulk heterojunction based OPV devices, we have studied current density-voltage (J-V) behavior and impedance spectroscopy of fresh and aged devices. The current-voltage characteristic of optimized fresh devices exhibit a short circuit current density (J sc) of 8.9 mA cm-2, open circuit voltage (V oc) of 0.79 V, fill factor (FF) of 54.6%, and power conversion efficiency (PCE) of 3.8%. For aged devices, J sc, V oc, FF, and PCE were reduced to 57.3%, 89.8%, 44.3% and 23.7% of its initial value, respectively. The impedance spectra measured under illumination for these devices were successfully fitted using a CPE-based circuit model. For aged devices, the low-frequency response in impedance spectra suggests an accumulation of the photo-generated charge carriers at the interfaces which leads to a significant lowering in fill factor. Such degradation in device performance is attributed to the incorporation of oxygen and water molecules in devices. An increase in the recombination resistance indicates a deterioration of free charge carrier generation and conduction in devices.

  8. 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.

  9. Seismic Fragility Analysis of a Condensate Storage Tank with Age-Related Degradations

    SciTech Connect

    Nie, J.; Braverman, J.; Hofmayer, C; Choun, Y-S; Kim, MK; Choi, I-K

    2011-04-01

    The Korea Atomic Energy Research Institute (KAERI) is conducting a five-year research project to develop a realistic seismic risk evaluation system which includes the consideration of aging of structures and components in nuclear power plants (NPPs). The KAERI research project includes three specific areas that are essential to seismic probabilistic risk assessment (PRA): (1) probabilistic seismic hazard analysis, (2) seismic fragility analysis including the effects of aging, and (3) a plant seismic risk analysis. Since 2007, Brookhaven National Laboratory (BNL) has entered into a collaboration agreement with KAERI to support its development of seismic capability evaluation technology for degraded structures and components. The collaborative research effort is intended to continue over a five year period. The goal of this collaboration endeavor is to assist KAERI to develop seismic fragility analysis methods that consider the potential effects of age-related degradation of structures, systems, and components (SSCs). The research results of this multi-year collaboration will be utilized as input to seismic PRAs. This report describes the research effort performed by BNL for the Year 4 scope of work. This report was developed as an update to the Year 3 report by incorporating a major supplement to the Year 3 fragility analysis. In the Year 4 research scope, an additional study was carried out to consider an additional degradation scenario, in which the three basic degradation scenarios, i.e., degraded tank shell, degraded anchor bolts, and cracked anchorage concrete, are combined in a non-perfect correlation manner. A representative operational water level is used for this effort. Building on the same CDFM procedure implemented for the Year 3 Tasks, a simulation method was applied using optimum Latin Hypercube samples to characterize the deterioration behavior of the fragility capacity as a function of age-related degradations. The results are summarized in Section 5

  10. Semi-degradable poly(β-amino ester) networks with temporally controlled enhancement of mechanical properties.

    PubMed

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

    2014-08-01

    Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss of 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.

  11. Mechanical loading of bovine pericardium accelerates enzymatic degradation.

    PubMed

    Ellsmere, J C; Khanna, R A; Lee, J M

    1999-06-01

    Bioprosthetic heart valves fail as the result of two simultaneous processes: structural deterioration and calcification. Leaflet deterioration and perforation have been correlated with regions of highest stress in the tissue. The failures have long been assumed to be due to simple mechanical fatigue of the collagen fibre architecture; however, we have hypothesized that local stresses-and particularly dynamic stresses-accelerate local proteolysis, leading to tissue failure. This study addresses that hypothesis. Using a novel, custom-built microtensile culture system, strips of bovine pericardium were subjected to static and dynamic loads while being exposed to solutions of microbial collagenase or trypsin (a non-specific proteolytic enzyme). The time to extend to 30% strain (defined here as time to failure) was recorded. After failure, the percentage of collagen solubilized was calculated based on the amount of hydroxyproline present in solution. All data were analyzed by analysis of variance (ANOVA). In collagenase, exposure to static load significantly decreased the time to failure (P < 0.002) due to increased mean rate of collagen solubilization. Importantly, specimens exposed to collagenase and dynamic load failed faster than those exposed to collagenase under the same average static load (P = 0.02). In trypsin, by contrast, static load never led to failure and produced only minimal degradation. Under dynamic load, however, specimens exposed to collagenase, trypsin, and even Tris/CaCl2 buffer solution, all failed. Only samples exposed to Hanks' physiological solution did not fail. Failure of the specimens exposed to trypsin and Tris/CaCl2 suggests that the non-collagenous components and the calcium-dependent proteolytic enzymes present in pericardial tissue may play roles in the pathogenesis of bioprosthetic heart valve degeneration.

  12. Molecular Mechanisms Associated with Xylan Degradation by Xanthomonas Plant Pathogens*

    PubMed Central

    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

    2014-01-01

    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

  13. 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.

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

    PubMed Central

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

    2015-01-01

    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

  16. Genetic analysis of mechanisms of aging.

    PubMed

    Rose, M R; Archer, M A

    1996-06-01

    A wide range of genetic models with postponed aging are now available, from selected mice and Drosophilia to mutant Caenorhabditis elegans and Saccharomyces cerevisiae. These systems allow efficient testing of alternative mechanistic hypotheses for aging. Genetic analysis is forging stronger connections between particular alleles and susceptibility to particular 'diseases of aging'; for example, two different genes for Alzheimer disease have been identified.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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...

  2. Mechanism for degradation of Nafion in PEM fuel cells from quantum mechanics calculations.

    PubMed

    Yu, Ted H; Sha, Yao; Liu, Wei-Guang; Merinov, Boris V; Shirvanian, Pezhman; Goddard, William A

    2011-12-14

    We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism.

  3. Molecular mechanisms of proteasome plasticity in aging.

    PubMed

    Rodriguez, Karl A; Gaczynska, Maria; Osmulski, Pawel A

    2010-02-01

    The ubiquitin-proteasome pathway plays a crucial role in regulation of intracellular protein turnover. Proteasome, the central protease of the pathway, encompasses multi-subunit assemblies sharing a common catalytic core supplemented by regulatory modules and localizing to different subcellular compartments. To better comprehend age-related functions of the proteasome we surveyed content, composition and catalytic properties of the enzyme in cytosolic, microsomal and nuclear fractions obtained from mouse livers subjected to organismal aging. We found that during aging subunit composition and subcellular distribution of proteasomes changed without substantial alterations in the total level of core complexes. We observed that the general decline in proteasomes functions was limited to nuclear and cytosolic compartments. Surprisingly, the observed changes in activity and specificity were linked to the amount of the activator module and distinct composition of the catalytic subunits. In contrast, activity, specificity and composition of the microsomal-associated proteasomes remained mostly unaffected by aging; however their relative contribution to the total activity was substantially elevated. Unexpectedly, the nuclear proteasomes were affected most profoundly by aging possibly triggering significant changes in cellular signaling and transcription. Collectively, the data indicate an age-related refocusing of proteasome from the compartment-specific functions towards general protein maintenance.

  4. Study of the degradation of gelatin in paper upon aging using aqueous size-exclusion chromatography.

    PubMed

    Dupont, Anne-Laurence

    2002-03-15

    We studied the aging behaviour of gelatin used to size paper. Thus far, research on the aging of paper has largely ignored the sizing agent. Degradation of the protein was characterised and the impact of paper components, such as cellulose, and aluminium potassium sulphate was evaluated. Whatman No. 1 filter papers sized with two types of gelatins (A and B) were prepared as model samples. Commercially sized modern papers (Arches) were also studied in order to compare laboratory samples with real artist papers. Both types of papers were artificially aged (80 degrees C, 50% relative humidity for 35 and 94 days). Historic papers were included in the study in order to compare artificially aged with naturally aged gelatin. The aqueous extracts from the papers were characterised by aqueous size-exclusion chromatography (SEC) using four PL-Aquagel-OH columns and UV photodiode array detection at 220, 254 and 280 nm. Results showed that gelatin undergoes hydrolysis upon aging, type A gelatin showing a faster degradation rate than type B. The result was an increase in the lower-molar-mass fractions, under 50,000 g mol(-1), and especially in a characteristic fraction with a peak molecular mass (MP) of 14,000 g mol(-1). A significant decrease in the extraction yields of alpha-, beta- and gamma-chains occurred after aging. This was attributed to crosslinking, leading to the formation of less-soluble polypeptides with very high molar mass (>800,000 g mol(-1)) Less than 10% alum had no impact on the degradation rate; higher alum contents accelerated hydrolysis reactions.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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…

  10. Cell-Nonautonomous Mechanisms Underlying Cellular and Organismal Aging.

    PubMed

    Medkour, Younes; Svistkova, Veronika; Titorenko, Vladimir I

    2016-01-01

    Cell-autonomous mechanisms underlying cellular and organismal aging in evolutionarily distant eukaryotes have been established; these mechanisms regulate longevity-defining processes within a single eukaryotic cell. Recent findings have provided valuable insight into cell-nonautonomous mechanisms modulating cellular and organismal aging in eukaryotes across phyla; these mechanisms involve a transmission of various longevity factors between different cells, tissues, and organisms. Herein, we review such cell-nonautonomous mechanisms of aging in eukaryotes. We discuss the following: (1) how low molecular weight transmissible longevity factors modulate aging and define longevity of cells in yeast populations cultured in liquid media or on solid surfaces, (2) how communications between proteostasis stress networks operating in neurons and nonneuronal somatic tissues define longevity of the nematode Caenorhabditis elegans by modulating the rates of aging in different tissues, and (3) how different bacterial species colonizing the gut lumen of C. elegans define nematode longevity by modulating the rate of organismal aging.

  11. Improved Learning and Memory in Aged Mice Deficient in Amyloid β-Degrading Neutral Endopeptidase

    PubMed Central

    Walther, Thomas; Albrecht, Doris; Becker, Matthias; Schubert, Manja; Kouznetsova, Elena; Wiesner, Burkard; Maul, Björn; Schliebs, Reinhard; Grecksch, Gisela; Furkert, Jens; Sterner-Kock, Anja; Schultheiss, Heinz-Peter; Becker, Axel; Siems, Wolf-Eberhard

    2009-01-01

    Background Neutral endopeptidase, also known as neprilysin and abbreviated NEP, is considered to be one of the key enzymes in initial human amyloid-β (Aβ) degradation. The aim of our study was to explore the impact of NEP deficiency on the initial development of dementia-like symptoms in mice. Methodology/Principal Findings We found that while endogenous Aβ concentrations were elevated in the brains of NEP-knockout mice at all investigated age groups, immunohistochemical analysis using monoclonal antibodies did not detect any Aβ deposits even in old NEP knockout mice. Surprisingly, tests of learning and memory revealed that the ability to learn was not reduced in old NEP-deficient mice but instead had significantly improved, and sustained learning and memory in the aged mice was congruent with improved long-term potentiation (LTP) in brain slices of the hippocampus and lateral amygdala. Our data suggests a beneficial effect of pharmacological inhibition of cerebral NEP on learning and memory in mice due to the accumulation of peptides other than Aβ degradable by NEP. By conducting degradation studies and peptide measurements in the brain of both genotypes, we identified two neuropeptide candidates, glucagon-like peptide 1 and galanin, as first potential candidates to be involved in the improved learning in aged NEP-deficient mice. Conclusions/Significance Thus, the existence of peptides targeted by NEP that improve learning and memory in older individuals may represent a promising avenue for the treatment of neurodegenerative diseases. PMID:19240795

  12. 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.

  13. Factors of skin ageing share common mechanisms.

    PubMed

    Giacomoni, P U; Rein, G

    2001-01-01

    Ageing has been defined as the accumulation of molecular modifications which manifest as macroscopic clinical changes. Human skin, unique among mammalians insofar as it is deprived of fur, is particularly sensitive to environmental stress. Major environmental factors have been recognized to induce modifications of the morphological and biophysical properties of the skin. Metabolites from ingested or inhaled substances do affect skin, which is also sensitive to endogenous hormone levels. Factors as diverse as ultraviolet radiation, atmospheric pollution, wounds, infections, traumatisms, anoxya, cigarette smoke, and hormonal status have a role in increasing the rate of accumulation of molecular modifications and have thus been termed 'factors of ageing'. All these factors share as a common feature, the capability to directly or indirectly induce one of the steps of the micro-inflammatory cycle, which includes the expression of ICAM-1 in endothelial cells. This triggers a process leading to the accumulation of damages in the skin resulting in skin ageing since ICAM-1 expression provokes recruitment and diapedesis of circulating immune cells, which digest the extracellular matrix (ECM) by secreting collagenases, myeloperoxidases and reactive oxygen species. The activation of these lytic processes provokes random damage to resident cells, which in turn secrete prostaglandines and leukotrienes. These signaling molecules induce the degranulation of resident mast cells which release the autacoid histamine and the cytokine TNF-alpha thus activating endothelial cells lining adjacent capillaries which release P-selectin and synthesize ICAM-1. This closes a self-maintained micro-inflammatory cycle, which results in the accumulation of ECM damage, i.e. skin aging. In this paper we review the evidence that two factors able to induce macroscopical and molecular modifications in the skin, protein glycation and stretch, activate the micro-inflammatory cycle. We further present

  14. Module Degradation Mechanisms Studied by a Multi-Scale Approach

    SciTech Connect

    Johnston, Steve; Al-Jassim, Mowafak; Hacke, Peter; Harvey, Steven P.; Jiang, Chun-Sheng; Gerber, Andreas; Guthrey, Harvey; Moutinho, Helio; Albin, David; To, Bobby; Tynan, Jerry; Moseley, John; Aguiar, Jeffery; Xiao, Chuanxiao; Waddle, John; Nardone, Marco

    2016-11-21

    A key pathway to meeting the Department of Energy SunShot 2020 goals is to reduce financing costs by improving investor confidence through improved photovoltaic (PV) module reliability. A comprehensive approach to further understand and improve PV reliability includes characterization techniques and modeling from module to atomic scale. Imaging techniques, which include photoluminescence, electroluminescence, and lock-in thermography, are used to locate localized defects responsible for module degradation. Small area samples containing such defects are prepared using coring techniques and are then suitable and available for microscopic study and specific defect modeling and analysis.

  15. Ethylene propylene cable degradation during LOCA research tests: tensile properties at the completion of accelerated aging

    SciTech Connect

    Bustard, L.D.

    1982-05-01

    Six ethylene-propylene rubber (EPR) insulation materials were aged at elevated temperature and radiation stress exposures common in cable LOCA qualification tests. Material samples were subjected to various simultaneous and sequential aging simulations in preparation for accident environmental exposures. Tensile properties subsequent to the aging exposure sequences are reported. The tensile properties of some, but not all, specimens were sensitive to the order of radiation and elevated temperature stress exposure. Other specimens showed more severe degradation when simultaneously exposed to radiation and elevated temperature as opposed to the sequential exposure to the same stresses. Results illustrate the difficulty in defining a single test procedure for nuclear safety-related qualification of EPR elastomers. A common worst-case sequential aging sequence could not be identified.

  16. Iron and ageing: an introduction to iron regulatory mechanisms.

    PubMed

    Levenson, Cathy W; Tassabehji, Nadine M

    2004-07-01

    While there have been significant advances made in our understanding of the cellular and molecular mechanisms that regulate iron absorption, transport, storage, and utilization, the effect of ageing on these mechanisms and the role of iron in the ageing process is not fully understood. Thus, this review will provide an overview of the iron regulatory mechanisms that may be a factor in the ageing process. Additional reviews in this volume represent an attempt to explore the very latest information on the regulation of iron with a particular emphasis on age-related pathology including mitochondrial function, Parkinson's disease, Alzheimer's disease, stroke, and cardiovascular disease.

  17. 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

  18. Degradation Mechanisms of SOFC Anodes in Coal Gas Containing Phosphorus

    SciTech Connect

    Marina, Olga A.; Coyle, Christopher A.; Thomsen, Edwin C.; Edwards, Danny J.; Coffey, Greg W.; Pederson, Larry R.

    2010-01-22

    The interaction of phosphorus in synthetic coal gas with the nickel-based anode of solid oxide fuel cells has been investigated. Tests with both anode-supported and electrolyte-supported button cells were performed at 700 to 800oC in synthetic coal gas containing 0.5 to 10 ppm phosphorus, introduced as phosphine. Two primary modes of degradation were observed. The most obvious was the formation of a series of bulk nickel phosphide phases, of which Ni3P, Ni5P2, Ni12P5 and Ni2P were identified. Phosphorus was essentially completely captured by the anode, forming a sharp boundary between converted and unconverted anode portions. These products partially coalesced into large grains, which eventually affected electronic percolation through the anode support. Thermodynamic calculations predict that formation of the first binary nickel phosphide phase is possible at sub-parts per billion concentrations in coal gas at temperatures relevant to fuel cell operation. A second mode of degradation is attributed to surface diffusion of phosphorus to the active anode/electrolyte interface to form an adsorption layer. Direct evidence for the presence of such an adsorption layer on nickel was obtained by surface spectroscopies on fracture surfaces. Further, cell performance losses were observed well before the entire anode was converted to bulk nickel phosphide. Impedance spectroscopy revealed that these losses were primarily due to growth in electrodic resistance, whereas large ohmic increases were visible when the entire anode was converted to nickel phosphide phases. The rate of resistance growth for anode-supported cells showed a very low dependence on phosphorus concentration, attributed to phosphorus activity control within the anode by bulk nickel phosphide products.

  19. Hydrothermal and mechanical stresses degrade fiber-matrix interfacial bond strength in dental fiber-reinforced composites.

    PubMed

    Bouillaguet, Serge; Schütt, Andrea; Alander, Pasi; Schwaller, Patrick; Buerki, Gerhard; Michler, Johann; Cattani-Lorente, Maria; Vallittu, Pekka K; Krejci, Ivo

    2006-01-01

    Fiber-reinforced composites (FRCs) show great promise as long-term restorative materials in dentistry and medicine. Recent evidence indicates that these materials degrade in vivo, but the mechanisms are unclear. The objective of this study was to investigate mechanisms of deterioration of glass fiber-polymer matrix bond strengths in dental fiber-reinforced composites during hydrothermal and mechanical aging. Conventional three-point bending tests on dental FRCs were used to assess flexural strengths and moduli. Micro push-out tests were used to measure glass fiber-polymer matrix bond strengths, and nanoindentation tests were used to determine the modulus of elasticity of fiber and polymer matrix phases separately. Bar-shaped specimens of FRCs (EverStick, StickTech, and Vectris Pontic, Ivoclar-Vivadent) were either stored at room temperature, in water (37 and 100 degrees C) or subjected to ageing (10(6) cycles, load: 49 N), then tested by three-point bending. Thin slices were prepared for micro push-out and nanoindentation tests. The ultimate flexural strengths of both FRCs were significantly reduced after aging (p < 0.05). Both water storage and mechanical loading reduced the interfacial bond strengths of glass fibers to polymer matrices. Nanoindentation tests revealed a slight reduction in the elastic modulus of the EverStick and Vectris Pontic polymer matrix after water storage. Mechanical properties of FRC materials degrade primarily by a loss of interfacial bond strength between the glass and resin phases. This degradation is detectable by micro push-out and nanoindentation methods.

  20. 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.

  1. 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.

  2. Analysis of the degradation and aging of a commercial photovoltaic installation

    NASA Astrophysics Data System (ADS)

    Bradley, Alexander; Hamzavy, Babak; Gambogi, William

    2014-10-01

    Simple and accurate methods are needed to monitor and assess PV systems. It is important to characterize and understand the value of the system with regard to safety and performance (including seasonal and geographical variations) as well as operation and maintenance. This documentation is becoming necessary for the secondary or resale value of PV assets. We report the results from an analysis of a commercial c-Si PV array owned and operated by DuPont. Our technical assessment consists of remote monitoring, field inspection with visual examination and thermal imaging to create a pareto chart of degradation modes, and laboratory analysis. A comparison of remote monitoring and site inspection is presented as well as laboratory analysis (nondestructive and destructive test methods) of modules removed from the service environment. Degradation modes and quality issues became evident as electrical, optical, physical or chemical defects developed with system age. This evaluation provided system data, documented quality issues, and quantified the cost of ownership.

  3. Mechanisms Underlying T Cell Immunosenescence: Aging and Cytomegalovirus Infection

    PubMed Central

    Tu, Wenjuan; Rao, Sudha

    2016-01-01

    The ability of the human immune system to protect against infectious disease declines with age and efficacy of vaccination reduces significantly in the elderly. Aging of the immune system, also termed as immunosenescence, involves many changes in human T cell immunity that is characterized by a loss in naïve T cell population and an increase in highly differentiated CD28- memory T cell subset. There is extensive data showing that latent persistent human cytomegalovirus (HCMV) infection is also associated with age-related immune dysfunction in the T cells, which might enhance immunosenescence. Understanding the molecular mechanisms underlying age-related and HCMV-related immunosenescence is critical for the development of effective age-targeted vaccines and immunotherapies. In this review, we will address the role of both aging and HCMV infection that contribute to the T cell senescence and discuss the potential molecular mechanisms in aged T cells. PMID:28082969

  4. 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.

  5. 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.

  6. 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.

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

    PubMed Central

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

    1991-01-01

    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

  8. Epigenetic mechanisms of dietary restriction induced aging in Drosophila.

    PubMed

    Lian, Ting; Gaur, Uma; Yang, Deying; Li, Diyan; Li, Ying; Yang, Mingyao

    2015-12-01

    Aging is a long-standing problem that people are always interested in. Thus, it is critical to understand the underlying molecular mechanisms in aging and explore the most efficient method to extend life expectancy. To achieve this goal, a wide range of systems including cells, rodent models, budding yeast, worms and flies have been employed for decades. In recent years, the effect of dietary restriction (DR) on lifespan is in the prime focus. Although we have confirmed that reduced insulin and/or insulin-like growth factor (IGF) and the target of rapamycin (TOR) signaling can increase Drosophila lifespan; the precise molecular mechanisms and nutritional response landscape of diet-mediated aging is ambiguous. Epigenetic events have been considered as the major contributors to lifespan extension with response to DR. The role of DNA methylation in aging is well acknowledged in mammals and rodents where it has been shown to impact aging by regulating the transcription, though the mechanism of regulation is not limited to only transcription. In Drosophila, the contribution of methylation during DR in aging is definitely less explored. In this review, we will update the advances in mechanisms of DR, with a particular focus on methylation as an upcoming target for aging studies and discuss Drosophila as a powerful model to understand mechanisms of aging with response to diet.

  9. 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.

  10. Elucidating PID Degradation Mechanisms and In Situ Dark I–V Monitoring for Modeling Degradation Rate in CdTe Thin-Film Modules

    SciTech Connect

    Hacke, Peter; Spataru, Sergiu; Johnston, Steve; Terwilliger, Kent; VanSant, Kaitlyn; Kempe, Michael; Wohlgemuth, John; Kurtz, Sarah; Olsson, Anders; Propst, Michelle

    2016-11-01

    A progression of potential-induced degradation (PID) mechanisms are observed in CdTe modules, including shunting/junction degradation and two different manifestations of series resistance depending on the stress level and water ingress. The dark I-V method for in-situ characterization of Pmax based on superposition was adapted for the thin-film modules undergoing PID in view of the degradation mechanisms observed. An exponential model based on module temperature and relative humidity was fit to the PID rate for multiple stress levels in chamber tests and validated by predicting the observed degradation of the module type in the field.

  11. Nano-Mechanical Studies on Polyglactin Sutures Subjected to In Vitro Hydrolytic and Enzymatic Degradation.

    PubMed

    Sun, Leming; Wanasekara, Nandula; Chalivendra, Vijaya; Calvert, Paul

    2015-01-01

    An experimental investigation on the effects of in vitro hydrolytic and enzymatic degradation on mechanical properties of polyglactin 910 monofilament sutures was performed by conducting nanoindentation studies using an atomic force microscope (AFM). For hydrolytic degradation, the sutures were incubated in phosphate buffered saline (PBS) solution at three different pH conditions, 5, 7.4, and 10. For enzymatic degradation, esterase was employed at pH condition of 7.4. The property of the sutures changed with time at different conditions were investigated by nanoindentation, tensile test experiments, image analysis using both of scanning electron microscopy (SEM) and AFM, and also Fourier transform infrared spectroscopy (FTIR). The effects of degradation on gradation of Young's modulus values across the cross section of the sutures were studied by doing progressive nanoindentation from center to surface. FTIR studies revealed the formation of new hydroxyl bonds due to both hydrolytic and enzymatic degradations. Nanoindentation results indicated that the degradation does not cause a gradient of Young's modulus of the polyglactin 910 monofilament sutures across the cross section from center to surface at different degradation times for both hydrolytic and enzymatic degradations. However, in general, the Young's modulus of all samples was decreased over 4 weeks of degradation. The microscopic evaluation of the samples also showed both qualitative changes in surface morphology and quantitative changes in surface roughness on the surface of degraded sutures. This study provided a deep understanding of the polyglactin sutures subjected to in vitro hydrolytic and enzymatic degradation, and also opened a new avenue to study the biomaterials at nano-scale.

  12. Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

    PubMed

    Moctezuma, Edgar; Leyva, Elisa; Aguilar, Claudia A; Luna, Raúl A; Montalvo, Carlos

    2012-12-01

    The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds.

  13. 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.

  14. 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.

  15. Hydrolytic degradation of N,N‧-ethylenedimaleimide: Crystal structures of key intermediates and proposed mechanisms

    NASA Astrophysics Data System (ADS)

    Tan, Xue-Jie; Cheng, Shuang-Shuang; Shi, Yan; Xing, Dian-Xiang; Liu, Yun; Li, Hui; Feng, Wen-Quan; Yang, Jian-Bo

    2016-12-01

    Maleimide groups are used extensively in bioconjugation reactions, but limited mechanistic studies are available regarding their hydrolysis reactions. In this paper, five single-crystal structures related with the reaction of four-step hydrolytic degradation of N,N‧-ethylenedimaleimide have been investigated. On the basis of experimental results, the reaction mechanisms without or with water catalysis are proposed, which could provide some enlightenment into the study of similar hydrolytic degradations.

  16. 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.

  17. 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.

  18. Progress in Understanding Degradation Mechanisms and Improving Stability in Organic Photovoltaics.

    PubMed

    Mateker, William R; McGehee, Michael D

    2017-03-01

    Understanding the degradation mechanisms of organic photovoltaics is particularly important, as they tend to degrade faster than their inorganic counterparts, such as silicon and cadmium telluride. An overview is provided here of the main degradation mechanisms that researchers have identified so far that cause extrinsic degradation from oxygen and water, intrinsic degradation in the dark, and photo-induced burn-in. In addition, it provides methods for researchers to identify these mechanisms in new materials and device structures to screen them more quickly for promising long-term performance. These general strategies will likely be helpful in other photovoltaic technologies that suffer from insufficient stability, such as perovskite solar cells. Finally, the most promising lifetime results are highlighted and recommendations to improve long-term performance are made. To prevent degradation from oxygen and water for sufficiently long time periods, OPVs will likely need to be encapsulated by barrier materials with lower permeation rates of oxygen and water than typical flexible substrate materials. To improve stability at operating temperatures, materials will likely require glass transition temperatures above 100 °C. Methods to prevent photo-induced burn-in are least understood, but recent research indicates that using pure materials with dense and ordered film morphologies can reduce the burn-in effect.

  19. 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…

  20. Fracture Resistance of Hybrid Glass Matrix Composite and Its Degradation Due to Thermal Ageing and Thermal Shock

    NASA Astrophysics Data System (ADS)

    Dlouhý, Ivo; Chlup, Zdenêk; Atiq, Shabbar; Boccaccini, Aldo R.

    In brittle matrix composites reinforced by continuous ceramic fibres, the favourable fracture behaviour is provided by the presence of weak fibre/matrix interfaces, which lead to the fibre pullout effect [1]. The thermal stability and high temperature mechanical properties of silicate matrix composites reinforced by carbon and SiC based fibres in oxidising environments have been investigated quite extensively in the past by conducting thermal aging and thermal cycling experiments over a wide range of temperatures [2-5]. A common result of investigations conducted at temperatures in the range 500-700°C is that there is a decrease of tensile and flexural strength of the composites. It has been shown that this is the consequence of oxidation of the fibres, in case of carbon fibre reinforced composites, or of degradation of the fibre/matrix interphase, which is in fact a carbon-rich nanometric interfacial layer, in SiC fibre reinforced composites [2-5].

  1. 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

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

    PubMed

    Speranza, Giovanna; Morelli, Carlo F; Cairoli, Paola; Müller, 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 -CH2-O- to =N-CH2- 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.

  3. 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.

  4. 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.

  5. 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

  6. Epigenetic mechanisms facilitating oligodendrocyte development, maturation, and aging.

    PubMed

    Copray, Sjef; Huynh, Jimmy Long; Sher, Falak; Casaccia-Bonnefil, Patrizia; Boddeke, Erik

    2009-11-15

    The process of oligodendrocyte differentiation is regulated by a dynamic interaction between a genetic and an epigenetic program. Recent studies, addressing nucleosomal histone modifications have considerably increased our knowledge regarding epigenetic regulation of gene expression during oligodendrocyte development and aging. These results have generated new hypotheses regarding the mechanisms underlying the decreased efficiency of endogenous remyelination in response to demyelinating injuries with increasing age. In this review, we present an overview of the epigenetic mechanisms regulating gene expression at specific stages of oligodendrocyte differentiation and maturation as well as the changes that occur with aging.

  7. 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.

  8. Evolution of water sorption in catalyst coated membranes subjected to combined chemical and mechanical degradation.

    PubMed

    Venkatesan, Senthil velan; Lim, Chan; Rogers, Erin; Holdcroft, Steven; Kjeang, Erik

    2015-06-07

    Catalyst coated perfluorosulfonic acid ionomer membranes (CCMs) were subjected to a combined chemical/mechanical accelerated stress test (AST) designed for rapid benchmarking of in situ membrane stability in polymer electrolyte fuel cells. In order to understand the evolution of the ionomer water sorption characteristics during combined chemical/mechanical degradation, CCM samples were periodically extracted from the AST and analyzed for ionomer mass fraction and water sorption properties. In spite of severe fluoride release and membrane thinning, the water uptake per unit mass of the partially degraded CCMs was found to be essentially constant. The mass fraction of ionomer in the CCM samples determined from thermogravimetric analysis (TGA) showed significant material loss throughout the AST process due to ionomer degradation and fluoride release, up to roughly 50% at end-of-life. The effects proceeding at different stages of degradation were therefore more accurately revealed by ionomer mass-normalized data. The water uptake per unit gram of ionomer was shown to increase significantly with degradation, in contrast to the previous results normalized by CCM dry mass. Although increased water sorption may indicate enlarged solvated hydrophilic domains in the membrane, which would be beneficial for enhanced proton mobility, the proton conductivity was found to decrease. This finding suggests that the additional water sorbed in the membrane was not contributing to proton conduction and was therefore likely situated in non-ionic cavities formed through degradation rather than in the ionic clusters.

  9. Cargo-dependent degradation of ESCRT-I as a feedback mechanism to modulate endosomal sorting.

    PubMed

    Malerød, Lene; Pedersen, Nina Marie; Sem Wegner, Catherine Elisabeth; Lobert, Viola Hélène; Leithe, Edward; Brech, Andreas; Rivedal, Edgar; Liestøl, Knut; Stenmark, Harald

    2011-09-01

    Ligand-mediated lysosomal degradation of growth factor receptors, mediated by the endosomal sorting complex required for transport (ESCRT) machinery, is a mechanism that attenuates the cellular response to growth factors. In this article, we present a novel regulatory mechanism that involves ligand-mediated degradation of a key component of the sorting machinery itself. We have investigated the endosomal localization of subunits of the four ESCRTs-Hrs (ESCRT-0), Tsg101 (ESCRT-I), EAP30/Vps22 (ESCRT-II) and charged multivesicular body protein 3/Vps24 (ESCRT-III). All the components were detected on the limiting membrane of multivesicular endosomes (MVEs). Surprisingly, however, Tsg101 and other ESCRT-I subunits were also detected within intraluminal vesicles (ILVs) of MVEs. Tsg101 was sequestered along with cargo during endosomal sorting into ILVs and further degraded in lysosomes. Importantly, ESCRT-mediated downregulation of two distinct cargoes, epidermal growth factor receptor (EGFR) and connexin43, mutually made cells refractory to degradation of the other cargo. Our observations indicate that the degradation of a key ESCRT component along with cargo represents a novel feedback control of endosomal sorting by preventing collateral degradation of cell surface receptors following stimulation of one specific pathway.

  10. 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

  11. 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.

  12. Mechanisms of aging-related proteinopathies in Caenorhabditis elegans

    PubMed Central

    Kim, Dong-Kyu; Kim, Tae Ho; Lee, Seung-Jae

    2016-01-01

    Aging is the most important risk factor for human neurodegenerative diseases such as Alzheimer's and Parkinson's diseases. Pathologically, these diseases are characterized by the deposition of specific protein aggregates in neurons and glia, representing the impairment of neuronal proteostasis. However, the mechanism by which aging affects the proteostasis system and promotes protein aggregation remains largely unknown. The short lifespan and ample genetic resources of Caenorhabditis elegans (C. elegans) have made this species a favorite model organism for aging research, and the development of proteinopathy models in this organism has helped us to understand how aging processes affect protein aggregation and neurodegeneration. Here, we review the recent literature on proteinopathies in C. elegans models and discuss the insights we have gained into the mechanisms of how aging processes are integrated into the pathogenesis of various neurodegenerative diseases. PMID:27713398

  13. Novel putative mechanisms to link circadian clocks to healthy aging.

    PubMed

    Popa-Wagner, Aurel; Catalin, Bogdan; Buga, Ana-Maria

    2015-08-01

    The circadian clock coordinates the internal physiology to increase the homeostatic capacity thereby providing both a survival advantage to the system and an optimization of energy budgeting. Multiple-oscillator circadian mechanisms are likely to play a role in regulating human health and may contribute to the aging process. Our aim is to give an overview of how the central clock in the hypothalamus and peripheral clocks relate to aging and metabolic disorders, including hyperlipidemia and hyperglycemia. In particular, we unravel novel putative mechanisms to link circadian clocks to healthy aging. This review may lead to the design of large-scale interventions to help people stay healthy as they age by adjusting daily activities, such as feeding behavior, and or adaptation to age-related changes in individual circadian rhythms.

  14. 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.

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

    PubMed Central

    Gurkar, Aditi U.; Niedernhofer, Laura J.

    2015-01-01

    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 is 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 amongst the strains may lead to the identification of fundamental pathways of aging. PMID:25617508

  16. The degradation mechanism of phenol induced by ozone in wastes system.

    PubMed

    Youmin, Sun; Xiaohua, Ren; Zhaojie, Cui; Guiqin, Zhang

    2012-08-01

    A distinct understanding for the degradation mechanism of phenol induced by ozone is very essential because the ozonation process, one of the advanced oxidation processes (AOPs), is attractive and popular in wastewater treatment. In the present work, the detailed reactions of ozone and phenol are investigated employing the density functional theory B3LYP method with the 6-311++G (d, p) basis set. The profiles of the potential energy surface are constructed and the possible reaction pathways are indicated. These detailed calculation results suggest two degradation reaction mechanisms. One is phenolic H atom abstraction mechanism, and the other is cyclo-addition and ring-opening mechanism. Considering the effect of solvent water, the calculated energy barriers and reaction enthalpies for the reaction of O3 and phenol in water phase are both lower than those in gas phase, though the degradation mechanisms are not changed. This reveals that these degradation reactions are more favorable in the water solvent. The main reaction products are C(6)H(5)OO· radical, a crucial precursor for forming PCDD/Fs and one ring-opening product, which are in good agreement with the experimental observations.

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

    PubMed

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

    2015-09-02

    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.

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

    PubMed

    Zhang, Yu-Zhong; Ran, Li-Yuan; Li, Chun-Yang; Chen, Xiu-Lan

    2015-09-01

    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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. Membrane degradation during combined chemical and mechanical accelerated stress testing of polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Lim, C.; Ghassemzadeh, L.; Van Hove, F.; Lauritzen, M.; Kolodziej, J.; Wang, G. G.; Holdcroft, S.; Kjeang, E.

    2014-07-01

    A cyclic open circuit voltage (COCV) accelerated stress test (AST) is designed to screen the simultaneous effect of chemical and mechanical membrane degradation in polymer electrolyte fuel cells. The AST consists of a steady state OCV phase to accelerate chemical degradation and periodic wet/dry cycles to provide mechanical degradation. The membrane degradation process induced by COCV AST operation is analyzed using a standard MEA with PFSA ionomer membrane. The OCV shows an initially mild decay rate followed by a higher decay rate in the later stages of the experiment. Membrane failure, defined by a threshold convective hydrogen leak rate, is obtained after 160 h of operation. Uniform membrane thinning is observed with pinhole formation being the primary cause of failure. Mechanical tensile tests reveal that the membrane becomes stiffer and more brittle during AST operation, which contributes to mechanical failure upon cyclic humidity induced stress. Solid state 19F NMR spectroscopy and fluoride emission measurements demonstrate fluorine loss from both side chain and main chain upon membrane exposure to high temperature and low humidity OCV condition.

  4. Programmatic features of aging originating in development: aging mechanisms beyond molecular damage?

    PubMed Central

    de Magalhães, João Pedro

    2012-01-01

    The idea that aging follows a predetermined sequence of events, a program, has been discredited by most contemporary authors. Instead, aging is largely thought to occur due to the accumulation of various forms of molecular damage. Recent work employing functional genomics now suggests that, indeed, certain facets of mammalian aging may follow predetermined patterns encoded in the genome as part of developmental processes. It appears that genetic programs coordinating some aspects of growth and development persist into adulthood and may become detrimental. This link between development and aging may occur due to regulated processes, including through the action of microRNAs and epigenetic mechanisms. Taken together with other results, in particular from worms, these findings provide evidence that some aging changes are not primarily a result of a build-up of stochastic damage but are rather a product of regulated processes. These processes are interpreted as forms of antagonistic pleiotropy, the product of a “shortsighted watchmaker,” and thus do not assume aging evolved for a purpose. Overall, it appears that the genome does, indeed, contain specific instructions that drive aging in animals, a radical shift in our perception of the aging process.—de Magalhães, J. P. Programmatic features of aging originating in development: aging mechanisms beyond molecular damage? PMID:22964300

  5. Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation.

    PubMed

    Xie, Xiaofang; Zhang, Yongqing; Huang, Weilin; Huang, Shaobing

    2012-01-01

    Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature, persulfate concentration and pH conditions were examined in batch experiments. The results showed that, the aniline degradation followed pseudo first-order reaction model. Aniline degradation rate increased with increasing temperature or persulfate concentration. In the pH range of 3 to 11, a low aniline degradation rate was obtained at strong acid system (pH 3), while a high degradation rate was achieved at strong alkalinity (pH 11). Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5, 7 and 9). Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology. And nitrobenzene, 4-4'-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation mechanism of aniline was also tentatively proposed.

  6. 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.

  7. Glycolic acid modulates the mechanical property and degradation of poly(glycerol, sebacate, glycolic acid).

    PubMed

    Sun, Zhi-Jie; Wu, Lan; Huang, Wei; Chen, Chang; Chen, Yan; Lu, Xi-Li; Zhang, Xiao-Lan; Yang, Bao-Feng; Dong, De-Li

    2010-01-01

    The development of biodegradable materials with controllable degradation properties is beneficial for a variety of applications. Poly(glycerol-sebacate) (PGS) is a promising candidate of biomaterials; so we synthesize a series of poly(glycerol, sebacate, glycolic acid) (PGSG) with 1:2:0, 1:2:0.2, 1:2:0.4, 1:2:0.6, 1:2:1 mole ratio of glycerol, sebacate, and glycolic acid to elucidate the relation of doped glycolic acid to the degradation rate and mechanical properties. The microstructures of the polymers with different doping of glycolic acid were dissimilar. PGSG with glycolic acid in the ratio of 0.2 displayed an integral degree of ordering, different to those with glycolic acid in the ratio of 0, 0.4, 0.6, and 1, which showed mild phase separation structure. The number, DeltaH(m), and temperature of the PGSG melting peaks tended to decrease with the increasing ratio of doped glycolic acid. In vitro and in vivo degradation tests showed that the degradation rate of PGSG with glycolic acid in the ratio of 0.2 was slowest, but in the ratio range of 0, 0.4, and 0.6, the degradation rate increased with the increase of glycolic acid. All PGSG samples displayed good tissue response and anticoagulant effects. Our data suggest that doping glycolic acid can modulate the microstructure and degree of crosslinking of PGS, thereby control the degradation rate of PGS.

  8. 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.

  9. 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

  10. Mechanisms involved in the aging-induced vascular dysfunction.

    PubMed

    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.

  11. The Possible Mechanisms Involved in Degradation of Patulin by Pichia caribbica

    PubMed Central

    Zheng, Xiangfeng; Yang, Qiya; Zhang, Hongyin; Cao, Jing; Zhang, Xiaoyun; Apaliya, Maurice Tibiru

    2016-01-01

    In this work, we examined the mechanisms involved in the degradation of patulin by Pichia caribbica. Our results indicate that cell-free filtrate of P. caribbica reduced patutlin content. The heat-killed cells could not degrade patulin. However, the live cells significantly reduced the concentration of the patulin. In furtherance to this, it was observed that patulin was not detected in the broken yeast cells and cell wall. The addition of cycloheximide to the P. caribbica cells decreased the capacity of degradation of patulin. Proteomics analyses revealed that patulin treatment resulted in an upregulated protein which was involved in metabolism and stress response processes. Our results suggested that the mechanism of degradation of patulin by P. caribbica was not absorption; the presence of patulin can induce P. caribbica to produce associated intracellular and extracellular enzymes, both of which have the ability to degrade patulin. The result provides a new possible method that used the enzymes produced by yeast to detoxify patulin in food and feed. PMID:27735830

  12. BC-box protein domain-related mechanism for VHL protein degradation

    PubMed Central

    Pozzebon, Maria Elena; Varadaraj, Archana; Mattoscio, Domenico; Jaffray, Ellis G.; Miccolo, Claudia; Galimberti, Viviana; Tommasino, Massimo; Hay, Ronald T.; Chiocca, Susanna

    2013-01-01

    The tumor suppressor VHL (von Hippel–Lindau) protein is a substrate receptor for Ubiquitin Cullin Ring Ligase complexes (CRLs), containing a BC-box domain that associates to the adaptor Elongin B/C. VHL targets hypoxia-inducible factor 1α to proteasome-dependent degradation. Gam1 is an adenoviral protein, which also possesses a BC-box domain that interacts with the host Elongin B/C, thereby acting as a viral substrate receptor. Gam1 associates with both Cullin2 and Cullin5 to form CRL complexes targeting the host protein SUMO enzyme SAE1 for proteasomal degradation. We show that Gam1 protein expression induces VHL protein degradation leading to hypoxia-inducible factor 1α stabilization and induction of its downstream targets. We also characterize the CRL-dependent mechanism that drives VHL protein degradation via proteasome. Interestingly, expression of Suppressor of Cytokine Signaling (SOCS) domain-containing viral proteins and cellular BC-box proteins leads to VHL protein degradation, in a SOCS domain-containing manner. Our work underscores the exquisite ability of viral domains to uncover new regulatory mechanisms by hijacking key cellular proteins. PMID:24145437

  13. Degradation mechanism of cyanobacterial toxin cylindrospermopsin by hydroxyl radicals in homogeneous UV/H₂O₂ process.

    PubMed

    He, Xuexiang; Zhang, Geshan; de la Cruz, Armah A; O'Shea, Kevin E; Dionysiou, Dionysios D

    2014-04-15

    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 spectrometry. Various byproducts identified indicated three common reaction pathways: hydroxyl addition (+16 Da), alcoholic oxidation or dehydrogenation (-2 Da), and elimination of sulfate (-80 Da). The initiation of the degradation was observed at the hydroxymethyl uracil and tricyclic guanidine groups; uracil moiety cleavage/fragmentation and further ring-opening of the alkaloid were also noted at an extended reaction time or higher UV fluence. The degradation rates of CYN decreased and less byproducts (species) were detected using natural water matrices; however, CYN was effectively eliminated under extended UV irradiation. This study demonstrates the efficiency of CYN degradation and provides a better understanding of the mechanism of CYN degradation by hydroxyl radical, a reactive oxygen species that can be generated by most AOPs and is present in natural water environment.

  14. 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

    2016-06-02

    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.

  15. Mechanical properties and microstructure of long term thermal aged WWER 440 RPV steel

    NASA Astrophysics Data System (ADS)

    Kolluri, M.; Kryukov, A.; Magielsen, A. J.; Hähner, P.; Petrosyan, V.; Sevikyan, G.; Szaraz, Z.

    2017-04-01

    The integrity assessment of the Reactor Pressure Vessel (RPV) is essential for the safe and Long Term Operation (LTO) of a Nuclear Power Plant (NPP). Hardening and embrittlement of RPV caused by neutron irradiation and thermal ageing are main reasons for mechanical properties degradation during the operation of an NPP. The thermal ageing-induced degradation of RPV steels becomes more significant with extended operational lives of NPPs. Consequently, the evaluation of thermal ageing effects is important for the structural integrity assessments required for the lifetime extension of NPPs. As a part of NRG's research programme on Structural Materials for safe-LTO of Light Water Reactor (LWR) RPVs, WWER-440 surveillance specimens, which have been thermal aged for 27 years (∼200,000 h) at 290 °C in a surveillance channel of Armenian-NPP, are investigated. Results from the mechanical and microstructural examination of these thermal aged specimens are presented in this article. The results indicate the absence of significant long term thermal ageing effect of 15Cr2MoV-A steel. No age hardening was detected in aged tensile specimens compared with the as-received condition. There is no difference between the impact properties of as-received and thermal aged weld metals. The upper shelf energy of the aged steel remains the same as for the as-received material at a rather high level of about 120 J. The T41 value did not change and was found to be about 10 °C. The microstructure of thermal aged weld, consisting carbides, carbonitrides and manganese-silicon inclusions, did not change significantly compared to as-received state. Grain-boundary segregation of phosphorus in long term aged weld is not significant either which has been confirmed by the absence of intergranular fracture increase in the weld. Negligible hardening and embrittlement observed after such long term thermal ageing is attributed to the optimum chemical composition of 15Cr2MoV-A for high thermal stability.

  16. Degradation of atenolol by UV/peroxymonosulfate: kinetics, effect of operational parameters and mechanism.

    PubMed

    Liu, Xiaowei; Zhang, Tuqiao; Zhou, Yongchao; Fang, Lei; Shao, Yu

    2013-11-01

    Photoactivation of peroxymonosulfate (PMS) with UV (254nm) irradiation was used to generate the SO4(-)-based advanced oxidation process, which was adopted to degrade atenolol (ATL) in water. The second-order reaction rate constants of ATL with HO and SO4(-) were determined, and the effects of operational parameters (dose of PMS, solution pH, HCO3(-), humic acids (HA), and N2 bubbling) were evaluated as well. Finally the main transformation intermediates were identified and possible degradation pathways were proposed. The results showed that there was a linear positive correlation between the degradation rate of ATL and specific dose of PMS (1-16M PMS/M ATL). Increasing solution pH from 3 to 9 promoted elimination of ATL due to the pH-dependent effect of PMS photodecomposition, while further pH increase from 9 to 11 caused slowing down of degradation because of apparent conversion of HO to SO4(-). 1-8mM HCO3(-) exerted no more than 5.3% inhibition effect on ATL destruction, suggesting HCO3(-) was a weak inhibitor. Absorption (or complexation) and photosensitized oxidation induced by HA improved ATL degradation during the first minute of degradation process, whereas photon competition and radical scavenging effects became the leading role afterward. Bubbling with nitrogen enhanced the degradation rate due to the stripping of dissolved oxygen. Hydroxylation of aromatic ring, cleavage of ether bond, oxidation of primary and secondary amine moieties, and dimerization were involved in the degradation mechanism of ATL by UV/PMS.

  17. 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.

  18. Protein synthesis as an integral quality control mechanism during ageing.

    PubMed

    Charmpilas, Nikolaos; Daskalaki, Ioanna; Papandreou, Margarita Elena; Tavernarakis, Nektarios

    2015-09-01

    Ageing is manifested as functional and structural deterioration that affects cell and tissue physiology. mRNA translation is a central cellular process, supplying cells with newly synthesized proteins. Accumulating evidence suggests that alterations in protein synthesis are not merely a corollary but rather a critical factor for the progression of ageing. Here, we survey protein synthesis regulatory mechanisms and focus on the pre-translational regulation of the process exerted by non-coding RNA species, RNA binding proteins and alterations of intrinsic RNA properties. In addition, we discuss the tight relationship between mRNA translation and two central pathways that modulate ageing, namely the insulin/IGF-1 and TOR signalling cascades. A thorough understanding of the complex interplay between protein synthesis regulation and ageing will provide critical insights into the pathogenesis of age-related disorders, associated with impaired proteostasis and protein quality control.

  19. 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.

  20. Molecular Mechanisms of Aging and Immune System Regulation in Drosophila

    PubMed Central

    Eleftherianos, Ioannis; Castillo, Julio Cesar

    2012-01-01

    Aging is a complex process that involves the accumulation of deleterious changes resulting in overall decline in several vital functions, leading to the progressive deterioration in physiological condition of the organism and eventually causing disease and death. The immune system is the most important host-defense mechanism in humans and is also highly conserved in insects. Extensive research in vertebrates has concluded that aging of the immune function results in increased susceptibility to infectious disease and chronic inflammation. Over the years, interest has grown in studying the molecular interaction between aging and the immune response to pathogenic infections. The fruit fly Drosophila melanogaster is an excellent model system for dissecting the genetic and genomic basis of important biological processes, such as aging and the innate immune system, and deciphering parallel mechanisms in vertebrate animals. Here, we review the recent advances in the identification of key players modulating the relationship between molecular aging networks and immune signal transduction pathways in the fly. Understanding the details of the molecular events involved in aging and immune system regulation will potentially lead to the development of strategies for decreasing the impact of age-related diseases, thus improving human health and life span. PMID:22949833

  1. Degradation mechanism beyond device self-heating in high power light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Yung, K. C.; Liem, H.; Choy, H. S.; Lun, W. K.

    2011-05-01

    A unique degradation property of high power InGaN/GaN multiple quantum well (MQW) white light-emitting diodes (LEDs) was identified. The LEDs were stressed under different forward-currents. The various ageing characteristics were analyzed for both the electrical response and electro-luminescence (EL) spectra. The Raman spectroscopy allowed noninvasive probing of LED junction temperature profiles which correlated well with the EL characteristics, showing a junction temperature drop during degradation at certain current levels. In addition to the common observations: (1) a broadening of the light intensity-current (L-I) characteristic in the nonlinear regime, and (2) a shift of the current-voltage (I-V) dependence to higher current levels, the EL spectra showed different temperature responses of the two blue emission peaks, 440 and 463 nm. The former was temperature sensitive and thus related to shallow defect levels, while the latter was thermally stable and deeper defect states were involved in the degradation process. This unique selection rule resulted in the enhancement of the blue emission peak at 463 nm after degrading the LEDs. This study suggests that LED device heating is not directly linked to the degradation process.

  2. 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.

  3. Deciphering the multi-step degradation mechanisms of carbonate-based electrolyte in Li batteries

    NASA Astrophysics Data System (ADS)

    Gachot, Gregory; Grugeon, Sylvie; Armand, Michel; Pilard, Serge; Guenot, Pierre; Tarascon, Jean-Marie; Laruelle, Stephane

    Electrolytes are crucial to the safety and long life of Li-ion batteries, however, the understanding of their degradation mechanisms is still sketchy. Here we report on the nature and formation of organic/inorganic degradation products generated at low potential in a lithium-based cell using cyclic and linear carbonate-based electrolyte mixtures. The global formation mechanism of ethylene oxide oligomers produced from EC/DMC (1/1 w/w)-LiPF 6 salt (1 M) electrolyte decomposition is proposed then mimicked via chemical tests. Each intermediary product structure/formula/composition is identified by means of combined NMR, FTIR and high resolution mass spectrometry (ESI-HRMS) analysis. The key role played by lithium methoxide as initiator of the electrolyte degradation is evidenced, but more importantly we isolated for the first time lithium methyl carbonate as a side product of the ethylene oxide oligomers chemical formation. The same degradation mechanism was found to hold on for another cyclic and linear carbonate-based electrolyte such as EC/DEC (1/1 w/w)-LiPF 6 salt (1 M). Such findings have important implications in the choice of chemical additives for developing highly performing electrolytes.

  4. Mechanical study of PLA-PCL fibers during in vitro degradation.

    PubMed

    Vieira, A C; Vieira, J C; Ferra, J M; Magalhães, F D; Guedes, R M; Marques, A T

    2011-04-01

    The aliphatic polyesters are widely used in biomedical applications since they are susceptible to hydrolytic and/or enzymatic chain cleavage, leading to α-hydroxyacids, generally metabolized in the human body. This is particularly useful for many biomedical applications, especially, for temporary mechanical supports in regenerative medical devices. Ideally, the degradation should be compatible with the tissue recovering. In this work, the evolution of mechanical properties during degradation is discussed based on experimental data. The decrease of tensile strength of PLA-PCL fibers follows the same trend as the decrease of molecular weight, and so it can also be modeled using a first order equation. For each degradation stage, hyperelastic models such as Neo-Hookean, Mooney-Rivlin and second reduced order, allow a reasonable approximation of the material behavior. Based on this knowledge, constitutive models that describe the mechanical behavior during degradation are proposed and experimentally validated. The proposed theoretical models and methods may be adapted and used in other biodegradable materials, and can be considered fundamental tools in the design of regenerative medical devices where strain energy is an important requirement, such as, for example, ligaments, cartilage and stents.

  5. Localised micro-mechanical stiffening in the ageing aorta

    PubMed Central

    Graham, Helen K.; Akhtar, Riaz; Kridiotis, Constantinos; Derby, Brian; Kundu, Tribikram; Trafford, Andrew W.; Sherratt, Michael J.

    2011-01-01

    Age-related loss of tissue elasticity is a common cause of human morbidity and arteriosclerosis (vascular stiffening) is associated with the development of both fatal strokes and heart failure. However, in the absence of appropriate micro-mechanical testing methodologies, multiple structural remodelling events have been proposed as the cause of arteriosclerosis. Therefore, using a model of ageing in female sheep aorta (young: <18 months, old: >8 years) we: (i) quantified age-related macro-mechanical stiffness, (ii) localised in situ micro-metre scale changes in acoustic wave speed (a measure of tissue stiffness) and (iii) characterised collagen and elastic fibre remodelling. With age, there was an increase in both macro-mechanical stiffness and mean microscopic wave speed (and hence stiffness; young wave speed: 1701 ± 1 m s−1, old wave speed: 1710 ± 1 m s−1, p < 0.001) which was localized to collagen fibril-rich regions located between large elastic lamellae. These micro-mechanical changes were associated with increases in both collagen and elastic fibre content (collagen tissue area, young: 31 ± 2%, old: 40 ± 4%, p < 0.05; elastic fibre tissue area, young: 55 ± 3%, old: 69 ± 4%, p < 0.001). Localised collagen fibrosis may therefore play a key role in mediating age-related arteriosclerosis. Furthermore, high frequency scanning acoustic microscopy is capable of co-localising micro-mechanical and micro-structural changes in ageing tissues. PMID:21777602

  6. 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

  7. 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

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

    DOE PAGES

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; ...

    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

  9. 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.

  10. 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.

  11. Aging Degradation of Austenitic Stainless Steel Weld Probed by Electrochemical Method and Impact Toughness Evaluation

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Das, Goutam; Mahato, B.; Singh, P. K.

    2017-01-01

    The present study discriminates the spinodal decomposition and G-phase precipitation in stainless steel welds by double loop electrochemical potentio-kinetic reactivation method and correlates it with the degradation in toughness property. The welds produced with different heat inputs were aged up to 10,000 hours at 673 K to 723 K (400 to 450 °C) and evaluated subsequently for the degree of sensitization (DOS) and impact toughness. The DOS values obtained were attributed to the spinodal decomposition and precipitation of G-phase. Study shows that the DOS correlates well with the impact toughness of the 304LN weld. Prolonged aging at 673 K and 723 K (400 °C and 450 °C) increased the DOS values while the impact toughness was decreased. The weld fabricated at 1 kJ/mm of heat input, produced higher DOS, compared to that at 3 kJ/mm. The geometrical location along the weld is shown to influence the DOS; higher values were obtained at the root than at the topside of the weld. Vermicular and columnar microstructure, in addition to the spinodal decomposition and G-phase precipitation, observed in the root side of the weld appear risky for the impact toughness.

  12. Aging Degradation of Austenitic Stainless Steel Weld Probed by Electrochemical Method and Impact Toughness Evaluation

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Das, Goutam; Mahato, B.; Singh, P. K.

    2017-03-01

    The present study discriminates the spinodal decomposition and G-phase precipitation in stainless steel welds by double loop electrochemical potentio-kinetic reactivation method and correlates it with the degradation in toughness property. The welds produced with different heat inputs were aged up to 10,000 hours at 673 K to 723 K (400 to 450 °C) and evaluated subsequently for the degree of sensitization (DOS) and impact toughness. The DOS values obtained were attributed to the spinodal decomposition and precipitation of G-phase. Study shows that the DOS correlates well with the impact toughness of the 304LN weld. Prolonged aging at 673 K and 723 K (400 °C and 450 °C) increased the DOS values while the impact toughness was decreased. The weld fabricated at 1 kJ/mm of heat input, produced higher DOS, compared to that at 3 kJ/mm. The geometrical location along the weld is shown to influence the DOS; higher values were obtained at the root than at the topside of the weld. Vermicular and columnar microstructure, in addition to the spinodal decomposition and G-phase precipitation, observed in the root side of the weld appear risky for the impact toughness.

  13. 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.

  14. 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.

  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. 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.

  17. 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

  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. Gas chromatography/mass spectrometry as a suitable tool for the Li-ion battery electrolyte degradation mechanisms study.

    PubMed

    Gachot, Grégory; Ribière, Perrine; Mathiron, David; Grugeon, Sylvie; Armand, Michel; Leriche, Jean-Bernard; Pilard, Serge; Laruelle, Stéphane

    2011-01-15

    To allow electric vehicles to be powered by Li-ion batteries, scientists must understand further their aging processes in view to extend their cycle life and safety. For this purpose, we focused on the development of analytical techniques aiming at identifying organic species resulting from the degradation of carbonate-based electrolytes (EC-DMC/LiPF(6)) at low potential. As ESI-HRMS provided insightful information to the mechanism and chronological formation of ethylene oxide oligomers, we implemented "gas" GC/MS experiments to explore the lower mass range corresponding to highly volatile compounds. With the help of chemical simulation tests, we were able to discriminate their formation pathways (thermal and/or electrochemical) and found that most of the degradation compounds originate from the electrochemically driven linear alkyl carbonate reduction upon cycling and to a lesser extent from a two-step EC reduction. Deduced from these results, we propose an overall electrolyte degradation scheme spanning the entire mass range and the chemical or electrochemical type of processes.

  20. 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

    2016-02-23

    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.

  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. Application of isotopic labeling, and gas chromatography mass spectrometry, to understanding degradation products and pathways in the thermal-oxidative aging of Nylon 6.6

    SciTech Connect

    White, Gregory Von; Clough, Roger L.; Hochrein, James M.; Bernstein, Robert

    2013-12-01

    Nylon 6.6 containing 13C isotopic labels at specific positions along the macromolecular backbone has been subjected to extensive thermal-oxidative aging at 138 °C for time periods up to 243 days. In complementary experiments, unlabeled Nylon 6.6 was subjected to the same aging conditions under an atmosphere of 18O2. Volatile organic degradation products were analyzed by cryofocusing gas chromatography mass spectrometry (cryo-GC/MS) to identify the isotopic labeling. The labeling results, combined with basic considerations of free radical reaction chemistry, provided insights to the origin of degradation species, with respect to the macromolecular structure. A number of inferences on chemical mechanisms were drawn, based on 1) the presence (or absence) of the isotopic labels in the various products, 2) the location of the isotope within the product molecule, and 3) the relative abundance of products as indicated by large differences in peak intensities in the gas chromatogram. The overall degradation results can be understood in terms of free radical pathways originating from initial attacks on three different positions along the nylon chain which include hydrogen abstraction from: the (CH2) group adjacent to the nitrogen atom, at the (CH2) adjacent the carbonyl group, and direct radical attack on the carbonyl. Understanding the pathways which lead to Nylon 6.6 degradation ultimately provides new insight into changes that can be leveraged to detect and reduce early aging and minimize problems associated with material degradation.

  4. 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.

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

    PubMed

    Colquhoun, R; Tanner, K E

    2015-12-23

    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.

  6. Genipin crosslinking of cartilage enhances resistance to biochemical degradation and mechanical wear.

    PubMed

    McGann, Megan E; Bonitsky, Craig M; Jackson, Mariah L; Ovaert, Timothy C; Trippel, Stephen B; Wagner, Diane R

    2015-11-01

    Collagen crosslinking enhances many beneficial properties of articular cartilage, including resistance to chemical degradation and mechanical wear, but many crosslinking agents are cytotoxic. The purpose of this study was to evaluate the effectiveness of genipin, a crosslinking agent with favorable biocompatibility and cytotoxicity, as a potential treatment to prevent the degradation and wear of articular cartilage. First, the impact of genipin concentration and treatment duration on the viscoelastic properties of bovine articular cartilage was quantified. Next, two short-term (15 min) genipin crosslinking treatments were chosen, and the change in collagenase digestion, cartilage wear, and the friction coefficient of the tissue with these treatments was measured. Finally, chondrocyte viability after exposure to these genipin treatments was assessed. Genipin treatment increased the stiffness of healthy, intact cartilage in a dose-dependent manner. The 15-min crosslinking treatments improved cartilage's resistance to both chemical degradation, particularly at the articular surface, and to damage due to mechanical wear. These enhancements were achieved without sacrificing the low coefficient of friction of the tissue and at a genipin dose that preserved chondrocyte viability. The results of this study suggest that collagen crosslinking via genipin may be a promising preventative treatment to slow the degradation of cartilage.

  7. A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies

    NASA Astrophysics Data System (ADS)

    Wu, Jinfeng; Yuan, Xiao Zi; Martin, Jonathan J.; Wang, Haijiang; Zhang, Jiujun; Shen, Jun; Wu, Shaohong; Merida, Walter

    This paper reviews publications in the literature on performance degradation of and mitigation strategies for polymer electrolyte membrane (PEM) fuel cells. Durability is one of the characteristics most necessary for PEM fuel cells to be accepted as a viable product. In this paper, a literature-based analysis has been carried out in an attempt to achieve a unified definition of PEM fuel cell lifetime for cells operated either at a steady state or at various accelerated conditions. Additionally, the dependence of PEM fuel cell durability on different operating conditions is analyzed. Durability studies of the individual components of a PEM fuel cell are introduced, and various degradation mechanisms are examined. Following this analysis, the emphasis of this review shifts to applicable strategies for alleviating the degradation rate of each component. The lifetime of a PEM fuel cell as a function of operating conditions, component materials, and degradation mechanisms is then established. Lastly, this paper summarizes accelerated stress testing methods and protocols for various components, in an attempt to prevent the prolonged test periods and high costs associated with real lifetime tests.

  8. GENIPIN CROSSLINKING OF CARTILAGE ENHANCES RESISTANCE TO BIOCHEMICAL DEGRADATION AND MECHANICAL WEAR

    PubMed Central

    Jackson, Mariah L.; Ovaert, Timothy C.; Trippel, Stephen B.; Wagner, Diane R.

    2015-01-01

    Collagen crosslinking enhances many beneficial properties of articular cartilage, including resistance to chemical degradation and mechanical wear, but many crosslinking agents are cytotoxic. The purpose of this study was to evaluate the effectiveness of genipin, a crosslinking agent with favorable biocompatibility and cytotoxicity, as a potential treatment to prevent the degradation and wear of articular cartilage. First, the impact of genipin concentration and treatment duration on the viscoelastic properties of bovine articular cartilage was quantified. Next, two short-term (15 minute) genipin crosslinking treatments were chosen, and the change in collagenase digestion, cartilage wear, and the friction coefficient of the tissue with these treatments was measured. Finally, chondrocyte viability after exposure to these genipin treatments was assessed. Genipin treatment increased the stiffness of healthy, intact cartilage in a dose-dependent manner. The 15-minute crosslinking treatments improved cartilage's resistance to both chemical degradation, particularly at the articular surface, and to damage due to mechanical wear. These enhancements were achieved without sacrificing the low coefficient of friction of the tissue and at a genipin dose that preserved chondrocyte viability. The results of this study suggest that collagen crosslinking via genipin may be a promising preventative treatment to slow the degradation of cartilage. PMID:25939430

  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. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

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

    PubMed

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

    2015-08-15

    A binary catalytic system, siderite-catalyzed hydrogen peroxide (H2O2) coupled with persulfate (S2O8(2-)), 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-S2O8(2-) system. In the absence of S2O8(2-) (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 S2O8(2-) 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 S2O8(2-), 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-S2O8(2-) 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.

  17. Nuclear autophagy: An evolutionarily conserved mechanism of nuclear degradation in the cytoplasm.

    PubMed

    Luo, Majing; Zhao, Xueya; Song, Ying; Cheng, Hanhua; Zhou, Rongjia

    2016-11-01

    Macroautophagy/autophagy is a catabolic process that is essential for cellular homeostasis. Studies on autophagic degradation of cytoplasmic components have generated interest in nuclear autophagy. Although its mechanisms and roles have remained elusive, tremendous progress has been made toward understanding nuclear autophagy. Nuclear autophagy is evolutionarily conserved in eukaryotes that may target various nuclear components through a series of processes, including nuclear sensing, nuclear export, autophagic substrate encapsulation and autophagic degradation in the cytoplasm. However, the molecular processes and regulatory mechanisms involved in nuclear autophagy remain largely unknown. Numerous studies have highlighted the importance of nuclear autophagy in physiological and pathological processes such as cancer. This review focuses on current advances in nuclear autophagy and provides a summary of its research history and landmark discoveries to offer new perspectives.

  18. A study on degradation mechanisms and low voltage operations in MNOS-type memory devices

    NASA Astrophysics Data System (ADS)

    Suzuki, E.

    1984-05-01

    Metal-nitride-oxide semiconductor (MNOS) type nonvolatile semiconductor memory devices that use electronic traps in the gate insulator as memory sites are studied. A method for measuring the separation of electrons and holes by utilizing the structure of insulated-gate field effect transistors is examined, and mechanisms of carrier conduction in MNOS structures are clarified. Degradation mechanisms of MNOS structure are investigated to improve the devices and to develop new memory devices. It is shown that positive holes, especially those injected from the gate into the nitride, play an important role in degrading the devices. A new electrically erasable programmable read-only memory with metal oxide nitride oxide semiconductor structures is proposed, and its superior memory properties are demonstrated.

  19. 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.

  20. Effects of mechanical treatment of digestate after anaerobic digestion on the degree of degradation.

    PubMed

    Lindner, Jonas; Zielonka, Simon; Oechsner, Hans; Lemmer, Andreas

    2015-02-01

    The aim of this study was to increase the biogas production from different substrates by applying a mechanical treatment only to the non-degraded digestate after the fermentation process in order to feed it back into the process. To evaluate this approach, digestates were grounded with a ball mill for four different treatment time periods (0, 2, 5, 10 min) and then the effects on the particle size, volatile organic substances, methane yield and degradation kinetic were measured. A decrease of volatile fatty acids based on this treatment was not detected. The mechanical treatment caused in maximum to a triplication of the methane yield and to a quadruplicating of the daily methane production.

  1. 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.

  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.

  3. Photo-cross-linked poly(ethylene carbonate) elastomers: synthesis, in vivo degradation, and determination of in vivo degradation mechanism.

    PubMed

    Cornacchione, L A; Qi, B; Bianco, J; Zhou, Z; Amsden, B G

    2012-10-08

    Low-molecular-weight poly(ethylene carbonate) diols of varying molecular weight were generated through catalyzed thermal degradation of high-molecular-weight poly(ethylene carbonate). These polymers were then end functionalized with acrylate groups. The resulting α,ω-diacrylates were effectively photo-cross-linked upon exposure to long-wave UV light in the presence of a photoinitiator to yield rubbery networks of low sol content. The degree of cross-linking effectively controlled the in vivo degradation rate of the networks by adherent macrophages; higher cross-link densities yielded slower degradation rates. The cross-link density did not affect the number of adherent macrophages at the elastomer/tissue interface, indicating that cross-linking affected the susceptibility of the elastomer to degradative species released by the macrophages. The reactive species likely responsible for in vivo degradation appears to be superoxide anion, as the in vivo results were in agreement with in vitro degradation via superoxide anion, while cholesterol esterase, known to degrade similar poly(alkylene carbonate)s, had no affect on elastomer degradation.

  4. 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.

  5. Reduced sampling efficiency causes degraded Vernier hyperacuity with normal aging: Vernier acuity in position noise.

    PubMed

    Li, Roger W; Brown, Brian; Edwards, Marion H; Ngo, Charlie V; Chat, Sandy W; Levi, Dennis M

    2012-01-01

    Vernier acuity, a form of visual hyperacuity, is amongst the most precise forms of spatial vision. Under optimal conditions Vernier thresholds are much finer than the inter-photoreceptor distance. Achievement of such high precision is based substantially on cortical computations, most likely in the primary visual cortex. Using stimuli with added positional noise, we show that Vernier processing is reduced with advancing age across a wide range of noise levels. Using an ideal observer model, we are able to characterize the mechanisms underlying age-related loss, and show that the reduction in Vernier acuity can be mainly attributed to the reduction in efficiency of sampling, with no significant change in the level of internal position noise, or spatial distortion, in the visual system.

  6. Mild MPP(+) exposure impairs autophagic degradation through a novel lysosomal acidity-independent mechanism.

    PubMed

    Miyara, Masatsugu; Kotake, Yaichiro; Tokunaga, Wataru; Sanoh, Seigo; Ohta, Shigeru

    2016-10-01

    Parkinson's disease (PD) is the second most common neurodegenerative disorder, but its underlying cause remains unknown. Although recent studies using PD-related neurotoxin MPP(+) suggest autophagy involvement in the pathogenesis of PD, the effect of MPP(+) on autophagic processes under mild exposure, which mimics the slow progressive nature of PD, remains largely unclear. We examined the effect of mild MPP(+) exposure (10 and 200 μM for 48 h), which induces a more slowly developing cell death, on autophagic processes and the mechanistic differences with acute MPP(+) toxicity (2.5 and 5 mM for 24 h). In SH-SY5Y cells, mild MPP(+) exposure predominantly inhibited autophagosome degradation, whereas acute MPP(+) exposure inhibited both autophagosome degradation and basal autophagy. Mild MPP(+) exposure reduced lysosomal hydrolase cathepsin D activity without changing lysosomal acidity, whereas acute exposure decreased lysosomal density. Lysosome biogenesis enhancers trehalose and rapamycin partially alleviated mild MPP(+) exposure induced impaired autophagosome degradation and cell death, but did not prevent the pathogenic response to acute MPP(+) exposure, suggesting irreversible lysosomal damage. We demonstrated impaired autophagic degradation by MPP(+) exposure and mechanistic differences between mild and acute MPP(+) toxicities. Mild MPP(+) toxicity impaired autophagosome degradation through novel lysosomal acidity-independent mechanisms. Sustained mild lysosomal damage may contribute to PD. We examined the effects of MPP(+) on autophagic processes under mild exposure, which mimics the slow progressive nature of Parkinson's disease, in SH-SY5Y cells. This study demonstrated impaired autophagic degradation through a reduction in lysosomal cathepsin D activity without altering lysosomal acidity by mild MPP(+) exposure. Mechanistic differences between acute and mild MPP(+) toxicity were also observed. Sustained mild damage of lysosome may be an underlying cause

  7. 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.

  8. Poly(amido-amine)-based hydrogels with tailored mechanical properties and degradation rates for tissue engineering.

    PubMed

    Martello, Federico; Tocchio, Alessandro; Tamplenizza, Margherita; Gerges, Irini; Pistis, Valentina; Recenti, Rossella; Bortolin, Monica; Del Fabbro, Massimo; Argentiere, Simona; Milani, Paolo; Lenardi, Cristina

    2014-03-01

    Poly(amido-amine) (PAA) hydrogels containing the 2,2-bisacrylamidoacetic acid-4-amminobutyl guanidine monomeric unit have a known ability to enhance cellular adhesion by interacting with the arginin-glycin-aspartic acid (RGD)-binding αVβ3 integrin, expressed by a wide number of cell types. Scientific interest in this class of materials has traditionally been hampered by their poor mechanical properties and restricted range of degradation rate. Here we present the design of novel biocompatible, RGD-mimic PAA-based hydrogels with wide and tunable degradation rates as well as improved mechanical and biological properties for biomedical applications. This is achieved by radical polymerization of acrylamide-terminated PAA oligomers in both the presence and absence of 2-hydroxyethylmethacrylate. The degradation rate is found to be precisely tunable by adjusting the PAA oligomer molecular weight and acrylic co-monomer concentration in the starting reaction mixture. Cell adhesion and proliferation tests on Madin-Darby canine kidney epithelial cells show that PAA-based hydrogels have the capacity to promote cell adhesion up to 200% compared to the control. Mechanical tests show higher compressive strength of acrylic chain containing hydrogels compared to traditional PAA hydrogels.

  9. 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.

  10. Skin aging and oxidative stress: Equol's anti-aging effects via biochemical and molecular mechanisms.

    PubMed

    Lephart, Edwin D

    2016-11-01

    Oxygen in biology is essential for life. It comes at a cost during normal cellular function, where reactive oxygen species (ROS) are generated by oxidative metabolism. Human skin exposed to solar ultra-violet radiation (UVR) dramatically increases ROS production/oxidative stress. It is important to understand the characteristics of human skin and how chronological (intrinsic) aging and photo-aging (extrinsic aging) occur via the impact of ROS production by cascade signaling pathways. The goal is to oppose or neutralize ROS insults to maintain good dermal health. Botanicals, as active ingredients, represent one of the largest categories used in dermatology and cosmeceuticals to combat skin aging. An emerging botanical is equol, a polyphenolic/isoflavonoid molecule found in plants and food products and via gastrointestinal metabolism from precursor compounds. Introductory sections cover oxygen, free radicals (ROS), oxidative stress, antioxidants, human skin aging, cellular/molecular ROS events in skin, steroid enzymes/receptors/hormonal actions and genetic factors in aging skin. The main focus of this review covers the characteristics of equol (phytoestrogenic, antioxidant and enhancement of extracellular matrix properties) to reduce skin aging along with its anti-aging skin influences via reducing oxidative stress cascade events by a variety of biochemical/molecular actions and mechanisms to enhance human dermal health.

  11. 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.

  12. 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.

  13. 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.

  14. Aging of the Immune System. Mechanisms and Therapeutic Targets.

    PubMed

    Weyand, Cornelia M; Goronzy, Jörg J

    2016-12-01

    Beginning with the sixth decade of life, the human immune system undergoes dramatic aging-related changes, which continuously progress to a state of immunosenescence. The aging immune system loses the ability to protect against infections and cancer and fails to support appropriate wound healing. Vaccine responses are typically impaired in older individuals. Conversely, inflammatory responses mediated by the innate immune system gain in intensity and duration, rendering older individuals susceptible to tissue-damaging immunity and inflammatory disease. Immune system aging functions as an accelerator for other age-related pathologies. It occurs prematurely in some clinical conditions, most prominently in patients with the autoimmune syndrome rheumatoid arthritis (RA); and such patients serve as an informative model system to study molecular mechanisms of immune aging. T cells from patients with RA are prone to differentiate into proinflammatory effector cells, sustaining chronic-persistent inflammatory lesions in the joints and many other organ systems. RA T cells have several hallmarks of cellular aging; most importantly, they accumulate damaged DNA. Because of deficiency of the DNA repair kinase ataxia telangiectasia mutated, RA T cells carry a higher burden of DNA double-strand breaks, triggering cell-indigenous stress signals that shift the cell's survival potential and differentiation pattern. Immune aging in RA T cells is also associated with metabolic reprogramming; specifically, with reduced glycolytic flux and diminished ATP production. Chronic energy stress affects the longevity and the functional differentiation of older T cells. Altered metabolic patterns provide opportunities to therapeutically target the immune aging process through metabolic interference.

  15. The Formation of Calcified Nanospherites during Micropetrosis Represents a Unique Mineralization Mechanism in Aged Human Bone.

    PubMed

    Milovanovic, Petar; Zimmermann, Elizabeth A; Vom Scheidt, Annika; Hoffmann, Björn; Sarau, George; Yorgan, Timur; Schweizer, Michaela; Amling, Michael; Christiansen, Silke; Busse, Björn

    2017-01-01

    Osteocytes-the central regulators of bone remodeling-are enclosed in a network of microcavities (lacunae) and nanocanals (canaliculi) pervading the mineralized bone. In a hitherto obscure process related to aging and disease, local plugs in the lacuno-canalicular network disrupt cellular communication and impede bone homeostasis. By utilizing a suite of high-resolution imaging and physics-based techniques, it is shown here that the local plugs develop by accumulation and fusion of calcified nanospherites in lacunae and canaliculi (micropetrosis). Two distinctive nanospherites phenotypes are found to originate from different osteocytic elements. A substantial deviation in the spherites' composition in comparison to mineralized bone further suggests a mineralization process unlike regular bone mineralization. Clearly, mineralization of osteocyte lacunae qualifies as a strong marker for degrading bone material quality in skeletal aging. The understanding of micropetrosis may guide future therapeutics toward preserving osteocyte viability to maintain mechanical competence and fracture resistance of bone in elderly individuals.

  16. An intrinsic mechanism of secreted protein aging and turnover.

    PubMed

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

    2015-11-03

    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.

  17. 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

  18. 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.

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

    DOE PAGES

    Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; ...

    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

  20. 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.

  1. 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.

  2. 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

  3. Research on the degradation mechanism of pyridine in drinking water by dielectric barrier discharge.

    PubMed

    Li, Yang; Yi, Rongjie; Yi, Chengwu; Zhou, Biyun; Wang, Huijuan

    2017-03-01

    Pyridine, an important chemical raw material, is widely used in industry, for example in textiles, leather, printing, dyeing, etc. In this research, a dielectric barrier discharge (DBD) system was developed to remove pyridine, as a representative type of nitrogen heterocyclic compound in drinking water. First, the influence of the active species inhibitors tertiary butanol alcohol (TBA), HCO3(-), and CO3(2-) on the degradation rate of pyridine was investigated to verify the existence of active species produced by the strong ionization discharge in the system. The intermediate and final products generated in the degradation process of pyridine were confirmed and analyzed through a series of analytical techniques, including liquid chromatography-mass spectrometry (LC-MS), high performance liquid chromatography (HPLC), ion chromatography (IC), total organic carbon (TOC) analysis, ultraviolet (UV) spectroscopy, etc. The results showed that the degradation of pyridine was mainly due to the strong oxidizing power of ozone and hydroxyl radical produced by the DBD system. Several intermediate products including 3-hydroxyl pyridine, fumaric acid, 2, 3-dihydroxypyridine, and oxalic acid were detected. Nitrogen was removed from the pyridine molecule to form nitrate. Through analysis of the degradation mechanism of pyridine, the oxidation pathway was deduced. The study provided a theoretical and experimental basis for the application of DBD strong ionization discharge in treatment of nitrogen heterocyclic compounds in drinking water.

  4. Polymeric endoaortic paving: Mechanical, thermoforming, and degradation properties of polycaprolactone/polyurethane blends for cardiovascular applications.

    PubMed

    Ashton, J H; Mertz, J A M; Harper, J L; Slepian, M J; Mills, J L; McGrath, D V; Vande Geest, J P

    2011-01-01

    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 m⁻². 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.

  5. Mechanism and kinetic properties for OH-initiated atmospheric degradation of the organophosphorus pesticide diazinon

    NASA Astrophysics Data System (ADS)

    Zhou, Qin; Sun, Xiaoyan; Gao, Rui; Hu, Jingtian

    2011-06-01

    Diazinon is a member of the organophosphorus class of insecticides. It has been regarded as an important atmospheric pollutant because of its high detection-frequency in the air and potential adverse effects on humans and wildlife. In this paper, the reaction mechanism and possible degradation products for the OH-initiated atmospheric degradation of diazinon were investigated and the rate constants of crucial elementary steps over the temperature range of 180-370 K were predicted. Present results show that OH addition to C4 atom in the pyrimidyl ring, H abstraction from the -CH- moiety as well as OH addition to P atom are the dominant pathways for the reaction of diazinon with OH radicals. The dominant degradation products are diazoxon, SO 2, P3, CH 3CHO, P4, CH 3CO, P14 as well as CH 3CHCH 3. This work provides a comprehensive investigation of the OH-initiated atmospheric degradation of diazinon and should help to clarify its potential risk to non-targets.

  6. Aging and Immune Function: Molecular Mechanisms to Interventions

    PubMed Central

    Ponnappan, Subramaniam

    2011-01-01

    Abstract The immune system of an organism is an essential component of the defense mechanism aimed at combating pathogenic stress. Age-associated immune dysfunction, also dubbed “immune senescence,” manifests as increased susceptibility to infections, increased onset and progression of autoimmune diseases, and onset of neoplasia. Over the years, extensive research has generated consensus in terms of the phenotypic and functional defects within the immune system in various organisms, including humans. Indeed, age-associated alterations such as thymic involution, T cell repertoire skewing, decreased ability to activate naïve T cells and to generate robust memory responses, have been shown to have a causative role in immune decline. Further, understanding the molecular mechanisms underlying the generation of proteotoxic stress, DNA damage response, modulation of ubiquitin proteasome pathway, and regulation of transcription factor NFκB activation, in immune decline, have paved the way to delineating signaling pathways that cross-talk and impact immune senescence. Given the role of the immune system in combating infections, its effectiveness with age may well be a marker of health and a predictor of longevity. It is therefore believed that a better understanding of the mechanisms underlying immune senescence will lead to an effective interventional strategy aimed at improving the health span of individuals. Antioxid. Redox Signal. 14, 1551–1585. PMID:20812785

  7. Advanced oxidation kinetics and mechanism of preservative propylparaben degradation in aqueous suspension of TiO2 and risk assessment of its degradation products.

    PubMed

    Fang, Hansun; Gao, Yanpeng; Li, Guiying; An, Jibin; Wong, Po-Keung; Fu, Haiying; Yao, Side; Nie, Xiangping; An, Taicheng

    2013-03-19

    The absolute kinetic rate constants of propylparaben (PPB) in water with different free radicals were investigated, and it was found that both hydroxyl radicals (HO(•)) and hydrated electrons could rapidly react with PPB. The advanced oxidation kinetics and mechanisms of PPB were investigated using photocatalytic process as a model technology, and the degradation was found to be a pseudo-first-order model. Oxidative species, particularly HO(•), were the most important reactive oxygen species mediating photocatalytic degradation of PPB, and PPB degradation was found to be significantly affected by pH because it was controlled by the radical reaction mechanism and was postulated to occur primarily via HO(•)-addition or H-abstraction reactions on the basis of pulse radiolysis measurements and observed reaction products. To investigate potential risk of PPB to humans and aqueous organisms, the estrogenic assays and bioassays were performed using 100 μM PPB solution degraded by photocatalysis at specific intervals. The estrogenic activity decreased as PPB was degraded, while the acute toxicity at three trophic levels first increased slowly and then decreased rapidly as the total organic carbon decreased during photocatalytic degradation.

  8. 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

  9. Controlling dynamic mechanical properties and degradation of composites for bone regeneration by means of filler content.

    PubMed

    Barbieri, Davide; de Bruijn, Joost D; Luo, Xiaoman; Farè, Silvia; Grijpma, Dirk W; Yuan, Huipin

    2013-04-01

    Bone tissue is a dynamic composite system that adapts itself, in response to the surrounding daily (cyclic) mechanical stimuli, through an equilibrium between growth and resorption processes. When there is need of synthetic bone grafts, the biggest issue is to support bone regeneration without causing mechanically-induced bone resorption. Apart from biological properties, such degradable materials should initially support and later leave room to bone formation. Further, dynamic mechanical properties comparable to those of bone are required. In this study we prepared composites comprising calcium phosphate and L-lactide/D-lactide copolymer in various content ratios using the extrusion method. We evaluated the effect of the inorganic filler amount on the polymer phase (i.e. on the post-extrusion intrinsic viscosity). We then studied their in vitro degradation and dynamic mechanical properties (in dry and humid conditions). By increasing the filler content, we observed significant decrease of the intrinsic viscosity of the polymer phase during the extrusion process. Composites containing higher amounts of apatite had faster degradation, and were also mechanically stiffer. But, due to the lower intrinsic viscosity of their polymer phase, they had larger damping properties. Besides this, higher amounts of apatite also rendered the composites more hydrophilic letting them absorb more water and causing them the largest decrease in stiffness. These results show the importance of filler content in controlling the properties of such composites. Further, in this study we observed that the viscoelastic properties of the composite containing 50wt% apatite were comparable to those of dry human cortical bone.

  10. 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.

  11. 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

  12. 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.

  13. Identification of the primary mechanism for fungal lignin degradation. Progress report

    SciTech Connect

    1997-06-01

    Many lignin-degrading fungi appear to lack lignin peroxidase (LiP), an enzyme generally thought important for fungal ligninolysis. The authors are working with one of these fungi, Ceriporiopsis subvermispora, an aggressive white-rotter that selectively removes lignin from wood. During this project period, they have obtained the following principal results: new polymeric lignin model compounds were developed to assist in the elucidation of fungal ligninolytic mechanisms; experiments with one of the polymeric lignin models showed that C. subvermispora cultures which express no detectable LiP activity are nevertheless able to degrade nonphenolic lignin structures, this result is significant because LiPs were previously considered essential for fungal attack on these recalcitrant structures, which constitute about 90% of lignin; manganese peroxidases (MnPs), which C. subvermispora does produce, catalyze the peroxidation of unsaturated fatty acids to give fatty acid hydroperoxides, fatty acid hydroperoxides are also used by MnP as oxidants (in place of H{sub 2}O{sub 2}) that support the MnP catalytic cycle, these results indicate that MnP turnover in the presence of unsaturated lipids generates reactive lipid oxyradicals that could act as oxidant of other molecules; MnP-mediated lipid peroxidation results in the co-oxidative cleavage of nonphenolic lignin structures, the MnP/lipid peroxidation system may therefore provide C. subvermispora and other LiP-negative fungi with a mechanism to degrade the principal structures of lignin.

  14. 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.

  15. Degradation behaviors of geometric cues and mechanical properties in a 3D scaffold for tendon repair.

    PubMed

    Wu, Yang; Wong, Yoke San; Fuh, Jerry Ying Hsi

    2017-04-01

    A three-dimensional (3D) scaffold fabricated via electrohydrodynamic jet printing (E-jetting) and thermally uniaxial stretching, has been developed for tendon tissue regeneration in our previous study. In this study, more in-depth biological test showed that the aligned cell morphology guided by the anisotropic geometries of the 3D tendon scaffolds, leading to up-regulated tendious gene expression including collagen type I, decorin, tenascin-C, and biglycan, as compared to the electrospun scaffolds. Given the importance of geometric cues to the biological function of the scaffolds, the degradation behaviors of the 3D scaffolds were investigated. Results from accelerated hydrolysis showed that the E-jetted portion followed bulk-controlled erosion, while the unaixially stretched portion followed surface-controlled erosion. The 3D tendon scaffold exhibited consistency between the weight loss and the decline of mechanical properties, which indicated by a 65% decrease in mass with a corresponding 56% loss in ultimate tensile strength after degradation. This study not only reveals that the anisotropic geometries of 3D tendon scaffold could affect cell morphology and lead to desired gene expression toward tendon tissue but also gives an insight into how the degradation impacts geometric cues and mechanical properties of the as-fabricated scaffold. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1138-1149, 2017.

  16. 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

  17. [Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon].

    PubMed

    Wang, Jia-Yu; Dai, Qi-Zhou; Yu, Jie; Yan, Yi-Zhou; Chen, Jian-Meng

    2013-04-01

    The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon (AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55.11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20.22%) and activated carbon alone (27.39%), showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction), indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values: the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.

  18. 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.

  19. [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.

  20. Evaluation of the micro-mechanical strength of resin bonded-dentin interfaces submitted to short-term degradation strategies.

    PubMed

    Feitosa, Victor P; Sauro, Salvatore; Watson, Timothy F; Correr, Américo B; Osorio, Raquel; Toledano, Manuel; Correr-Sobrinho, Lourenço; Sinhoreti, Mário Alexandre C

    2012-11-01

    The aim of this study was to evaluate the microtensile bond strength (μTBS) and confocal micropermeability of resin bonded-dentin specimens created using two representative two-step/self-etch adhesives submitted to short-term period degradation strategies such as simulated pulpal pressure, thermo- or mechanical-cycling challenges. Clearfil SE Bond (CSE) and Silorane adhesive (SIL) were bonded to flat deep dentin from seventy extracted human molars and light-cured for 10 s. Composite build-ups were constructed using with Filtek Z350 XT and Filtek P90 respectively. The specimens of each adhesive group were subjected to three different accelerated aging methods: (1) thermo-cycling challenge (5000 cycles); (2) mechanical-cycling load (200,000 cycles); (3) experiment and (4) conventional method for simulated pulpal pressure (20 cm H₂O). Control resin-bonded specimens were stored in distilled water for 24 h. μTBS and confocal microscopy (CLSM) micropermeability evaluation were performed and the results were analyzed using Two-way ANOVA and Tukey's tests (α=0.05). The CLSM evaluation revealed micro-cracks within the Silorane-bonded dentin subsequent to mechanical-cycling load, whereas, the simulated pulpal pressure induced evident micropermeability in both bonding agents. Mechanical loading provides discernible bonding degradation in a short-term period in resin-bonded dentin created using two-step/self-etch adhesives. However, simulated pulpal pressure may reduce the sealing ability of self-etch adhesives causing greater water uptake within the resin-dentin interface.

  1. A mechanism underlying NOTCH-induced and ubiquitin-mediated JAK3 degradation.

    PubMed

    Wu, Wei; Sun, Xiao-Hong

    2011-12-02

    Although NOTCH signaling is well known to regulate lymphopoiesis, Janus kinase 3 (JAK3) also plays a critical role in promoting lymphocyte development. We have previously found that NOTCH signaling leads to the degradation of JAK3 in B lineage cells, suggesting that NOTCH signaling exerts its biological effect on lymphopoiesis through modulating JAK3 levels. Here, we delineate the biochemical mechanisms involved in NOTCH-induced JAK3 ubiquitination and degradation. NOTCH signaling is known to transcriptionally activate the genes encoding ASB2 (ankyrin-repeat SOCS box containing protein 2) and SKP2 (S-phase kinase-associated protein 2). We show that not only NOTCH but also ASB2 and SKP2 can promote the ubiquitination and degradation of JAK3. Both ASB2 and SKP2 can interact with JAK3 through different domains; the FERM and pseudo-kinase domains each had high affinities for ASB2, whereas the kinase domain primarily associated with SKP2. ASB2 and SKP2 previously have been shown to associate with each other to bridge the formation of a non-canonical Cullin1 and Cullin5-containing dimeric E3 ligase complex. Interestingly, the R980W mutant of JAK3 exhibited diminished interaction with SKP2 and resistance to NOTCH or ASB2-induced degradation. Furthermore, dominant-negative mutants of either Cullin1 or Cullin5, which lack the C terminus responsible for recruiting the E2 enzymes, were able to prevent JAK3 degradation induced by both ASB2/SKP2 and NOTCH signaling. Together, these results suggest that JAK3 ubiquitination involves the non-canonical dimeric E3 ligase complex, and the R980W mutant will serve as an excellent tool for investigating the biological significance of NOTCH-mediated JAK3 turnover.

  2. Reactive molecule species and antioxidative mechanisms in normal skin and skin aging.

    PubMed

    Wölfle, Ute; Seelinger, Günter; Bauer, Georg; Meinke, Martina C; Lademann, Jürgen; Schempp, Christoph M

    2014-01-01

    Reactive oxygen and nitrogen species (ROS/RNS) which may exist as radicals or nonradicals, as well as reactive sulfur species and reactive carbon species, play a major role in aging processes and in carcinogenesis. These reactive molecule species (RMS), often referred to as 'free radicals' or oxidants, are partly by-products of the physiological metabolism. When RMS concentrations exceed a certain threshold, cell compartments and cells are injured and destroyed. Endogenous physiological mechanisms are able to neutralize RMS to some extent, thereby limiting damage. In the skin, however, pollutants and particularly UV irradiation are able to produce additional oxidants which overload the endogenous protection system and cause early aging, debilitation of immune functions, and skin cancer. The application of antioxidants from various sources in skin care products and food supplements is therefore widespread, with increasingly effective formulations being introduced. The harmful effects of RMS (aside from impaired structure and function of DNA, proteins, and lipids) are: interference with specific regulatory mechanisms and signaling pathways in cell metabolism, resulting in chronic inflammation, weakening of immune functions, and degradation of tissue. Important control mechanisms are: MAP-kinases, the aryl-hydrocarbon receptor (AhR), the antagonistic transcription factors nuclear factor-κB and Nrf2 (nuclear factor erythroid 2-related factor 2), and, especially important, the induction of matrix metalloproteinases which degrade dermal connective tissue. Recent research, however, has revealed that RMS and in particular ROS/RNS are apparently also produced by specific enzyme reactions in an evolutionarily adapted manner. They may fulfill important physiologic functions such as the activation of specific signaling chains in the cell metabolism, defense against infectious pathogens, and regulation of the immune system. Normal physiological conditions are characterized by

  3. Understanding the Degradation Mechanism of Lithium Nickel Oxide Cathodes for Li-Ion Batteries

    SciTech Connect

    Xu, Jing; Hu, Enyuan; Nordlund, Dennis; Mehta, Apurva; Ehrlich, Steven N.; Yang, Xiao-Qing; Tong, Wei

    2016-11-01

    The phase transition, charge compensation, and local chemical environment of Ni in LiNiO2 were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge–discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surface over the extended cycles. In conclusion, the degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO2.

  4. Understanding the Degradation Mechanism of Lithium Nickel Oxide Cathodes for Li-Ion Batteries

    DOE PAGES

    Xu, Jing; Hu, Enyuan; Nordlund, Dennis; ...

    2016-11-01

    The phase transition, charge compensation, and local chemical environment of Ni in LiNiO2 were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge–discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surface overmore » the extended cycles. In conclusion, the degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO2.« less

  5. Characterization of biaxial mechanical behavior of porcine aorta under gradual elastin degradation.

    PubMed

    Zeinali-Davarani, Shahrokh; Chow, Ming-Jay; Turcotte, Raphaël; Zhang, Yanhang

    2013-07-01

    Arteries are composed of multiple constituents that endow the wall with proper structure and function. Many vascular diseases are associated with prominent mechanical and biological alterations in the wall constituents. In this study, planar biaxial tensile test data of elastase-treated porcine aortic tissue (Chow et al. in Biomech Model Mechanobiol 2013) is re-examined to characterize the altered mechanical behavior at multiple stages of digestion through constitutive modeling. Exponential-based as well as recruitment-based strain energy functions are employed and the associated constitutive parameters for individual digestion stages are identified using nonlinear parameter estimation. It is shown that when the major portion of elastin is degraded from a cut-open artery in the load-free state, the embedded collagen fibers are recruited at lower stretch levels under biaxial loads, leading to a rapid stiffening behavior of the tissue. Multiphoton microscopy illustrates that the collagen waviness decreases significantly with the degradation time, resulting in a rapid recruitment when the tissue is loaded. It is concluded that even when residual stresses are released, there exists an intrinsic mechanical interaction between arterial elastin and collagen that determines the mechanics of arteries and carries important implications to vascular mechanobiology.

  6. Multisite Phosphorylation Provides an Effective and Flexible Mechanism for Switch-Like Protein Degradation

    PubMed Central

    Varedi K., S. Marjan; Ventura, Alejandra C.; Merajver, Sofia D.; Lin, Xiaoxia Nina

    2010-01-01

    determine the exact extent to which the degradation profile is switch-like. Our results suggest design principles for protein degradation switches which might be a widespread mechanism for precise regulation of cellular processes such as cell cycle progression. PMID:21179196

  7. Multisite phosphorylation provides an effective and flexible mechanism for switch-like protein degradation.

    PubMed

    Varedi K, S Marjan; Ventura, Alejandra C; Merajver, Sofia D; Lin, Xiaoxia Nina

    2010-12-13

    determine the exact extent to which the degradation profile is switch-like. Our results suggest design principles for protein degradation switches which might be a widespread mechanism for precise regulation of cellular processes such as cell cycle progression.

  8. Degradation mechanism(s) of GaAs solar cells with Cu contacts.

    PubMed

    van Leest, R H; de Kleijne, K; Bauhuis, G J; Mulder, P; Cheun, H; Lee, H; Yoon, W; van der Heijden, R; Bongers, E; Vlieg, E; Schermer, J J

    2016-04-21

    Substrate-based GaAs solar cells having a dense Au/Cu front contact grid with 45% surface coverage were exposed to accelerated life testing at temperatures between 200 and 300 °C. TEM analysis of the front contacts was used to gain a better understanding of the degradation process. During accelerated life testing at 200 °C only intermixing of the Au and Cu in the front contact occurs, without any significant influence on the J-V curve of the cells, even after 1320 h (55 days) of accelerated life testing. At temperatures ≥250 °C a recrystallization process occurs in which the metals of the contact and the GaAs front contact layer interact. Once the grainy recrystallized layer starts to approach the window, diffusion via grain boundaries to the window and into the active region of the solar cells occurs, causing a decrease in Voc due to enhanced non-radiative recombination via Cu trap levels introduced in the active region of the solar cell. To be a valid simulation of space conditions the accelerated life testing temperature should be <250 °C in future experiments, in order to avoid recrystallization of the metals with the GaAs contact layer.

  9. 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.

  10. 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.

  11. 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

  12. Mechanism of inflammation in age-related macular degeneration.

    PubMed

    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.

  13. Nonmonotonic Aging and Memory Retention in Disordered Mechanical Systems

    NASA Astrophysics Data System (ADS)

    Lahini, Yoav; Gottesman, Omer; Amir, Ariel; Rubinstein, Shmuel M.

    2017-02-01

    We observe nonmonotonic aging and memory effects, two hallmarks of glassy dynamics, in two disordered mechanical systems: crumpled thin sheets and elastic foams. Under fixed compression, both systems exhibit monotonic nonexponential relaxation. However, when after a certain waiting time the compression is partially reduced, both systems exhibit a nonmonotonic response: the normal force first increases over many minutes or even hours until reaching a peak value, and only then is relaxation resumed. The peak time scales linearly with the waiting time, indicating that these systems retain long-lasting memory of previous conditions. Our results and the measured scaling relations are in good agreement with a theoretical model recently used to describe observations of monotonic aging in several glassy systems, suggesting that the nonmonotonic behavior may be generic and that athermal systems can show genuine glassy behavior.

  14. 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.

  15. 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.

  16. 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.

  17. Microstructure evolution and degradation mechanisms of reactor internal steel irradiated with heavy ions

    NASA Astrophysics Data System (ADS)

    Borodin, O. V.; Bryk, V. V.; Kalchenko, A. S.; Parkhomenko, A. A.; Shilyaev, B. A.; Tolstolutskaya, G. D.; Voyevodin, V. N.

    2009-03-01

    Structure evolution and degradation mechanisms during irradiation of 18Cr-10Ni-Ti steel (material of VVER-1000 reactor internals are investigated). Using accelerator irradiations with Cr3+ and Ar+ ions allowed studying effects of dose rate, different initial structure state and implanted ions on features of structure evolution and main mechanisms of degradation including low temperature swelling and embrittlement of the 18Cr-10Ni-Ti steel. It is shown that differences in dose rate at most irradiation temperatures mainly exert their influence on the duration of the swelling transient regime. Calculations of possible transmutation products during irradiation of this steel in a VVER-1000 spectrum were performed. It is shown that gaseous atoms (He and H), which are generated simultaneously with radiation defects, stabilize the elements of radiation microstructure and influence the swelling. The nature of deformation under different temperatures of irradiation and of mechanical testing is investigated. It is shown that the temperature sensitivity of swelling behaviour in the investigated steel, with different initial structures can be connected with the dynamic behaviour of point defect sinks.

  18. Clinical relevance of trans 1,4-polyisoprene aging degradation on the longevity of root canal treatment.

    PubMed

    Maniglia-Ferreira, Cláudio; Valverde, Guilherme Bönecker; Silva, João Batista Araújo; de Paula, Regina Célia Monteiro; Feitosa, Judith Pessoa Andrade; de Souza-Filho, Francisco José

    2007-01-01

    This in vivo study investigated the time of degradation of root filling material (trans 1,4-polyisoprene) retrieved from endodontically treated teeth and correlated the occurrence of degradation with the longevity of endodontics. Thirty-six root-filled teeth with different filling times (2 to 30 years) and with and without periapical lesions were selected. All teeth presented clinical indication for root canal retreatment. The association among filling time, presence of periapical lesion and root filling material degradation was investigated. Root filling samples were retrieved from the root canals using a Hedströ m file without solvent. The trans 1,4-polyisoprene was isolated by root filling solubilization in chloroform followed by filtration and centrifugation. GPC and FT-IR were the analytical techniques utilized. Degradation of trans 1,4-polyisoprene occurred with time, as a slow process. It is an oxidative process, and production of carboxyl and hydroxyl groups in the residual polymer were observed. Statistically significant decrease of molar mass was observed after 5 (p=0.0001) and 15 (p=0.01) years in teeth with and without periapical lesion, respectively. Bacteria participated in polymer degradation. Gutta-percha aging was proven an important factor for the long-term success of endodontic treatment. The findings of the present study showed that, after 15 years, polymer weight loss may decrease the capacity of the filling mass to seal the root canal space and prevent re-infection, thus compromising significantly the longevity of root canal therapy.

  19. Cathepsin S Cannibalism of Cathepsin K as a Mechanism to Reduce Type I Collagen Degradation*

    PubMed Central

    Barry, Zachary T.; Platt, Manu O.

    2012-01-01

    Cathepsins S and K are potent mammalian proteases secreted into the extracellular space and have been implicated in elastin and collagen degradation in diseases such as atherosclerosis and osteoporosis. Studies of individual cathepsins hydrolyzing elastin or collagen have provided insight into their binding and kinetics, but cooperative or synergistic activity between cathepsins K and S is less described. Using fluorogenic substrate assays, Western blotting, cathepsin zymography, and computational analyses, we uncovered cathepsin cannibalism, a novel mechanism by which cathepsins degrade each other as well as the substrate, with cathepsin S predominantly degrading cathepsin K. As a consequence of these proteolytic interactions, a reduction in total hydrolysis of elastin and type I collagen was measured compared with computationally predicted values derived from individual cathepsin assays. Furthermore, type I collagen was preserved from hydrolysis when a 10-fold ratio of cathepsin S cannibalized the highly collagenolytic cathepsin K, preventing its activity. Elastin was not preserved due to strong elastinolytic ability of both enzymes. Together, these results provide new insight into the combined proteolytic activities of cathepsins toward substrates and each other and present kinetic models to consider for more accurate predictions and descriptions of these systems. PMID:22730330

  20. Study of mechanical degradation of UHMWPE acetabular components due to clinical X-ray procedures.

    PubMed

    Vasconcellos, Letícia A; Blando, Eduardo; Souto, André A; Oliveira, Marilia G; Woitchunas, Gilséia F P; Hübler, Roberto

    2007-08-01

    The use of multi-component femoral implants to replace the femur head and re-establish bone motion has been widespread since the 70s. Frequently these implants have spherical metallic heads made of, for example, 316-L stainless steel or Cr-Co alloys, which allow rotational motion towards a polymeric component (UHMWPE). One of the major causes of implant rejection is the generation of UHMWPE debris on the surface between the implant head and the polymeric component. The gamma ray sterilization of implants and the periodical X-ray medical control could contribute to premature degradation of the polymeric surface, resulting in increased wear and shortened lifetime of the implant. In this work we study the degradation degree of the polymeric UHMWPE component as function of the X-ray dose. The elasto-plastic deformation and recovery were carried out by means of a nanohardness tester equipment and the polymer degradation was measured using a fast Fourier transform infra-red (FT-IR) equipment. The results show the compromise among the irradiation doses, the surface oxidation and the mechanical properties of the samples.

  1. Degradable phosphate glass fiber reinforced polymer matrices: mechanical properties and cell response.

    PubMed

    Brauer, Delia S; Rüssel, Christian; Vogt, Sebastian; Weisser, Jürgen; Schnabelrauch, Matthias

    2008-01-01

    The development of biodegradable materials for internal fracture fixation is of great interest, as they would both eliminate the problem of stress shielding and obviate the need for a second operation to remove fixation devices. Preliminary investigations for the production of degradable fiber reinforced polymer composite materials are detailed. Composites were produced of phosphate invert glass fibers of the glass system P(2)O(5)-CaO-MgO-Na(2)O-TiO(2), which showed a low solubility in previous work. The fibers were embedded into a matrix of a degradable organic polymer network based on methacrylate-modified oligolactide. Fracture behavior, bending strength and elastic modulus were evaluated during 3-point bending tests and the fracture surface of the composites was investigated using a scanning electron microscope. Short-term biocompatibility was tested in an FDA/EtBr viability assay using MC3T3-E1 murine pre-osteoblast cells and showed a good cell compatibility of the composite materials. Results suggested that these composite materials are biocompatible and show mechanical properties which are of interest for the production of degradable bone fixation devices.

  2. 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.

  3. Mechanisms for light induced degradation in MAPbI3 perovskite thin films and solar cells

    NASA Astrophysics Data System (ADS)

    Abdelmageed, Ghada; Jewell, Leila; Hellier, Kaitlin; Seymour, Lydia; Luo, Binbin; Bridges, Frank; Zhang, Jin Z.; Carter, Sue

    2016-12-01

    Organometal halide perovskites are highly promising materials for photovoltaic applications, yet their rapid degradation remains a significant challenge. Here, the light-induced structural degradation mechanism of methylammonium lead iodide (MAPbI3) perovskite films and devices is studied in low humidity environment using X-Ray Diffraction, Ultraviolet-Visible (UV-Vis) absorption spectroscopy, Extended X-ray Absorption Fine Structure spectroscopy, Fourier Transform Infrared spectroscopy, and device measurements. Under dry conditions, the perovskite film degrades only in the presence of both light and oxygen, which together induce the formation of halide anions through donation of electrons to the surrounding oxygen. The halide anions generate free radicals that deprotonate the methylammonium cation and form the highly volatile CH3NH2 molecules that escape and leave pure PbI2 behind. The device findings show that changes in the local structure at the TiO2 mesoporous layer occur with light, even in the absence of oxygen, and yet such changes can be prevented by the application of UV blocking layer on the cells. Our results indicate that the stability of mp-TiO2-MAPbI3 photovoltaics can be dramatically improved with effective encapsulation that protects the device from UV light, oxygen, and moisture.

  4. 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).

  5. 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.

  6. Statistical analysis of degradation modes and mechanisms in various thin-film photovoltaic module technologies

    NASA Astrophysics Data System (ADS)

    Schneller, Eric; Shiradkar, Narendra S.; Pereira, Camila L.; Fonseca, Leandro C.; Dhere, Neelkanth G.

    2014-10-01

    PV arrays of various thin film modules technologies such as CIGS, rigid single-junction amorphous Silicon (glass-to-glass package) and flexible triple-junction amorphous Silicon have been deployed for over 10 years in hot and humid climate at Florida Solar Energy Center. The performance of selected modules from each array was characterized using visual inspection, dark I-V, flasher I-V, electroluminescence and infrared imaging techniques. Performance was evaluated to determine which, if any, degradation mechanisms are a concern for the long-term reliability of this technology.

  7. 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.

  8. 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.

  9. AGE-DEPENDENT ASCENDING AORTA MECHANICS ASSESSED THROUGH MULTIPHASE CT

    PubMed Central

    Martin, Caitlin; Sun, Wei; Primiano, Charles; McKay, Raymond; Elefteriades, John

    2013-01-01

    Quantification of the age- and gender-specific in vivo mechanical characteristics of the ascending aorta (AA) will allow for identification of abnormalities aside from changes brought on by aging alone. Multiphase clinical CT scans of 45 male patients between the ages of 30 and 79 years were analyzed to assess age-dependent in vivo AA characteristics. The three-dimensional AA geometry for each patient was reconstructed from the CT scans for 9–10 phases throughout the cardiac cycle. The AA circumference was measured during each phase and was used to determine the corresponding diameter, circumferential strain, and wall tension at each phase. The pressure-strain modulus was also determined for each patient. The mean diastolic AA diameter was significantly smaller among young (42.6±5.2 years) at 29.9±2.8 mm than old patients (69.0±5.2 years) at 33.2±3.2 mm. The circumferential AA strain from end-diastole to peak-systole decreased from 0.092±0.03 in young to 0.056±0.03 in old patients. The pressure-strain modulus increased two-fold from 68.4±30.5 kPa in young to 162.0±93.5 kPa in old patients, and the systolic AA wall tension increased from 268.5±31.3 kPa in young to 304.9±49.2 kPa in old patients. The AA dilates and stiffens with aging which increases the vessel wall tension, likely predisposing aneurysm and dissection. PMID:23817767

  10. 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

  11. 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

  12. Tubulin acetylation protects long-lived microtubules against mechanical ageing.

    PubMed

    Portran, Didier; Schaedel, Laura; Xu, Zhenjie; Théry, Manuel; Nachury, Maxence V

    2017-04-01

    Long-lived microtubules endow the eukaryotic cell with long-range transport abilities. While long-lived microtubules are acetylated on Lys40 of α-tubulin (αK40), acetylation takes place after stabilization and does not protect against depolymerization. Instead, αK40 acetylation has been proposed to mechanically stabilize microtubules. Yet how modification of αK40, a residue exposed to the microtubule lumen and inaccessible to microtubule-associated proteins and motors, could affect microtubule mechanics remains an open question. Here we develop FRET-based assays that report on the lateral interactions between protofilaments and find that αK40 acetylation directly weakens inter-protofilament interactions. Congruently, αK40 acetylation affects two processes largely governed by inter-protofilament interactions, reducing the nucleation frequency and accelerating the shrinkage rate. Most relevant to the biological function of acetylation, microfluidics manipulations demonstrate that αK40 acetylation enhances flexibility and confers resilience against repeated mechanical stresses. Thus, unlike deacetylated microtubules that accumulate damage when subjected to repeated stresses, long-lived microtubules are protected from mechanical ageing through their acquisition of αK40 acetylation. In contrast to other tubulin post-translational modifications that act through microtubule-associated proteins, motors and severing enzymes, intraluminal acetylation directly tunes the compliance and resilience of microtubules.

  13. 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.

  14. [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.

  15. 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

  16. 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.

  17. Passive biaxial mechanical response of aged human iliac arteries.

    PubMed

    Schulze-Bauer, Christian A J; Mörth, Christian; Holzapfel, Gerhard A

    2003-06-01

    Inflation and extension tests of arteries are essential for the understanding of arterial wall mechanics. Data for such tests of human arteries are rare. At autopsy we harvested 10 non-diseased external iliac arteries of aged subjects (52-87 yrs). Structural homogeneity was ensured by means of ultrasound imaging, and anamneses of patients were recorded. We measured the axial in situ stretches, load-free geometries and opening angles. Passive biaxial mechanical responses of preconditioned cylindrical specimens were studied in 37 degrees C calcium-free Tyrode solution under quasistatic loading conditions. Specimens were subjected to pressure cycles varying from 0 to 33.3 kPa (250 mmHg) at nine fixed axial loads, varying from 0 to 9.90N. For the description of the load-deformation behavior we employed five "two-dimensional" orthotropic strain-energy functions frequently used in arterial wall mechanics. The associated constitutive models were compared in regard to their ability of representing the experimental data. Histology showed that the arteries were of the muscular type. In contrast to animal arteries they exhibited intimal layers of considerable thickness. The average ratio of wall thickness to outer diameter was 7.7, which is much less than observed for common animal arteries. We found a clear correlation between age and the axial in situ stretch lambda is (r = -0.72, P = 0.03), and between age and distensibility of specimens, i.e. aged specimens are less distensible. Axial in situ stretches were clearly smaller (1.07 +/- 0.09, mean +/- SD) than in animal arteries. For one specimen lambda is was even smaller than 1.0, i.e. the vessel elongated axially upon excision. The nonlinear and anisotropic load-deformation behavior showed small hystereses. For the majority of specimens we observed axial stretches smaller than 1.3 and circumferential stretches smaller than 1.1 for the investigated loading range. Data from in situ inflation tests showed a significant

  18. Identification of autophagy as a longevity-assurance mechanism in the aging model Podospora anserina

    PubMed Central

    Knuppertz, Laura; Hamann, Andrea; Pampaloni, Francesco; Stelzer, Ernst; Osiewacz, Heinz D

    2014-01-01

    The filamentous ascomycete Podospora anserina is a well-established aging model in which a variety of different pathways, including those involved in the control of respiration, ROS generation and scavenging, DNA maintenance, proteostasis, mitochondrial dynamics, and programmed cell death have previously been demonstrated to affect aging and life span. Here we address a potential role of autophagy. We provide data demonstrating high basal autophagy levels even in strains cultivated under noninduced conditions. By monitoring an N-terminal fusion of EGFP to the fungal LC3 homolog PaATG8 over the lifetime of the fungus on medium with and without nitrogen supplementation, respectively, we identified a significant increase of GFP puncta in older and in nitrogen-starved cultures suggesting an induction of autophagy during aging. This conclusion is supported by the demonstration of an age-related and autophagy-dependent degradation of a PaSOD1-GFP reporter protein. The deletion of Paatg1, which leads to the lack of the PaATG1 serine/threonine kinase active in early stages of autophagy induction, impairs ascospore germination and development and shortens life span. Under nitrogen-depleted conditions, life span of the wild type is increased almost 4-fold. In contrast, this effect is annihilated in the Paatg1 deletion strain, suggesting that the ability to induce autophagy is beneficial for this fungus. Collectively, our data identify autophagy as a longevity-assurance mechanism in P. anserina and as another surveillance pathway in the complex network of pathways affecting aging and development. These findings provide perspectives for the elucidation of the mechanisms involved in the regulation of individual pathways and their interactions. PMID:24584154

  19. 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.

  20. Degradation mechanisms of bioresorbable polyesters. Part 2. Effects of initial molecular weight and residual monomer.

    PubMed

    Gleadall, Andrew; Pan, Jingzhe; Kruft, Marc-Anton; Kellomäki, Minna

    2014-05-01

    This paper presents an understanding of how initial molecular weight and initial monomer fraction affect the degradation of bioresorbable polymers in terms of the underlying hydrolysis mechanisms. A mathematical model was used to analyse the effects of initial molecular weight for various hydrolysis mechanisms including noncatalytic random scission, autocatalytic random scission, noncatalytic end scission or autocatalytic end scission. Different behaviours were identified to relate initial molecular weight to the molecular weight half-life and to the time until the onset of mass loss. The behaviours were validated by fitting the model to experimental data for molecular weight reduction and mass loss of samples with different initial molecular weights. Several publications that consider initial molecular weight were reviewed. The effect of residual monomer on degradation was also analysed, and shown to accelerate the reduction of molecular weight and mass loss. An inverse square root law relationship was found between molecular weight half-life and initial monomer fraction for autocatalytic hydrolysis. The relationship was tested by fitting the model to experimental data with various residual monomer contents.

  1. 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.

  2. 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.

  3. Visualization and quantification of electrochemical and mechanical degradation in Li ion batteries.

    PubMed

    Ebner, Martin; Marone, Federica; Stampanoni, Marco; Wood, Vanessa

    2013-11-08

    High-energy-density materials that undergo conversion and/or alloying reactions hold promise for next-generation lithium (Li) ion batteries. However, these materials experience substantial volume change during electrochemical operation, which causes mechanical fracture of the material and structural disintegration of the electrode, leading to capacity loss. In this work, we use x-ray tomography during battery operation to visualize and quantify the origins and evolution of electrochemical and mechanical degradation. Tomography provides the time-resolved, three-dimensional chemical composition and morphology within individual particles and throughout the electrode. In the model material tin(II) oxide, we witness distributions in onset and rate of core-shell lithiation, crack initiation and growth along preexisting defects, and irreversible distortion of the electrode, highlighting tomography as a tool to guide the development of durable materials and strain-tolerant electrodes.

  4. 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.

  5. 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

  6. 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.

  7. 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

    2015-11-02

    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.

  8. New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

    NASA Astrophysics Data System (ADS)

    Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

    2016-05-01

    The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

  9. Studies on the degradative mechanism of phosphoenolpyruvate carboxykinase from yeast Saccharomyces cerevisiae.

    PubMed

    Burlini, N; Morandi, S; Pellegrini, R; Tortora, P; Guerritore, A

    1989-11-20

    Previous work carried out in our laboratory (Burlini, N., Lamponi S., Radrizzani, M., Monti, E. and Tortora P. (1987) Biochim. Biophys. Acta 930, 220-229) led to the immunological identification of a yeast 65-kDa phosphoprotein as a modified form of phosphoenolpyruvate carboxykinase; moreover the appearance of this phospho form was proven to be independent of cAMP, whereas the glucose-induced inactivation of the native enzyme is cAMP-dependent. Here, we report further investigations on the mechanism of the glucose-triggered degradation of the enzyme which led to the following results: (a) the aforementioned phospho form displayed a binding pattern to 5 AMP-Sepharose 4B quite similar to that of native enzyme, although it did not retain its oligomeric structure, nor was it catalytically active; (b) its phosphate content was of about two residues per monomer; (c) its isoelectric point was slightly higher than that of native enzyme, this shows that the enzyme undergoes additional modifications besides phosphorylation; (d) it represented about 4% of the native enzyme in glucose-depressed cells; (e) other forms immunologically cross-reactive with the native enzyme were also isolated, whose molecular mass was in the range of 60-62 kDa, and they are probable candidates as degradation products of the phospho form; (f) time courses of the native and phospho forms in the presence and the absence of glucose provided data consistent with a kinetic model involving a strong stimulation of the decay of both forms effected by the sugar; (g) in the mutant ABYS1 (Achstetter, T., Emter, O., Ehmann, C. and Wolf, D.H. (1984) J. Biol. Chem. 259, 13334-13343) which is devoid of the four major vacuolar proteinases, the decay pattern was essentially the same as in wild-type; (h) effectors lowering intracellular ATP also retarded the first step of enzyme degradation; this points to an ATP-dependence of this step. Based on these results we propose a degradation mechanism consisting of an

  10. Mechanisms of renal tubular defects in old age.

    PubMed Central

    Dontas, A. S.; Marketos, S. G.; Papanayiotou, P.

    1972-01-01

    The mechanisms of renal tubular dysfunction in old age have been examined in twenty-eight clinically healthy elderly subjects without infection, and in fourteen subjects of similar age with laboratory evidence of intrarenal infection. The data were compared with those from thirteen clinically healthy young subjects. Studied were: proximal tubular (Tm(PAH)) and distal tubular (CH2O) activity, minimal and maximal osmolal U/P ratios, maximal osmolal excretion in hydropenia, and GFR levels under standard hydration and under water-loading. The reduction of GFR in old age is evident particularly in men under conditions of standard hydration: it is accentuated in the presence of renal infection. Proximal tubular activity is also significantly lower in elderly men, especially if they have chronic bacteriuria. The reduction is closely related to GFR levels, with identical Tm(PAH):C(in) ratios in all groups. This supports the intact nephron hypothesis for this part of the nephron. Distal tubular activity is depressed in old age in both sexes proportionately more than proximal tubular activity or the GFR. The lower CH2O: GFR ratios imply a selective distal tubular damage. Maximal osmolal U/P ratios in hydropenia are significantly higher in the young (mean 367) than in either the elderly non-infected (mean 279) or the elderly infected subjects (mean 212). Conversely, minimal U/P ratios in water-loading are lower in the young (mean 0.247) than in either elderly group (means 0.418 and 0.668). Osmolal excretion in hydropenia is not different between the groups, but urine flows in water-loading clearly separate them. The data indicate that simple functions of the distal-collecting tubule (e.g. the CH2O), are less affected in old age than are functions involving several medullary structures (as is the maximal U(osm) or U/P ratio). They suggest that the main impairment of the distal tubular cell involves the failure to achieve a proper osmotic gradient between tubular fluid and

  11. Fabrication of novel magnesium-matrix composites and their mechanical properties prior to and during in vitro degradation.

    PubMed

    Dezfuli, Sina Naddaf; Leeflang, Sander; Huan, Zhiguang; Chang, Jiang; Zhou, Jie

    2017-03-01

    In our previous study, we developed Mg-matrix composites with bredigite as the reinforcing phase and achieved improved degradation resistance in comparison with Mg. However, the effects of materials processing method and process parameters on the mechanical behavior of the composites before and during degradation were still unknown. This research was aimed at determining the mechanical properties of Mg-bredigite composites prior to and during degradation. It was found that by optimizing the process parameters of Pressure Assisted Sintering (PAS), low-porosity Mg-bredigite composites with strong interfaces between homogeneously distributed bredigite particles and the Mg matrix could be fabricated. By reinforcing Mg with 20vol% bredigite particles, the ultimate compressive strength and ductility of Mg increased by 67% and 111%, respectively. The in vitro degradation rate of the Mg-20% bredigite composite in a cell culture medium was 24 times lower than that of monolithic Mg. As a result of retarded degradation, the mechanical properties of the composite after 12 days of immersion in the cell culture medium were comparable to those of cortical bone. The encouraging results of this research warrant further investigations on the in vivo degradation behavior and mechanical properties of the composites.

  12. Fibro-porous poliglecaprone/polycaprolactone conduits: synergistic effect of composition and in vitro degradation on mechanical properties.

    PubMed

    Patel, Harsh N; Garcia, Roman; Schindler, Carrie; Dean, Derrick; Pogwizd, Steven M; Singh, Raj; Vohra, Yogesh K; Thomas, Vinoy

    2015-04-01

    Blends of poliglecaprone (PGC) and polycaprolactone (PCL) of varying compositions were electrospun into tubular conduits and their mechanical, morphological, thermal and in vitro degradation properties were evaluated under simulated physiological conditions. Generally, mechanical strength, modulus and hydrophilic nature were enhanced by the addition of PGC to PCL. An in vitro degradation study in phosphate-buffered saline (pH 7.3) was carried out for up to 1 month to understand the hydrolytic degradation effect on the mechanical properties in both the longitudinal and circumferential directions. Pure PCL and 4:1 PCL/PGC blend scaffolds exhibited considerable elastic stiffening after a 1 month in vitro degradation. Fourier transform infrared spectroscopic and DSC techniques were used to understand the degradation behavior and the changes in structure and crystallinity of the polymeric blends. A 3:1 PCL/PGC blend was concluded to be a judicious blend composition for tubular grafts based on overall results on the mechanical properties and performance after a 1 month in vitro degradation study.

  13. Endocytic collagen degradation: a novel mechanism involved in protection against liver fibrosis.

    PubMed

    Madsen, Daniel H; Jürgensen, Henrik J; Ingvarsen, Signe; Melander, Maria C; Vainer, Ben; Egerod, Kristoffer L; Hald, Andreas; Rønø, Birgitte; Madsen, Charlotte A; Bugge, Thomas H; Engelholm, Lars H; Behrendt, Niels

    2012-05-01

    Fibrosis of the liver and its end-stage, cirrhosis, represent major health problems worldwide. In these fibrotic conditions, activated fibroblasts and hepatic stellate cells display a net deposition of collagen. This collagen deposition is a major factor leading to liver dysfunction, thus making it crucially important to understand both the collagen synthesis and turnover mechanisms in this condition. Here we show that the endocytic collagen receptor, uPARAP/Endo180, is a major determinant in governing the balance between collagen deposition and degradation. Cirrhotic human livers displayed a marked up-regulation of uPARAP/Endo180 in activated fibroblasts and hepatic stellate cells located close to the collagen deposits. In a hepatic stellate cell line, uPARAP/Endo180 was shown to be active in, and required for, the uptake and intracellular degradation of collagen. To evaluate the functional importance of this collagen receptor in vivo, liver fibrosis was induced in uPARAP/Endo180-deficient mice and littermate wild-type mice by chronic CCl(4) administration. A strong up-regulation of uPARAP/Endo180 was observed in wild-type mice, and a quantitative comparison of collagen deposits in the two groups of mice clearly revealed a fibrosis protective role of uPARAP/Endo180. This effect appeared to directly reflect the activity of the collagen receptor, since no compensatory events were noted when comparing the mRNA expression profiles of the two groups of mice in an array system focused on matrix-degrading components. This function of uPARAP/Endo180 defines a novel role of intracellular collagen turnover in fibrosis protection.

  14. Mechanism and kinetics of electrochemical degradation of uric acid using conductive-diamond anodes.

    PubMed

    Dbira, Sondos; Bensalah, Nasr; Bedoui, Ahmed

    2016-12-01

    Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-doped diamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

  15. 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

  16. 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

  17. Comparable mechanisms of working memory interference by auditory and visual motion in youth and aging.

    PubMed

    Mishra, Jyoti; Zanto, Theodore; Nilakantan, Aneesha; Gazzaley, Adam

    2013-08-01

    Intrasensory interference during visual working memory (WM) maintenance by object stimuli (such as faces and scenes), has been shown to negatively impact WM performance, with greater detrimental impacts of interference observed in aging. Here we assessed age-related impacts by intrasensory WM interference from lower-level stimulus features such as visual and auditory motion stimuli. We consistently found that interference in the form of ignored distractions and secondary task interruptions presented during a WM maintenance period, degraded memory accuracy in both the visual and auditory domain. However, in contrast to prior studies assessing WM for visual object stimuli, feature-based interference effects were not observed to be significantly greater in older adults. Analyses of neural oscillations in the alpha frequency band further revealed preserved mechanisms of interference processing in terms of post-stimulus alpha suppression, which was observed maximally for secondary task interruptions in visual and auditory modalities in both younger and older adults. These results suggest that age-related sensitivity of WM to interference may be limited to complex object stimuli, at least at low WM loads.

  18. [Ageing rate in workers of mechanic workshops of machinery construction industry in Armenia].

    PubMed

    Sarkisian, G T; Barkhudarov, M S; Kogan, V Iu

    2004-01-01

    Studies of biologic age formation and ageing rate in workers of mechanic workshops revealed that able-bodied population grew old demographically. That is proved by absent age group of 20-29 years and increased share of able-bodied workers older than 50. Young workers aged 30-39 appeared the most vulnerable for occupational hazards--they demonstrated increased ageing rate and maximal excess of biologic age over chronological age and due biologic age.

  19. 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.

  20. Hydrolytically degradable hyperbranched PEG-polyester adhesive with low swelling and robust mechanical properties.

    PubMed

    Zhang, Hong; Zhao, Tianyu; Duffy, Patrick; Dong, Yixiao; Annaidh, Aisling Ní; O'Cearbhaill, Eoin; Wang, Wenxin

    2015-10-28

    Photocrosslinkable and water soluble hyperbranched PEG-polyester polymers (HPEGDA) have been developed as robust degradable adhesives. The HPEGDA polymers have been synthesized from controlled homopolymerization of poly(ethylene glycol) diacrylate (PEGDA700 ) via in situ deactivation enhanced atom transfer radical polymerization (DE-ATRP). By introducing a high initiator-to-monomer ratio, the obtained HPEGDA polymer is composed of extremely short carbon-carbon backbones interconnected together by the long PEG chains as well as pendent photocrosslinkable acrylate moieties. Due to the extremely short C-C backbone, the long PEG chains can therefore be seen as the main chain, thus, HPEGDA polymers behave more like polyester which is a category of polymers that contain the ester functional group in their main chain. Photo-cured HPEGDA can be readily adhered to tissue forming a patch with robust mechanical and adhesive strengths. The degradation profile by hydrolysis of polyester blocks as well as a significantly low swelling ratio of HPEGDA gels in an aqueous environment allow them to have great potential for sealing and repair of internal tissue. Furthermore, HPEGDA gels appear to have minor significant cytotoxicity in vitro. These unique properties indicate that the reported HPEGDA polymers are well poised for the development of adhesive tissue engineering matrixes, wound dressings, and sealants.

  1. 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.

  2. Solar active photocatalyst for effective degradation of RR 120 with dye sensitized mechanism.

    PubMed

    Subash, B; Senthilraja, A; Dhatshanamurthi, P; Swaminathan, M; Shanthi, M

    2013-11-01

    Solar active WO3 loaded Ag-ZnO (WO3-Ag-ZnO) was successfully synthesized by precipitation-decomposition method. XPS reveals that the presence of metallic silver in the catalyst. The photocatalytic activity of WO3-Ag-ZnO was investigated for the degradation of Reactive Red 120 (RR 120) in aqueous solution using solar light. WO3-Ag-ZnO is found to be more efficient than Ag-ZnO, WO3-ZnO, Ag-WO3, commercial ZnO, prepared ZnO, Degussa TiO2-P25, pure WO3 and TiO2 (Merck) at pH 7 for the mineralization of RR 120. The effects of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo mineralization of RR 120 have been analyzed. The mineralization of RR 120 has been confirmed by COD measurements. A dual mechanism has been proposed for efficient degradation of RR 120 dye with WO3-Ag-ZnO under solar light at neutral pH. This catalyst is found to be reusable.

  3. 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.

  4. 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.

  5. In vitro kinetic analysis of oligofructose consumption by Bacteroides and Bifidobacterium spp. indicates different degradation mechanisms.

    PubMed

    Van der Meulen, Roel; Makras, Lefteris; Verbrugghe, Kristof; Adriany, Tom; De Vuyst, Luc

    2006-02-01

    The growth of pure cultures of Bacteroides thetaiotaomicron LMG 11262 and Bacteroides fragilis LMG 10263 on fructose and oligofructose was examined and compared to that of Bifidobacterium longum BB536 through in vitro laboratory fermentations. Gas chromatography (GC) analysis was used to determine the different fractions of oligofructose and their degradation during the fermentation process. Both B. thetaiotaomicron LMG 11262 and B. fragilis LMG 10263 were able to grow on oligofructose as fast as on fructose, succinic acid being the major metabolite produced by both strains. B. longum BB536 grew slower on oligofructose than on fructose. Acetic acid and lactic acid were the main metabolites produced when fructose was used as the sole energy source. Increased amounts of formic acid and ethanol were produced when oligofructose was used as an energy source at the cost of lactic acid. Detailed kinetic analysis revealed a preferential metabolism of the short oligofructose fractions (e.g., F2 and F3) for B. longum BB536. After depletion of the short fractions, the larger oligofructose fractions (e.g., F4, GF4, F5, GF5, and F6) were metabolized, too. Both Bacteroides strains did not display such a preferential metabolism and degraded all oligofructose fractions simultaneously, transiently increasing the fructose concentration in the medium. This suggests a different mechanism for oligofructose breakdown between the strain of Bifidobacterium and both strains of Bacteroides, which helps to explain the bifidogenic nature of inulin-type fructans.

  6. 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.

  7. 1,3-Dinitrobenzene reductive degradation by alkaline ascorbic acid - Reaction mechanisms, degradation pathways and reagent optimization.

    PubMed

    Ciou, Chiya; Liang, Chenju

    2017-01-01

    Nitro-aromatic compounds (NACs) such as 1,3-dinitrobenzene (1,3-DNB) contain the nitrogroup (-NO2), in which the N with a +III oxidation state accepts electrons. Water soluble ascorbic acid (AsA) at elevated pH produces electron transfer and governs the electron-donating pathway. The influence of the NaOH/AsA molar ratio on the degradation of 1,3-DNB was investigated. Using 0.21-2 M NaOH and 20-100 mM AsA, nearly complete 1,3-DNB removals (90-100%) were achieved within 0.5 h. On the basis of intermediates identified using GC/MS, the reduction pathways of 1,3-DNB can be categorized into step-by-step electron transfer, and condensation routes. A higher NaOH/AsA molar ratio would result in relatively higher AsA decomposition, promote the condensation route into the formation of azo- and azoxy-compounds, and ultimately reduce 1,3-DNB to 1,3-phenylenediamine. Contaminated soil flushing using 500 mM NaOH/100 mM AsA revealed that 1,3-DNB was completely degraded within 2 h. Based on these test results, the alkaline AsA treatment method is a potential remediation process for NACs contaminated soils.

  8. Circular geometric moiré for degradation prediction of mechanical components performing angular oscillations

    NASA Astrophysics Data System (ADS)

    Palevicius, P.; Aleksa, A.; Maskeliunas, R.; Ragulskis, M.

    2017-03-01

    An experimental technique based on time-averaged circular geometric moiré for optical measurement of angular oscillations is presented in this paper. The pitch of the circular moiré is preselected in such a way that angular oscillations of different amplitudes yield time-averaged moiré fringes at different locations of the cover image. This optical effect enables to construct an optical scale for direct measurement of angular oscillations. The proposed technique is similar to visual cryptography, which is a cryptographic technique that allows encryption of visual information in such a way, that decryption can be done without use of any computational device. The efficiency and the applicability of the proposed technique for performance degradation prediction of rotating mechanical components is illustrated and validated by computational simulations and experimental tests.

  9. AGE/RAGE/Akt pathway contributes to prostate cancer cell proliferation by promoting Rb phosphorylation and degradation.

    PubMed

    Bao, Ji-Ming; He, Min-Yi; Liu, Ya-Wei; Lu, Yong-Jie; Hong, Ying-Qia; Luo, Hai-Hua; Ren, Zhong-Lu; Zhao, Shan-Chao; Jiang, Yong

    2015-01-01

    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 investigated 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). 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. 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. 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.

  10. Photo degradation of methyl orange an azo dye by advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism.

    PubMed

    Gomathi Devi, L; Girish Kumar, S; Mohan Reddy, K; Munikrishnappa, C

    2009-05-30

    Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The

  11. 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.

  12. 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.

  13. Wear Resistant Carbide-based Thermal Sprayed Coatings: Process, Properties, Mechanical Degradation and Wear

    NASA Astrophysics Data System (ADS)

    Ghabchi, Arash

    Thermally sprayed ceramic-metallic composite (CerMet) materials consist of ceramic particles mainly in form of carbides reinforced by metallic binder exhibit unique microstructural and mechanical characteristics. Such structure brings in a novel combination of hardness and toughness enabling application of this class of material in wear resistant surfaces. Final deposit microstructure that defines the mechanical properties and wear performance of material depends on process parameters and starting material characteristics. Complex interaction of in-flight particles with supersonic flame, formation of complex defective deposit structure comprising of pores, cracks and splat boundaries make comprehending of interrelation of process, microstructure, properties and performance a difficult task. Additional challenge is development of systematic understanding on mechanical degradation, damage and wear mechanisms of cermet coatings due to their complex structure. This dissertation attempts to address these issues first by taking a systematic step by step approach, process map, to establish a correlation between process, particle state, microstructure and properties. Different strategies were proposed and examined to control the high velocity thermal spray process. This strategy assessment enabled a better control over in-flight particles state in high velocity thermal spray process and provided better understanding on interaction of in-flight particles with the flame. Further, possible advantages of reducing the carbide particle size from micron to nano in terms of mechanical properties and different wear performance were explored. It was suggested that poor wear performance of nano-structured coating is due to presence of brittle phases and less available binder promotes the excessive stress detrimental to load carrying capability of material. Material damage and wear mechanisms of coating under different tribological conditions were examined. The results suggest a

  14. Improved mechanical properties of chitosan fibers with applications to degradable radar countermeasure chaff

    NASA Astrophysics Data System (ADS)

    Knaul, Jonathan Zvi

    The objective of this work has been to improve the mechanical properties of wet spun chitosan fibers for applications to a degradable form of radar countermeasure chaff. The first part of the study characterizes the chitosan used for spinning. Three methods for determining the degree of deacetylation (% DDA) were used and they include titration, elemental analysis, and first derivative ultraviolet (UV) spectrometry. The molecular weight of the chitosan was determined in a solvent system of 0.25 M CH3COOH/0.25 M CH3COONa, using viscometry and gel permeation chromatography (GPC). Several samples of chitosan were used with the % DDA varying from 64.3 to 96.0%. The Mark-Houwink-Sakurada constants used for the determination of viscosity average molecular weight and the universal calibration of the HPLC system were K = 1.40 x 10 -4 dL/g and a = 0.83, respectively. A literature review of molecular weight analysis of chitosan is included. Preliminary wet spinning experiments involved a coagulation rate study which demonstrated that 1 M KOH was an effective coagulant for wet spinning and that the rate of coagulation increases with decreasing solvent ratio in the spin dope. A drying study confirmed the effectiveness of a methanol drying bath followed by a heated roller at 50°C. Following these studies, a wet spinning system was constructed and used. A lack of published data exists concerning the subjects of chitosan fiber spinning and mechanical improvements to both wet and dry chitosan fibers. Several post-spinning modification experiments focused on the reaction of the dried as-spun chitosan fibers with aqueous agents including potassium dihydrogen phosphate (KH2PO4), potassium hydrogen phthalate (KHP), glutaraldehyde (GA), and glyoxal (GLY). For the aqueous buffering agents of KH2PO4, and KHP, the highest mechanical properties resulted from solutions containing phthalate ions at pH 5.00, and from solutions containing phosphate ions at pH 5.39. The best time and

  15. Aging interferes central control mechanism for eccentric muscle contraction.

    PubMed

    Yao, Wan X; Li, Jinqi; Jiang, Zhiguo; Gao, Jia-Hong; Franklin, Crystal G; Huang, Yufei; Lancaster, Jack L; Yue, Guang H

    2014-01-01

    Previous studies report greater activation in the cortical motor network in controlling eccentric contraction (EC) than concentric contraction (CC) despite lower muscle activation level associated with EC vs. CC in healthy, young individuals. It is unknown, however, whether elderly people exhibiting increased difficulties in performing EC than CC possess this unique cortical control mechanism for EC movements. To address this question, we examined functional magnetic resonance imaging (fMRI) data acquired during EC and CC of the first dorsal interosseous (FDI) muscle in 11 young (20-32 years) and 9 old (67-73 years) individuals. During the fMRI experiment, all subjects performed 20 CC and 20 EC of the right FDI with the same angular distance and velocity. The major findings from the behavioral and fMRI data analysis were that (1) movement stability was poorer in EC than CC in the old but not the young group; (2) similar to previous electrophysiological and fMRI reports, the EC resulted in significantly stronger activation in the motor control network consisting of primary, secondary and association motor cortices than CC in the young and old groups; (3) the biased stronger activation towards EC was significantly greater in the old than the young group especially in the secondary and association cortices such as supplementary and premotor motor areas and anterior cingulate cortex; and (4) in the primary motor and sensory cortices, the biased activation towards EC was significantly greater in the young than the old group. Greater activation in higher-order cortical fields for controlling EC movement by elderly adults may reflect activities in these regions to compensate for aging-related impairments in the ability to control complex EC movements. Our finding is useful for potentially guiding the development of targeted therapies to counteract age-related movement deficits and to prevent injury.

  16. 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.

  17. Mechanism of production of troponin T fragments during postmortem aging of porcine muscle.

    PubMed

    Kitamura, Shin-ichi; Muroya, Susumu; Tanabe, Soichi; Okumura, Tomoyuki; Chikuni, Koichi; Nishimura, Toshihide

    2005-05-18

    Troponin T (TnT) is one of the myofibrillar proteins that is easily degraded during postmortem aging of pork. In this study, we determined the N-terminal amino acid sequences of TnT degradation fragments produced during postmortem aging and by m-calpain hydrolysis. The N-terminal amino acid sequences of TnT fragments produced during postmortem aging were EVHEPEEKPRPKLTAP, EKPRPKLTAPKIPEG, and APKIPEGEKVDF. On the other hand, the N-terminal amino acid sequences of TnT fragments produced by the action of m-calpain were APPPPAEV, EVHEPEEK, and APK. These sequences of degradation fragments could be mapped on fast type TnT isoform 2. The peptide bonds of His37-Glu38 and Thr51-Ala52 in fTnT2 were cleaved during postmortem aging as well as by the calpain hydrolysis; therefore, calpain was concluded to have an important role in TnT degradation during postmortem aging. It was also found that the sourness-suppressing peptide APPPPAEVHEVHEEVH (Okumura et al. Biosci. Biotechnol. Biochem. 2004, 68, 1657-1662) derived from TnT degradation could be produced by the action of calpains on Glu21-Ala22 and His37-Glu38 sites.

  18. Saltstone Disposal Facility Mechanically Stabilized Earth Vault Closure Cap Degradation Base Case: Institutional Control To Pine Forest Scenario

    SciTech Connect

    Phifer, MA

    2004-03-19

    As part of the current Saltstone Disposal Facility (SDF) Performance Assessment (PA) revision, the closure cap configuration was reevaluated and closure cap degradation mechanisms and their impact upon infiltration through the closure cap was evaluated for the existing SDF concrete vaults (i.e. vaults 1 and 4) for the base case land use scenario (i.e. institutional control to pine forest scenario) and documented in Phifer and Nelson (2003). The closure cap configuration was modified from a compacted kaolin barrier layer concept to a geosynthetic clay layer (GCL) barrier layer concept. The degradation mechanisms developed included pine forest succession, erosion, and colloidal clay migration. These degradation mechanisms resulted in changes in the hydraulic properties of the closure cap layers and resulting increases in infiltration through the closure cap over time.

  19. Establishing in situ conditions of Hanford waste tanks subjected to the aging effects of thermal degradation and creep of concrete

    SciTech Connect

    Julyk, L.J.; Weis, M.P.; Dyrness, A.D.

    1993-10-01

    Some of the underground reinforced-concrete waste-storage tanks at the US Department of Energy`s Hanford Site have been exposed to high temperatures (greater than 200{degrees}F) generated by radioactive liquid wastes. Establishment of the in situ conditions of these tanks is the first step toward their remediation. In this environment concrete damage can result in the form of mechanical property degradation, increased creep response, and cracking from thermal expansion and load redistribution. Regression analyses of data from tests on Hanford-concrete mix designs conducted in the mid-1970`s provided mechanical property correlations that are a function of time at temperature. Creep compliance functions were developed on the bases of literature reviews and limited Hanford Site test data. The property-degradation correlations are thermal-history dependent because of the irreversible nature of the degradation processes. In addition, tests were conducted to determine the thermal expansion coefficient of the Hanford concrete. This paper discusses the implementation of these correlations into a nonlinear concrete constitutive subroutine that is linked to a general-purpose finite- element computer code. The methodology used to treat variable temperature histories is illustrated. A case study of the Hanford Site`s buried, high-heat, single-shell, waste storage tank 241-C-106 illustrates the degradation history predicted over its service life. In addition, this paper provides a statistically based discussion of the effects of potential batch-to-batch variation of concrete strength. It addresses material property uncertainties, including the thermal-expansion coefficient.

  20. 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

  1. 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.

  2. Gene expression metadata analysis reveals molecular mechanisms employed by Phanerochaete chrysosporium during lignin degradation and detoxification of plant extractives.

    PubMed

    Kameshwar, Ayyappa Kumar Sista; Qin, Wensheng

    2017-03-08

    Lignin, most complex and abundant biopolymer on the earth's surface, attains its stability from intricate polyphenolic units and non-phenolic bonds, making it difficult to depolymerize or separate from other units of biomass. Eccentric lignin degrading ability and availability of annotated genome make Phanerochaete chrysosporium ideal for studying lignin degrading mechanisms. Decoding and understanding the molecular mechanisms underlying the process of lignin degradation will significantly aid the progressing biofuel industries and lead to the production of commercially vital platform chemicals. In this study, we have performed a large-scale metadata analysis to understand the common gene expression patterns of P. chrysosporium during lignin degradation. Gene expression datasets were retrieved from NCBI GEO database and analyzed using GEO2R and Bioconductor packages. Commonly expressed statistically significant genes among different datasets were further considered to understand their involvement in lignin degradation and detoxification mechanisms. We have observed three sets of enzymes commonly expressed during ligninolytic conditions which were later classified into primary ligninolytic, aromatic compound-degrading and other necessary enzymes. Similarly, we have observed three sets of genes coding for detoxification and stress-responsive, phase I and phase II metabolic enzymes. Results obtained in this study indicate the coordinated action of enzymes involved in lignin depolymerization and detoxification-stress responses under ligninolytic conditions. We have developed tentative network of genes and enzymes involved in lignin degradation and detoxification mechanisms by P. chrysosporium based on the literature and results obtained in this study. However, ambiguity raised due to higher expression of several uncharacterized proteins necessitates for further proteomic studies in P. chrysosporium.

  3. A constitutive model for bonded geomaterials subject to mechanical and/or chemical degradation

    NASA Astrophysics Data System (ADS)

    Nova, R.; Castellanza, R.; Tamagnini, C.

    2003-08-01

    The mechanical behaviour of bonded geomaterials is described by means of an elastoplastic strain-hardening model. The internal variables, taking into account the history of the material, depend on the plastic strains experienced and on a conveniently defined scalar measure of damage induced by weathering and/or chemical degradation.For the sake of simplicity, it is assumed that only internal variables are affected by mechanical and chemical history of the material. Despite this simplifying assumption, it can be shown that many interesting phenomena exhibited by weathered bonded geomaterials can be successfully described. For instance, (i) the transition from brittle to ductile behaviour with increasing pressure of a calcarenite with collapsing internal structure, (ii) the complex behaviour of chalk and other calcareous materials in oedometric tests, (iii) the chemically induced variation of the stress and strain state of such kind of materials, are all phenomena that can be qualitatively reproduced. Several comparisons with experimental data show that the model can capture the observed behaviour also quantitatively.

  4. Mechanisms of photocatalytical degradation of monomethylarsonic and dimethylarsinic acids using nanocrystalline titanium dioxide.

    PubMed

    Xu, Zhonghou; Jing, Chuanyong; Li, Fasheng; Meng, Xiaoguang

    2008-04-01

    Photodegradation mechanisms of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) with nanocrystalline titanium dioxide under UV irradiation were investigated. In the presence of UV irradiation and 0.02 g/L TiO2, 93% MMA (initial concentration is 10 mg-As/L) was transformed into inorganic arsenate, [As(V)], after 72 h of a batch reaction. The mineralization of DMA to As(V) occurred in two steps with MMA as an intermediate product. The photodegradation rate of MMA and DMA could be described using first-order kinetics, where the apparent rate constant is 0.033/h and 0.013/h for MMA and DMA, respectively. Radical scavengers, including superoxide dimutase (SOD), sodium bicarbonate, tert-butanol, and sodium azide, were used to study the photodegradation mechanisms of MMA and DMA. The results showed that hydroxyl radicals (HO*) was the primary reactive oxygen species for the photodegradation of MMA and DMA. The methyl groups in MMA and DMAweretransformed into organic carbon, including formic acid and possibly methanol, also through photochemical reactions. The results showed that nanocrystalline TiO2 can be used for the photocatalytical degradation of MMA and DMA and subsequent removal of the converted As(V), since the high adsorption capacity of the material for inorganic arsenic species has been demonstrated in previous studies.

  5. Lithium chloride prevents interleukin-1β induced cartilage degradation and loss of mechanical properties.

    PubMed

    Thompson, Clare L; Yasmin, Habiba; Varone, Anna; Wiles, Anna; Poole, C Antony; Knight, Martin M

    2015-10-01

    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.

  6. 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. PMID:27879719

  7. Thermal Degradation, Mechanical Properties and Morphology of Wheat Straw Flour Filled Recycled Thermoplastic Composites.

    PubMed

    Mengeloglu, Fatih; Karakus, Kadir

    2008-01-24

    Thermal behaviors of wheat straw flour (WF) filled thermoplastic compositeswere measured applying the thermogravimetric analysis and differential scanningcalorimetry. Morphology and mechanical properties were also studied using scanningelectron microscope and universal testing machine, respectively. Presence of WF inthermoplastic matrix reduced the degradation temperature of the composites. One for WFand one for thermoplastics, two main decomposition peaks were observed. Morphologicalstudy showed that addition of coupling agent improved the compatibility between WFs andthermoplastic. WFs were embedded into the thermoplastic matrix indicating improvedadhesion. However, the bonding was not perfect because some debonding can also be seenon the interface of WFs and thermoplastic matrix. In the case of mechanical properties ofWF filled recycled thermoplastic, HDPE and PP based composites provided similar tensileand flexural properties. The addition of coupling agents improved the properties ofthermoplastic composites. MAPE coupling agents performed better in HDPE while MAPPcoupling agents were superior in PP based composites. The composites produced with thecombination of 50-percent mixture of recycled HDPE and PP performed similar with theuse of both coupling agents. All produced composites provided flexural properties requiredby the ASTM standard for polyolefin-based plastic lumber decking boards.

  8. 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.

  9. Mechanism and pathways of chlorfenapyr photocatalytic degradation in aqueous suspension of TiO2.

    PubMed

    Cao, Yongsong; Yi, Lei; Huang, Lu; Hou, Ying; Lu, Yitong

    2006-05-15

    The light-induced degradation of chlorfenapyr under UV was investigated in aqueous solutions containing TiO2 as photocatalyst. The photocatalytic degradation of chlorfenapyr followed pseudo-first-order degradation kinetics (Ct = C0e(-kt)). The study focused on the identification of possible intermediate products during the degradation, using gas chromatography mass-spectrometry (GC-MS) and 1HNMR. Six aromatic intermediates were identified by several techniques during the treatment and some of them were further confirmed by matching authentic standards. Structure analysis of the degradation products suggested two degradation pathways: (1) The aliphatic ether group was cleaved from chlorfenapyr to form pyrrole-alph-carboxylic acid, then the pyrrole group was broken to form 4-chloroglycine; (2) Chlorfenapyr was debrominated and the aliphatic ether group was cleaved from the pyrrole group, which was further broken to form 4-chlorophenylglycine. The glycine was degraded into 4-chlorobenzoic acids, which was further broken into inorganic ions and CO2.

  10. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    NASA Astrophysics Data System (ADS)

    Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej

    2016-12-01

    The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800-900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic "cauliflower-shape protrusions". The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires' surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires' preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better understanding of the precious metals etching and deposition processes during oxidation.

  11. 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.

  12. 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.

  13. 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.

  14. 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).

  15. Explaining the variation in lamb longissimus shear force across and within ageing periods using protein degradation, sarcomere length and collagen characteristics.

    PubMed

    Starkey, Colin P; Geesink, Geert H; Oddy, V Hutton; Hopkins, David L

    2015-07-01

    Meat tenderness is known to be affected by sarcomere length (SL), proteolysis and collagen content (CC). Sixty lambs were slaughtered and the Longissimus muscle was sampled. Samples for shear force (SF), SL, proteolysis indicators (desmin degradation, particle size: PS) and CC were taken after the allotted ageing periods (1, 7, and 14 days). PS explained a large part of the variation in shear force (approximately 34%) when modelled across ageing periods. Other factors (CC, SL) combined with proteolysis indicators (PS, desmin degradation) explained just under 40% of the variation in shear force. Within ageing periods SL explained a small, but significant, part of the variation in shear force after 14 days of ageing (8%) and at day 1 of ageing desmin degradation explained 17% of the variation in shear force. Methods to improve the tenderness of lamb longissimus muscle should focus on increasing the extent of post-mortem proteolysis, when processing conditions are sufficient to prevent muscle fibre shortening.

  16. Stereoselective Degradation and Molecular Ecological Mechanism of Chiral Pesticides Beta-Cypermethrin in Soils with Different pH Values.

    PubMed

    Yang, Zhong-Hua; Ji, Guo-Dong

    2015-12-15

    For decades, pesticides have been widely used for agricultural activities around the world, and the environmental problems caused by these compounds have raised widespread concern. However, the different enantioselective behaviors of chiral pesticide enantiomers are often ignored. Here, the selective degradation patterns and mechanisms of chiral pesticide enantiomers were successfully investigated for the first time in the soils of three cultivation areas with different pH values. Beta-cypermethrin was chosen as the target analyte. We found that the degradation rates of the four isomers of beta-cypermethrin were different. We used stepwise regression equations between degradation rates and functional genes to quantitatively study their relationships. Quantitative response analysis revealed that different isomers have different equations even under identical conditions. The results of path analysis showed that a single functional gene can make different direct and indirect contributions to the degradation of different isomers. Finally, the high-throughput technology was used to analysis the genome of the three tested soils and then compared the main microbial communities in them. We have successfully devised a method to investigate the molecular biological mechanisms of the selective degradation behavior of chiral compounds, thus enabling us to better understand these mechanisms.

  17. 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.

  18. 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.

  19. 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...

  20. Degradation mechanism of sulfonated poly(ether ether ketone) (SPEEK) ion exchange membranes under vanadium flow battery medium.

    PubMed

    Yuan, Zhizhang; Li, Xianfeng; Hu, Jinbo; Xu, Wanxing; Cao, Jingyu; Zhang, Huamin

    2014-10-07

    The degradation mechanism of hydrocarbon ion exchange membranes under vanadium flow battery (VFB) medium was investigated and clarified for the first time. This work will be highly beneficial for improving the chemical stability of hydrocarbon ion exchange membranes, which is one of the most challenging issues for VFB application.

  1. Unraveling the Degradation Mechanism of Purine Nucleotides Photosensitized by Pterins: The Role of Charge-Transfer Steps.

    PubMed

    Serrano, Mariana P; Lorente, Carolina; Borsarelli, Claudio D; Thomas, Andrés H

    2015-07-20

    Photosensitized reactions contribute to the development of skin cancer and are used in many applications. Photosensitizers can act through different mechanisms. It is currently accepted that if the photosensitizer generates singlet molecular oxygen ((1) O2 ) upon irradiation, the target molecule can undergo oxidation by this reactive oxygen species and the reaction needs dissolved O2 to proceed, therefore the reaction is classified as (1) O2 -mediated oxidation (type II mechanism). However, this assumption is not always correct, and as an example, a study on the degradation of 2'-deoxyguanosine 5'-monophosphate photosensitized by pterin is presented. A general mechanism is proposed to explain how the degradation of biological targets, such as nucleotides, photosensitized by pterins, naturally occurring (1) O2 photosensitizers, takes place through an electron-transfer-initiated process (type I mechanism), whereas the contribution of the (1) O2 -mediated oxidation is almost negligible.

  2. 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…

  3. Mechanical-property degradation of cast stainless steel components from the Shippingport reactor

    SciTech Connect

    Chopra, O.K.

    1991-10-01

    The mechanical properties of cast stainless steels from the Shippingport reactor have been characterized. Baseline properties for unaged materials were obtained from tests on either recovery-annealed material or material from a cooler region of the component. The materials exhibited modest decrease in impact energy and fracture toughness and a small increase in tensile strength. The fracture toughness J-R curve, J{sub IC} value, tensile flow stress, and Charpy-impact energy of the materials showed very good agreement with estimations based on accelerated laboratory aging studies. The kinetics of thermal embrittlement and degree of embrittlement at saturation, i.e., the minimum impact energy that would be achieved after long-term aging, were established from materials that were aged further in the laboratory at temperatures between 320 and 400{degrees}C. The results showed very good agreement with estimates; the activation energies ranged from 125 to 250 kJ/mole and the minimum room temperature impact energy was <75 J/cm{sup 2}. The estimated impact energy and fracture toughness J-R curve for materials from the Ringhals reactor hot and crossover-leg elbows are also presented.

  4. Oxidative degradation of organic acid conjugated with sulfite oxidation in flue gas desulfurization: products, kinetics and mechanism

    SciTech Connect

    Lee, Y.J.; Rochelle, G.T.

    1987-03-01

    Organic acid degradation conjugated with sulfite oxidation has been studied under flue gas desulfurization (FGD) conditions. The oxidative degradation constant k/sub 12/ is defined as the ratio of organic acid degradation rate and sulfite oxidation rate times the ratio of the concentration of dissolved S(IV) and organic acid. It is not significantly affected by pH or dissolved oxygen in the absence of manganese or iron. However, k/sub 12/ is increased by certain transition metals such as Fe, Co, and Ni and is decreased by Mn and halides. Lower dissolved S(IV) magnifies these effects. A free radical mechanism was proposed to describe the kinetics. Hydroxy and sulfonated carboxylic acids degrade approximately 3 times slower than saturated dicarboxylic acids, while maleic acid, an unsaturated dicarboxylic acid, degraded an order of magnitude factor. A wide spectrum of degradation products of adipic acid were found, including carbon dioxide - the major product - smaller dicarboxylic acids, monocarboxylic acids, other carbonyl compounds, and hydrocarbons. 30 references, 7 figures, 7 tables.

  5. 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.

  6. 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.

  7. 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.

  8. Active site structure and catalytic mechanism of phosphodiesterase for degradation of intracellular second messengers

    NASA Astrophysics Data System (ADS)

    Zhan, Chang-Guo

    2002-03-01

    Phosphodiesterases are clinical targets for a variety of biological disorders, because this superfamily of enzymes regulate intracellular concentration of cyclic nucleotides that serve as the second messengers playing a critical role in a variety of physiological processes. Understanding structure and mechanism of a phosphodiesterase will provide a solid basis for rational design of the more efficient therapeutics. Although a three-dimensional X-ray crystal structure of the catalytic domain of human phosphodiesterase 4B2B was recently reported, it was uncertain whether a critical bridging ligand in the active site is a water molecule or a hydroxide ion. The identity of this bridging ligand has been determined by performing first-principles quantum chemical calculations on models of the active site. All the results obtained indicate that this critical bridging ligand in the active site of the reported X-ray crystal structure is a hydroxide ion, rather than a water molecule, expected to serve as the nucleophile to initialize the catalytic degradation of the intracellular second messengers.

  9. Exploring the mechanical behavior of degrading swine neural tissue at low strain rates via the fractional Zener constitutive model.

    PubMed

    Bentil, Sarah A; Dupaix, Rebecca B

    2014-02-01

    The ability of the fractional Zener constitutive model to predict the behavior of postmortem swine brain tissue was examined in this work. Understanding tissue behavior attributed to degradation is invaluable in many fields such as the forensic sciences or cases where only cadaveric tissue is available. To understand how material properties change with postmortem age, the fractional Zener model was considered as it includes parameters to describe brain stiffness and also the parameter α, which quantifies the viscoelasticity of a material. The relationship between the viscoelasticity described by α and tissue degradation was examined by fitting the model to data collected in a previous study (Bentil, 2013). This previous study subjected swine neural tissue to in vitro unconfined compression tests using four postmortem age groups (<6h, 24h, 3 days, and 1 week). All samples were compressed to a strain level of 10% using two compressive rates: 1mm/min and 5mm/min. Statistical analysis was used as a tool to study the influence of the fractional Zener constants on factors such as tissue degradation and compressive rate. Application of the fractional Zener constitutive model to the experimental data showed that swine neural tissue becomes less stiff with increased postmortem age. The fractional Zener model was also able to capture the nonlinear viscoelastic features of the brain tissue at low strain rates. The results showed that the parameter α was better correlated with compressive rate than with postmortem age.

  10. Polymer Coatings Degradation Properties

    DTIC Science & Technology

    1985-02-01

    release; distribution unlimited. 17. DISTRIBUTION STATEMENT (of 1*. 460060 00md ( Ag 8106k 2.It 4011--t - RepiI) Is. SUPPLEMENTARY NOTES IS. KEY WORDS...two radicals interact The photodegradation mechanism of poly(urethanes) is not known in detail, however, much has been added to our understanding. The...red PAS is also consistent with the probable degradation mechanism, i.e. disappearance of the urethane link- ages . This is another sensitive technique

  11. 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.

  12. 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.

  13. 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

  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. Regional Patterns of Ice-Wedge Degradation Across Northern Alaska: What Does Asynchronous Timing of Onset Tell Us Regarding Triggering Mechanisms, Thresholds, and Impacts?

    NASA Astrophysics Data System (ADS)

    Frost, G. V., Jr.; Macander, M. J.; Liljedahl, A. K.; Walker, D. A.

    2015-12-01

    Ice-wedge polygons are conspicuous and widespread in arctic landscapes, creating complex microtopography and strong, meter-scale contrasts in hydrology, soil, vegetation, and ground ice conditions. Thaw of the upper portion of ice-wedges results in ground subsidence (thermokarst), plant mortality and the formation of small, flooded pits along the polygon margins. Secondary impacts, such as changes in flowpaths, spatially-variable flooding and drainage of polygon centers, and thermal erosion of permafrost, extend well beyond the thermokarst pits themselves. We delineated small waterbodies in historical airphotos and modern high-resolution satellite imagery and made ground observations across a network of 45 km2 study areas spanning the western and central regions of Alaska's North Slope. The imagery archive covers three epochs: 1948-1955, 1979-1985, and 2009-2012. Our analysis focused on residual upland surfaces dominated by Holocene-aged ice wedges, where surface water is mainly restricted to degraded ice-wedges. Total extent of flooded pits increased at most landscapes since circa 1980 (range -27 - +135%; median +10.6%). An intriguing regional pattern was evident: degradation of Holocene ice-wedges was already well underway by 1950 across much of the western North Slope, but degradation initiated much more recently on eolian sand and silt (yedoma) deposits prevalent to the east. Our results indicate that recent degradation of Holocene ice wedges across northern Alaska cannot be explained by late-20th century warmth alone. Possible mechanisms for earlier onset of degradation on the western North Slope include differences in recent climate history, snow regime, and thermal and physical properties of surficial materials. These findings provide context for interpreting and predicting ice-wedge thermokarst processes, thresholds, and impacts in Alaska and elsewhere in the circumpolar arctic.

  16. 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

  17. Modeling mechanical degradation in lithium ion batteries during cycling: Solid electrolyte interphase fracture

    NASA Astrophysics Data System (ADS)

    Laresgoiti, Izaro; Käbitz, Stefan; Ecker, Madeleine; Sauer, Dirk Uwe

    2015-12-01

    During cycling, mechanical stresses can occur in the composite electrode, inside the active material, but also in the solid electrolyte interphase layer. A mechanical model is proposed based on a system made of a spherical graphite particle surrounded by the solid electrolyte interphase layer. During lithium intercalation or de-intercalation, stresses in the graphite are produced, governed by the diffusion induced stress phenomena and in the solid electrolyte interphase, driven by the graphite expansion. The stresses in both materials were simulated and a sensitivity analysis was performed to clarify the influence of principal parameters on both processes. Finally, assuming that the solid electrolyte interphase is the weakest material and therefore more prone to fracture than graphite, the experimental capacity fade during cycling was modeled based on its break and repair effect rather than on the fracture of the active material. The mechanical model of the solid electrolyte interphase was implemented in a single particle lithium ion battery model in order to reproduce capacity fade during battery lifetime. The model results were compared against cycle life aging experimental data, reproducing accurately the influence of the depth of discharge as well as the average state of charge on the capacity fade.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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

  9. Nanohydroxyapatite Effect on the Degradation, Osteoconduction and Mechanical Properties of Polymeric Bone Tissue Engineered Scaffolds

    PubMed Central

    Salmasi, Shima; Nayyer, Leila; Seifalian, Alexander M.; Blunn, Gordon W.

    2016-01-01

    BACKGROUND Statistical reports show that every year around the world approximately 15 million bone fractures occur; of which up to 10% fail to heal completely and hence lead to complications of non-union healing. In the past, autografts or allografts were used as the “gold standard” of treating such defects. However, due to various limitations and risks associated with these sources of bone grafts, other avenues have been extensively investigated through which bone tissue engineering; in particular engineering of synthetic bone graft substitutes, has been recognised as a promising alternative to the traditional methods. METHODS A selective literature search was performed. RESULTS Bone tissue engineering offers unlimited supply, eliminated risk of disease transmission and relatively low cost. It could also lead to patient specific design and manufacture of implants, prosthesis and bone related devices. A potentially promising building block for a suitable scaffold is synthetic nanohydroxyapatite incorporated into synthetic polymers. Incorporation of nanohydroxyapatite into synthetic polymers has shown promising bioactivity, osteoconductivity, mechanical properties and degradation profile compared to other techniques previously considered. CONCLUSION Scientific research, through extensive physiochemical characterisation, in vitro and in vivo assessment has brought together the optimum characteristics of nanohydroxyapatite and various types of synthetic polymers in order to develop nanocomposites of suitable nature for bone tissue engineering. The aim of the present article is to review and update various aspects involved in incorporation of synthetic nanohydroxyapatite into synthetic polymers, in terms of their potentials to promote bone growth and regeneration in vitro, in vivo and consequently in clinical applications. PMID:28217213

  10. 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

  11. Mechanisms of age-related macular degeneration and therapeutic opportunities.

    PubMed

    van Lookeren Campagne, Menno; LeCouter, Jennifer; Yaspan, Brian L; Ye, Weilan

    2014-01-01

    As the age of the population increases in many nations, age-related degenerative diseases pose significant socioeconomic challenges. One of the key degenerative diseases that compromise quality of life is age-related macular degeneration (AMD). AMD is a multi-faceted condition that affects the central retina, which ultimately leads to blindness in millions of people worldwide. The pathophysiology and risk factors for AMD are complex, and the symptoms manifest in multiple related but distinct forms. The ability to develop effective treatments for AMD will depend on a thorough understanding of the underlying pathophysiology, risk factors, and driver molecular pathways, as well as the ability to develop useful animal models. This review provides an overview of the aforementioned aspects in AMD.

  12. Aging mechanisms in amorphous phase-change materials.

    PubMed

    Raty, Jean Yves; Zhang, Wei; Luckas, Jennifer; Chen, Chao; Mazzarello, Riccardo; Bichara, Christophe; Wuttig, Matthias

    2015-06-24

    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.

  13. Determining the degradation efficiency and mechanisms of ethyl violet using HPLC-PDA-ESI-MS and GC-MS

    PubMed Central

    2012-01-01

    Background The discharge of wastewater that contains high concentrations of reactive dyes is a well-known problem associated with dyestuff activities. In recent years, semiconductor photocatalysis has become more and more attractive and important since it has a great potential to contribute to such environmental problems. One of the most important aspects of environmental photocatalysis is in the selection of semiconductor materials like ZnO and TiO2, which are close to being two of the ideal photocatalysts in several respects. For example, they are relatively inexpensive, and they provide photo-generated holes with high oxidizing power due to their wide band gap energy. In this work, nanostructural ZnO film on the Zn foil of the Alkaline-Manganese Dioxide-Zinc Cell was fabricated to degrade EV dye. The major innovation of this paper is to obtain the degradation mechanism of ethyl violet dyes resulting from the HPLC-PDA-ESI-MS analyses. Results The fabrication of ZnO nanostructures on zinc foils with a simple solution-based corrosion strategy and the synthesis, characterization, application, and implication of Zn would be reported in this study. Other objectives of this research are to identify the reaction intermediates and to understand the detailed degradation mechanism of EV dye, as model compound of triphenylmethane dye, with active Zn metal, by HPLC-ESI-MS and GC-MS. Conclusions ZnO nanostructure/Zn-foils had an excellent potential for future applications on the photocatalytic degradation of the organic dye in the environmental remediation. The intermediates of the degradation process were separated and characterized by the HPLC-PDA-ESI-MS and GC-MS, and twenty-six intermediates were characterized in this study. Based on the variation of the amount of intermediates, possible degradation pathways for the decolorization of dyes are also proposed and discussed. PMID:22748361

  14. 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

  15. 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.

  16. Efficient degradation of sulfamethoxazole by the Fe(II)/HSO5(-) process enhanced by hydroxylamine: Efficiency and mechanism.

    PubMed

    Liu, Guifang; Li, Xuchun; Han, Bangjun; Chen, Liwei; Zhu, Linan; Campos, Luiza C

    2017-01-15

    Fenton or Fenton-like processes have been regarded as feasible methods to degrade a wide variety of contaminants by generating reactive species, but the efficiency is still challenged by the slow transformation from Fe(III) to Fe(II) and pH. This study employed hydroxylamine (HA) to improve the oxidation efficiency of Fe(II)/HSO5(-) (Fe(II)/PMS) process, by selecting sulfamethoxazole (SMX) as the target compound. The degradation efficiency and mechanism of SMX by the HA/Fe(II)/PMS process were elucidated for the first time. Compared with Fe(II)/PMS process, the HA/Fe(II)/PMS process showed about 4 times higher degradation efficiency of SMX at pH 3.0. The analysis of steady-state concentration of Fe species indicated that HA enhanced the transformation of Fe(III) to Fe(II), sustaining the rapid Fenton-like reactions. Both sulfate radicals and hydroxyl radicals accounted for the degradation of SMX, with the latter regarded as the dominant reactive species. Degradation intermediates of SMX were further analyzed, and three main transformation pathways were thus proposed. The HA/Fe(II)/PMS process was also effective in the removal of SMX and total organic carbon from real pharmaceutical wastewater. This work would broaden the scope of application of Fenton and Fenton-like processes enhanced by HA in contaminants treatment.

  17. Ozonation of metoprolol in aqueous solution: ozonation by-products and mechanisms of degradation.

    PubMed

    Tay, Kheng Soo; Rahman, Noorsaadah Abd; Abas, Mhd Radzi Bin

    2013-05-01

    This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O3) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (•OH).

  18. 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.

  19. 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

  20. Cellular senescence in aging and age-related disease: from mechanisms to therapy.

    PubMed

    Childs, Bennett G; Durik, Matej; Baker, Darren J; van Deursen, Jan M

    2015-12-01

    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.

  1. Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO(2) aqueous solution.

    PubMed

    Cao, Hua; Lin, Xiulian; Zhan, Haiying; Zhang, Hong; Lin, Jingxin

    2013-01-01

    5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO(2) heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that ()OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.

  2. Investigating the morphological, mechanical and degradation properties of scaffolds comprising collagen, gelatin and elastin for use in soft tissue engineering.

    PubMed

    Grover, Chloe N; Cameron, Ruth E; Best, Serena M

    2012-06-01

    Collagen-based scaffolds can be used to mimic the extracellular matrix (ECM) of soft tissues and provide support during tissue regeneration. To better match the native ECM composition and mechanical properties as well as tailor the degradation resistance and available cell binding motifs, other proteins or different collagen types may be added. The present study has explored the use of components such as gelatin or elastin and investigated their effect on the bulk physical properties of the resulting scaffolds compared to those made from pure collagen type I. The effect of altering the composition and crosslinking was evaluated in terms of the scaffold structure, mechanical properties, swelling, degradation and cell attachment. Results demonstrate that scaffolds based on gelatin had reduced tensile stiffness and degradation time compared with collagen. The addition of elastin reduced the overall strength and stiffness of the scaffolds, with electron microscopy results suggesting that insoluble elastin interacts best with collagen and soluble elastin interacts best with gelatin. Carbodiimide crosslinking was essential for structural stability, strength and degradation resistance for scaffolds of all compositions. In addition, preliminary cell adhesion studies showed these highly porous structures (pore size 130-160 μm) to be able to support HT1080 cell infiltration and growth. Therefore, this study suggests that the use of gelatin in place of collagen, with additions of elastin, can tailor the physical properties of scaffolds and could be a design strategy for reducing the overall material costs.

  3. Oxalate enhanced mechanism of hydroxyl-Fe-pillared bentonite during the degradation of Orange II by UV-Fenton process.

    PubMed

    Chen, Jianxin; Zhu, Lizhong

    2011-01-30

    An enhanced method of hydroxyl-Fe-pillared bentonite (H-Fe-P-B) during the degradation of Orange II was studied to provide novel insight to interactions of degradation intermediates with heterogeneous catalyst in UV-Fenton system. Based on the degradation mechanism of Orange II, oxalate enhanced mechanism of H-Fe-P-B in heterogeneous UV-Fenton system was developed. The results showed that additional oxalate could increase the Fe leaching of H-Fe-P-B during heterogeneous UV-Fenton process, which led to higher mineralization efficiency of Orange II and lower energy consumption of treatment. When the concentrations of additional sodium oxalate increased up to 0.1 mmol L(-1), 0.2 mmol L(-1) and 0.4 mmol L(-1), the rate of Orange II degradation could increase 30%, 46% and 63%, respectively. The iron ions leached from catalyst could be adsorbed back to the catalyst again after the organic intermediates were mineralized completely. Then the catalyst of H-Fe-P-B could be reused and additional pollution caused by iron ions could be avoided.

  4. 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.

  5. Formation and Degradation of Furfuryl Alcohol, 5-Methylfurfuryl Alcohol, Vanillyl Alcohol, and Their Ethyl Ethers in Barrel-Aged Wines.

    PubMed

    Spillman; Pollnitz; Liacopoulos; Pardon; Sefton

    1998-02-16

    Furfural, 5-methylfurfural, and vanillin co-occurred in 64 barrel-aged red, white, and model wines with the reduction products, furfuryl alcohol, 5-methylfurfuryl alcohol, and vanillyl alcohol, and with the corresponding ethyl ethers of these alcohols. Hydrolytic studies in a model wine have shown that 5-methylfurfuryl ethyl ether is formed rapidly from 5-methylfurfuryl alcohol, but both decomposed quickly under the conditions. Vanillyl ethyl ether was also formed relatively rapidly, and both this ether and vanillyl alcohol were stable in the model wine. The formation of furfuryl ethyl ether from furfuryl alcohol and the subsequent decomposition of these two compounds were comparatively slow. The relative concentration of these aromatic alcohols and ethers in the barrel-aged wines was consistent with the observed stability of the furan derivatives, but low concentrations of vanillyl alcohol and vanillyl ethyl ether observed in all samples showed that factors other than solvolytic degradation were responsible for reducing the concentration of these compounds in wine. Furfuryl ethyl ether, which had an aroma threshold of 430 µg/L in a white wine, was found at approximate concentrations of up to 230 µg/L in the wines.

  6. 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

  7. Mechanical Properties of Mass Concrete at Early Ages

    DTIC Science & Technology

    1991-08-01

    material properties during the time that concrete is undergoing the greatest amount of thermal activity and physical change (i.e. early ages, less than 3...Type II, low alkali (LA) portland cement meeting ASTM C 150 and a Class C fly ash meeting ASTM C 618 [11 i]. The fine aggregate was a natural sand...usually require that specially developed or modified models be used. It should also be noted that the use- of high percentages of pozzolans in mass

  8. The effect of low temperature aging on the mechanical property & phase stability of Y-TZP ceramics

    PubMed Central

    Kim, Hyung-Tae; Yang, Jae-Ho; Lee, Jai-Bong; Kim, Sung-Hun

    2009-01-01

    STATEMENT OF PROBLEM Recently Yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) has been introduced due to superior flexural strength and fracture toughness compared to other dental ceramic systems. Although zirconia has outstanding mechanical properties, the phenomenon of decrease in the life-time of zirconia resulted from degradation in flexural strength after low temperature aging has been reported. PURPOSE The objective of this study was to investigate degradation of flexural strength of Y-TZP ceramics after various low temperature aging treatments and to evaluate the phase stability and micro-structural change after aging by using X-ray diffraction analysis and a scanning electron microscope (SEM). MATERIAL AND METHODS Y-TZP blocks of Vita In-Ceram YZ (Vita Zahnfabrik, Bad Säckingen, Germany) were prepared in 40 mm (length) × 4 mm (width) × 3 mm (height) samples. Specimens were artificially aged in distilled water by heat-treatment at a temperature of 75, 100, 125, 150, 175, 200, and 225℃ for 10 hours, in order to induce the phase transformation at the surface. To measure the mechanical property, the specimens were subjected to a four-point bending test using a universal testing machine (Instron model 3365; Instron, Canton, Mass, USA). In addition, X-ray diffraction analysis (DMAX 2500; Rigaku, Tokyo, Japan) and SEM (Hitachi s4700; Jeol Ltd, Tokyo, Japan) were performed to estimate the phase transformation. The statistical analysis was done using SAS 9.1.3 (SAS institute, USA). The flexural strength data of the experimental groups were analyzed by one-way analysis of variance and to detect statistically significant differences (α= .05). RESULTS The mean flexural strength of sintered Vita In-Ceram YZ without autoclaving was 798 MPa. When applied aging temperature at below 125℃ for 10 hours, the flexural strength of Vita In-Ceram YZ increased up to 1,161 MPa. However, at above 150℃, the flexural strength started to decrease. Although low

  9. 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

  10. Chelation: a fundamental mechanism of action of AGE inhibitors, AGE breakers, and other inhibitors of diabetes complications.

    PubMed

    Nagai, Ryoji; Murray, David B; Metz, Thomas O; Baynes, John W

    2012-03-01

    This article outlines evidence that advanced glycation end product (AGE) inhibitors and breakers act primarily as chelators, inhibiting metal-catalyzed oxidation reactions that catalyze AGE formation. We then present evidence that chelation is the most likely mechanism by which ACE inhibitors, angiotensin receptor blockers, and aldose reductase inhibitors inhibit AGE formation in diabetes. Finally, we note several recent studies demonstrating therapeutic benefits of chelators for diabetic cardiovascular and renal disease. We conclude that chronic, low-dose chelation therapy deserves serious consideration as a clinical tool for prevention and treatment of diabetes complications.

  11. Kinetics and mechanism of sonochemical degradation of pharmaceuticals in municipal wastewater.

    PubMed

    Xiao, Ruiyang; Wei, Zongsu; Chen, Dong; Weavers, Linda K

    2014-08-19

    A series of six pharmaceuticals were degraded by continuous wave (CW) and pulsed wave (PW) ultrasound at 205 kHz using deionized water, wastewater effluent, and its isolated organic matter matrices. In deionized water, we observed that hydrophobicity is superior to diffusivity (D(W)) for predicting degradation kinetics. Enhancements in degradation kinetics by the PW mode were greatest for the highest DW (i.e., fluorouracil (5-FU)) and K(OW) (i.e., lovastatin (LOVS)) compounds, indicating that a pharmaceutical with either high diffusivity and low hydrophobicity or low diffusivity and high hydrophobicity benefits from additional time to populate the bubble-water interface during the silent cycle of PW ultrasound. Degradation of 5-FU and LOVS were inhibited by wastewater effluent to a greater extent than the other pharmaceuticals. In addition, a pulse enhancement (PE) for 5-FU and LOVS was not present in wastewater effluent. Irradiating 5-FU and LOVS in hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) fractions of effluent organic matter (EfOM) showed that the TPI fraction reduced the PE the most, followed by the HPI and HPO fractions. The smaller size of the TPI over the HPO fraction and higher hydrophobicity of TPI over HPI implicate both size and hydrophobicity of EfOM in hindering degradation of pharmaceuticals.

  12. 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

  13. 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.

  14. Experimental and theoretical insights into photochemical transformation kinetics and mechanisms of aqueous propylparaben and risk assessment of its degradation products.

    PubMed

    An, Taicheng; Fang, Hansun; Li, Guiying; Wang, Shilong; Yao, Side

    2014-08-01

    The kinetics and mechanisms of ultraviolet photochemical transformation of propylparaben (PPB) were studied. Specific kinetics scavenging experiments coupled with quantum yield determinations were used to distinguish the roles of various reactive species induced by self-sensitized and direct photolysis reactions, and the excited triplet state of PPB ((3) PPB*) was identified as the most important species to initiate the photochemical degradation of PPB in aquatic environments. The computational results of time-resolved absorption spectra proved that (3) PPB* is a highly reactive electron acceptor, and a head-to-tail hydrogen transfer mechanism probably occurs through electron coupled with proton transfer. Physical quenching by, or chemical reaction of (3) PPB* with, O2 was confirmed as a key step affecting the initial PPB transformation pathways and degradation mechanisms. The transformation products were identified and the toxicity evolutions of PPB solutions during photochemical degradation under aerobic and anaerobic conditions were compared. The results indicate that anaerobic conditions are more likely than aerobic conditions to lead to the elimination and detoxification of PPB but less likely to lead to PPB mineralization.

  15. 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.

  16. 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.

  17. 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

  18. Functional unity of the thymus and pineal gland and study of the mechanisms of aging.

    PubMed

    Polyakova, V O; Linkova, N S; Kvetnoy, I M; Khavinson, V Kh

    2011-09-01

    The data on the morphology and functions of the thymus and pineal gland in individuals of different age are analyzed and common mechanisms of involution of these organs during aging and the consequencies of this process are discussed. Based on the data on the molecular changes in the thymus and pineal gland during aging, the authors hypothesize the functional unity of these organs and their mutual complementarity in the maintenance of normal immune and endocrine status during aging.

  19. Effect of Aging on the Microstructure and Mechanical Properties of Magnesium Alloy AZ31

    NASA Astrophysics Data System (ADS)

    Kerenciler, H.; Gündüz, S.; Erden, M. Akif; Türkmen, M.; Karabulut, H.

    2016-07-01

    The structure and mechanical properties of magnesium alloy AZ31 are studied after conventional and deformation aging under conditions corresponding to the thermal cycle of polymerization in paint coating of cars. The aging is conducted after 3-h solution treatment at 400°C, water quenching, and aging at 180°C for from 10 min to 6 h. Some of the specimens are deformed by 0.5% right after the solution treatment and then aged by the same regime.

  20. 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.

  1. Mechanical signatures of degradation of the photovoltaic perovskite CH3NH3PbI3 upon water vapor exposure

    NASA Astrophysics Data System (ADS)

    Spina, Massimo; Karimi, Ayat; Andreoni, Wanda; Pignedoli, Carlo A.; Náfrádi, Bálint; Forró, László; Horváth, Endre

    2017-03-01

    We report on the mechanical properties of CH3NH3PbI3 photovoltaic perovskite measured by nanoindentation. The Young's modulus (E) of the pristine sample is 20.0 ± 1.5 GPa, while the hardness (H) is 1.0 ± 0.1 GPa. Upon extended exposure to water vapor, both quantities decrease dramatically and the sample changes color from silver-black to yellow. Calculations based on density functional theory support this trend in the mechanical response. Chemical treatment of the degraded crystal in methylammonium iodide solution recovers the color of the pristine sample and the values of E and H within 50%.

  2. 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.

  3. Kinetics and mechanism of carbamazepine degradation by a modified Fenton-like reaction with ferric-nitrilotriacetate complexes.

    PubMed

    Sun, Sheng-Peng; Zeng, Xia; Lemley, Ann T

    2013-05-15

    This study investigated the kinetics and mechanism of carbamazepine (CBZ) degradation over an initial pH range of 5.0-9.0 by a modified Fenton-like reaction using ferric-nitrilotriacetate (Fe(III)-NTA) complexes. The results indicate that CBZ degradation by Fe(III)-NTA/H2O2 can be described by pseudo first-order kinetics and mainly attributed to hydroxyl radical (OH) attack. Ten intermediates were identified during the degradation process, including hydroxy-CBZs, 10,11-epoxy-CBZ, quinonid CBZ derivatives, dihydroxy-CBZs, and hydroxy-CBZ-10,11-diols. The steady-state concentration of OH, ranging from 3.8 × 10(-16) to 2.1 × 10(-13)M, was strongly dependent on the concentration of Fe(III), the initial pH, and H2O2:Fe(III) and NTA:Fe(III) molar ratios. Optimal conditions of [Fe(III)]=1 × 10(-4)M, [H2O2:Fe(III)]=155:1 and [NTA:Fe(III)]=3:1 were obtained for the degradation of CBZ at neutral pH (7.0) and ambient temperature (25 °C); the corresponding degradation rate constant of CBZ, kapp, was 0.0419 (± 0.002) min(-1). The value of kapp increased with increasing pH from 5.0 to 9.0 due to the strong pH-dependence of Fe(III)-NTA complexes; Fe(III)(NTA)(OH)2(2-) was the most likely active iron species to activate H2O2 to produce OH. The temperature dependence of CBZ degradation by Fe(III)-NTA/H2O2 was characterized by an activation energy of 76.16 kJ mol(-1). A potential mechanism for the formation of OH by Fe(III)-NTA/H2O2 and possible degradation pathways of CBZ are proposed.

  4. Effect of extended postmortem aging and steak location on myofibrillar protein degradation and Warner-Bratzler shear force of beef M. semitendinosus steaks.

    PubMed

    Phelps, K J; Drouillard, J S; Silva, M B; Miranda, L D F; Ebarb, S M; Van Bibber-Krueger, C L; O'Quinn, T G; Gonzalez, J M

    2016-01-01

    The objective of this study was to evaluate the effect of steak location and postmortem aging on cooked meat tenderness and myofibrillar protein degradation of steaks from M. semitendinosus (ST). Following harvest and a 6 d chill period, the left ST was removed from carcasses of crossbred feedlot steers ( = 60, average hot carcass weight 427 ± 24 kg). Each ST was fabricated into ten 2.54-cm thick steaks originating from the proximal to distal end of the muscle. Steaks cut adjacent to each other were paired, vacuum packaged, and randomly assigned to 7, 14, 21, 42, or 70 d of aging at 2 ± 1°C. After aging, within each steak pair, steaks were randomly assigned to Warner-Bratzler shear force or myofibrillar proteolysis analysis (calpain activity and desmin and troponin-T degradation). Muscle fiber type and size were also determined at the 2 ends of the muscle. There was no location × d of aging interaction ( = 0.25) for ST steak WBSF. Steak location affected (quadratic, < 0.01) WBSF. As steaks were fabricated from the proximal to distal end, WBSF values decreased toward the middle of the muscle and then increased toward the distal end. Activity of all calpains and myofibrillar protein proteolysis were unaffected by steak location ( > 0.13). Type I, IIA, and IIX muscle fibers were larger at the proximal end of the muscle than the distal end ( < 0.01). Increasing d of aging improved WBSF (quadratic, < 0.01) for the duration of the 70 d postmortem period. As d of aging increased, intact calpain-1 activity decreased (quadratic, < 0.01) with activity detected through 42 d. Day of aging affected autolyzed calpain-1 (linear, < 0.01) and calpain-2 activity (quadratic, < 0.01). Through d 70 of aging, the intensity of intact 55 kDa desmin band decreased (linear, < 0.01), while there was an increase (linear, < 0.01) in the degraded 38 kDa band. Similarly, d of aging increased troponin-T proteolysis, indicated by a decrease (quadratic, < 0.01) in intensity of the intact 40 k

  5. 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.

  6. 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.

  7. Mechanisms of humic acids degradation by white rot fungi explored using 1H NMR spectroscopy and FTICR mass spectrometry.

    PubMed

    Grinhut, Tzafrir; Hertkorn, Norbert; Schmitt-Kopplin, Philippe; Hadar, Yitzhak; Chen, Yona

    2011-04-01

    Enzymatic activities involved in decay processes of natural aromatic macromolecules, such as humic acids (HA) and lignin by white rot fungi, have been widely investigated. However, the physical and chemical analysis of degradation products of these materials has not been intensively explored. Fourier transform cyclotron resonance mass spectrometry (FTICR MS) and 1H NMR as well as CHNOS and size exclusion chromatography were employed to study the mechanisms of HA degradation by Trametes sp. M23 and Phanerochaete sp. Y6. Size exclusion chromatography analyses demonstrate and provide evidence for HA breakdown into low MW compounds. The 1H NMR analysis revealed oxidation, a decrease in the aromatic content, and an indication of demethylation of the HA during biodegradation. Evidence for oxidation was also obtained using CHNOS. Analysis of FTICR MS results using a new software program developed by our group (David Mass Sort) revealed consecutive series of masses suggesting biochemical degradation trends such as oxidation, aromatic cleavage, and demethylation. These results are in agreement with the 1H NMR analysis and with the suggested role of the ligninolytic system leading to HA degradation.

  8. 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

  9. Decomposition mechanisms in thermally-aged thin-film explosives

    SciTech Connect

    Erickson, K.L.; Trott, W.M.; Renlund, A.M.

    1994-10-01

    The isothermal decomposition of nitrocellulose (NC) has been examined using two substantially different experimental techniques, involving both confined and unconfined samples. The confined isothermal aging technique involved confined thin-film samples heated to temperatures of 150 to 170{degrees}C, for 1 to 72 hours. Condensed-phase chemistry was monitored real-time using FTIR. Results indicated that the first step in decomposition was scission of the O-NO{sub 2} bond and subsequent formation of carbonyl and hydroxyl products. Scission of the O-NO{sub 2} bond appeared to occur by a first-order reaction. The Arrhenius expression for the first-order reaction rate constant was evaluated from the experimental data. The unconfined rapid isothermal decomposition technique involved both high speed-photography and time-of-flight mass spectrometry (TOFMS). Mass spectra obtained from experiments at 420{degrees}C indicated that NO{sub 2} formation and, therefore, scission of the O-NO{sub 2} bond occurred by a first order reaction, the rate constant for which was evaluated from the experimental data. The rate constant for global pseudo-first order decomposition of NC at 450{degrees}C was also estimated from high speed photography results. Rate constants at 420 and 450{degrees}C were predicted using the Arrhenius expression developed from the confined isothermal aging results and were in good agreement with the rate constants obtained at those temperatures in the unconfined rapid decomposition experiments using TOFMS and high-speed photography. Results from these substantially different measurements gave consistent results over a temperature range of about 300{degrees}C, in which reaction rates vary by nine orders of magnitude, and indicate that the two experimental techniques being developed have good potential for studying condensed-phase decomposition of energetic materials.

  10. Fibril reinforced poroelastic model predicts specifically mechanical behavior of normal, proteoglycan depleted and collagen degraded articular cartilage.

    PubMed

    Korhonen, Rami K; Laasanen, Mikko S; Töyräs, Juha; Lappalainen, Reijo; Helminen, Heikki J; Jurvelin, Jukka S

    2003-09-01

    Degradation of collagen network and proteoglycan (PG) macromolecules are signs of articular cartilage degeneration. These changes impair cartilage mechanical function. Effects of collagen degradation and PG depletion on the time-dependent mechanical behavior of cartilage are different. In this study, numerical analyses, which take the compression-tension nonlinearity of the tissue into account, were carried out using a fibril reinforced poroelastic finite element model. The study aimed at improving our understanding of the stress-relaxation behavior of normal and degenerated cartilage in unconfined compression. PG and collagen degradations were simulated by decreasing the Young's modulus of the drained porous (nonfibrillar) matrix and the fibril network, respectively. Numerical analyses were compared to results from experimental tests with chondroitinase ABC (PG depletion) or collagenase (collagen degradation) digested samples. Fibril reinforced poroelastic model predicted the experimental behavior of cartilage after chondroitinase ABC digestion by a major decrease of the drained porous matrix modulus (-64+/-28%) and a minor decrease of the fibril network modulus (-11+/-9%). After collagenase digestion, in contrast, the numerical analyses predicted the experimental behavior of cartilage by a major decrease of the fibril network modulus (-69+/-5%) and a decrease of the drained porous matrix modulus (-44+/-18%). The reduction of the drained porous matrix modulus after collagenase digestion was consistent with the microscopically observed secondary PG loss from the tissue. The present results indicate that the fibril reinforced poroelastic model is able to predict specifically characteristic alterations in the stress-relaxation behavior of cartilage after enzymatic modifications of the tissue. We conclude that the compression-tension nonlinearity of the tissue is needed to capture realistically the mechanical behavior of normal and degenerated articular cartilage.

  11. A Review of the Mechanism and Kinetics of Electrochemical Hydrogen Entry and Degradation of Metallic Systems

    DTIC Science & Technology

    1990-01-01

    EN’IRY AN * DEGRADATION OF MET~ALLIC SYSTEM[ S H. W. Pickering ;Q.’r Department of Materials Science and Engineering The Pennsylvania State Universiiy...Met~ s Science and Engineering, Polymer Science; Mineral Economics; Mining Engineering, Petroleum ad Nailuzal Gas Engineering; Earth Sciences...Deposits Research Group. Analytical and Characterization Laborarqie s (Mineral Constitution Laboratories) Services available include: classical

  12. Chlorobenzene degradation by electro-heterogeneous catalysis in aqueous solution: intermediates and reaction mechanism.

    PubMed

    Wang, Jiade; Mei, Yu; Liu, Chenliang; Chen, Jianmeng

    2008-01-01

    This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis. The effects of current density, pH, and electrolyte concentration on CB degradation were determined. The degradation efficiency of CB was almost 100% with an initial CB concentration of 50 mg/L, current density 15 mA/cm2, initial pH 10, electrolyte concentration 0.1 mol/L, and temperature 25 degrees C after 90 min of reaction. Under the same conditions, the degradation efficiency of CB was only 51% by electrochemical (EC) process, which showed that electro-heterogeneous catalysis was more efficient than EC alone. The analysis results of Purge-and-Trap chromatography-mass spectrometry (P&T/GC/MS) and ion chromatography (IC) indicated that in the reaction process, the initial *OH attack could occur at the C-Cl bond of CB, yielding phenol and biphenyl with the release of Cl-. Further oxidation of phenol and biphenyl produced p-Vinylbenzoic acid and hydroquinol. Finally, the compounds were oxidized to butenedioic acid and other small-molecule acids.

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

    NASA Astrophysics Data System (ADS)

    Lathrop, J. W.

    1986-09-01

    This is the final report of a reliability research program to study the response of amorphous silicon colar cells to accelerated temperature testing. The goal of the research was to utilize accelerated testing to identify failure/degradation modes and to relate them to basic physical, chemical, and metallurgical phenomena. Four types of single junction commercial modules were subjected to 140 C testing, both in the dark and under illuminated conditions. The before and after electrical characteristics of individual cells were measured and compared and correlated with physical evidence. A fifth module type could not be tested because of poor adherence of the films to the glass superstrate. A short term effect of stressing was noted which dramatically improved cells with low Voc on one type of construction. All cells eventually showed long term irreversible degradation, but the time to 50% Pm reduction varied by as much as two orders of magnitude depending on construction. No basic difference could be detected between degradation under illuminated or non-illuminated conditions, when cells were either open or short circuited. Comparison with one type of tendem cell and with published results of Japanese cell testing indicated the marked superiority of the tandem cell to all other types. Cells were examined physically by optical, IR, and scanning electron microscopy and by Auger spectroscopy, spectroscopy, secondary ion mass spectroscopy, and energy dispersive x-ray analysis. The long term degradation was felt to be due to localized penetration of aluminum through the amorphous film.

  14. Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms.

    PubMed

    Zhong, Junbo; Wang, Jianli; Tao, Lin; Gong, Maochu; Zhimin, Liu; Chen, Yaoqiang

    2007-01-10

    Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.

  15. Adaptation mechanisms of bacteria during the degradation of polychlorinated biphenyls in the presence of natural and synthetic terpenes as potential degradation inducers.

    PubMed

    Zorádová-Murínová, Slavomíra; Dudášová, Hana; Lukáčová, Lucia; Certík, Milan; Silharová, Katarína; Vrana, Branislav; Dercová, Katarína

    2012-06-01

    In this study, we examined the effect of polychlorinated biphenyls (PCBs) in the presence of natural and synthetic terpenes and biphenyl on biomass production, lipid accumulation, and membrane adaptation mechanisms of two PCB-degrading bacterial strains Pseudomonas stutzeri and Burkholderia xenovorans LB400. According to the results obtained, it could be concluded that natural terpenes, mainly those contained in ivy leaves and pine needles, decreased adaptation responses induced by PCBs in these strains. The adaptation processes under investigation included growth inhibition, lipid accumulation, composition of fatty acids, cis/trans isomerization, and membrane saturation. Growth inhibition effect decreased upon addition of these natural compounds to the medium. The amount of unsaturated fatty acids that can lead to elevated membrane fluidity increased in both strains after the addition of the two natural terpene sources. The cells adaptation changes were more prominent in the presence of carvone, limonene, and biphenyl than in the presence of natural terpenes, as indicated by growth inhibition, lipid accumulation, and cis/trans isomerization. Addition of biphenyl and carvone simultaneously with PCBs increased the trans/cis ratio of fatty acids in membrane fractions probably as a result of fluidizing effects of PCBs. This stimulation is more pronounced in the presence of PCBs as a sole carbon source. This suggests that PCBs alone have a stronger effect on bacterial membrane adaptation mechanisms than when added together with biphenyl or natural or synthetic terpenes.

  16. 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.

  17. [The mechanism of phenoptosis: I. Age-dependent decrease of the overall rate of protein synthesis is caused by the programmed attenuation of bio-energetics].

    PubMed

    Trubitsyn, A G

    2009-01-01

    The age-dependent degradation of all vital processes of an organism can be result of influences of destructive factors (the stochastic mechanism of aging), or effect of realizations of the genetic program (phenoptosis). The stochastic free-radical theory of aging dominating now contradicts the set of empirical data, and the semicentenial attempts to create the means to slow down aging did not give any practical results. It makes obvious that the stochastic mechanism of aging is incorrect. At the same time, the alternative mechanism of the programmed aging is not developed yet but preconditions for it development have already been created. It is shown that the genes controlling process of aging exist (contrary to the customary opinion) and the increase in the level of damaged macromolecules (basic postulate of the free-radical theory) can be explained by programmed attenuation of bio-energetics. As the bio-energetics is a driving force of all vital processes, decrease of its level is capable to cause degradation of all functions of an organism. However to transform this postulate into a basis of the theory of phenoptosis it is necessary to show, that attenuation of bio-energetics predetermines such fundamental processes accompanying aging as decrease of the overall rate of protein biosynthesis, restriction of cellular proliferations (Hayflick limit), loss of telomeres etc. This article is the first step in this direction: the natural mechanism of interaction of overall rate of protein synthesis with a level of cellular bio-energetics is shown. This is built-in into the translation machine and based on dependence of recirculation rate of eukaryotic initiation factor 2 (elF2) from ATP/ADP value that is created by mitochondrial bio-energetic machine.

  18. 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

  19. 77 FR 41457 - Aging Management Associated With Wall Thinning Due to Erosion Mechanisms

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-13

    ... 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 LR... erosion mechanisms for piping and components within the scope of the Requirements for Renewal of...

  20. Nanocomposite scaffolds with tunable mechanical and degradation capabilities: co-delivery of bioactive agents for bone tissue engineering.

    PubMed

    Cattalini, Juan P; Roether, Judith; Hoppe, Alexander; Pishbin, Fatemeh; Haro Durand, Luis; Gorustovich, Alejandro; Boccaccini, Aldo R; Lucangioli, Silvia; Mouriño, Viviana

    2016-10-21

    Novel multifunctional nanocomposite scaffolds made of nanobioactive glass and alginate crosslinked with therapeutic ions such as calcium and copper were developed for delivering therapeutic agents, in a highly controlled and sustainable manner, for bone tissue engineering. Alendronate, a well-known antiresorptive agent, was formulated into microspheres under optimized conditions and effectively loaded within the novel multifunctional scaffolds with a high encapsulation percentage. The size of the cation used for the alginate crosslinking impacted directly on porosity and viscoelastic properties, and thus, on the degradation rate and the release profile of copper, calcium and alendronate. According to this, even though highly porous structures were created with suitable pore sizes for cell ingrowth and vascularization in both cases, copper-crosslinked scaffolds showed higher values of porosity, elastic modulus, degradation rate and the amount of copper and alendronate released, when compared with calcium-crosslinked scaffolds. In addition, in all cases, the scaffolds showed bioactivity and mechanical properties close to the endogenous trabecular bone tissue in terms of viscoelasticity. Furthermore, the scaffolds showed osteogenic and angiogenic properties on bone and endothelial cells, respectively, and the extracts of the biomaterials used promoted the formation of blood vessels in an ex vivo model. These new bioactive nanocomposite scaffolds represent an exciting new class of therapeutic cell delivery carrier with tunable mechanical and degradation properties; potentially useful in the controlled and sustainable delivery of therapeutic agents with active roles in bone formation and angiogenesis, as well as in the support of cell proliferation and osteogenesis for bone tissue engineering.

  1. 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.

  2. 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.

  3. Cover Picture: Slow mode degradation mechanism of ZnSe based white LEDs

    NASA Astrophysics Data System (ADS)

    Adachi, Masahiro; Ando, Koshi; Abe, Tomoki; Tsutsumi, Shigeyuki; Inoue, Noboru; Kasada, Hirofumi; Katayama, Koji; Nakamura, Takao

    2004-02-01

    The cover picture is a photograph showing a row of ZnSe based white LEDs. In this issue's Editor's Choice [1], the point defect induced degradation in these high quality diodes is investigated by electroluminescence, deep level transient spectroscopy, and isothermal capacitance transient spectroscopy investigations.The first author, Masahiro Adachi, is member of the Optoelectronics Laboratory at Tattori University, where he is working on microscopic defects in ZnSe based devices, defect induced degradation, and defect behaviour.The paper is an invited presentation from the II-VI '03 Conference held in Niagara Falls, New York, USA, 22-26 September 2003.The full Proceedings of the Eleventh International Conference on II-VI Compounds are published in physica status solidi (c) - conferences and critical reviews 1, No. 4 (March 2004) (ISBN 3-527-40510-0).

  4. 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.

  5. 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

  6. Metabolic acidosis stimulates protein degradation in rat muscle by a glucocorticoid-dependent mechanism.

    PubMed Central

    May, R C; Kelly, R A; Mitch, W E

    1986-01-01

    Metabolic acidosis is associated with enhanced renal ammonia-genesis which is regulated, in part, by glucocorticoids. The interaction between glucocorticoids and chronic metabolic acidosis on nitrogen utilization and muscle protein metabolism is unknown. In rats pair-fed by gavage, we found that chronic acidosis stunted growth and caused a 43% increase in urinary nitrogen and an 87% increase in urinary corticosterone. Net protein degradation in incubated epitrochlearis muscles from chronically acidotic rats was stimulated at all concentrations of insulin from 0 to 10(4) microU/ml. This effect of acidosis persisted despite supplementation of the media with amino acids with or without insulin, indomethacin, and inhibitors of lysosomal thiol cathepsins. Acidosis did not change protein synthesis; hence, the increase in net protein degradation was caused by stimulation of proteolysis. Acidosis did not increase glutamine production in muscle. The protein catabolic effect of acidosis required glucocorticoids; protein degradation was stimulated in muscle of acidotic, adrenalectomized rats only if they were treated with dexamethasone. Moreover, when nonacidotic animals were given 3 micrograms/100 g of body weight dexamethasone twice a day, muscle protein degradation was increased if the muscles were simply incubated in acidified media. We conclude that chronic metabolic acidosis depresses nitrogen utilization and increases glucocorticoid production. The combination of increased glucocorticoids and acidosis stimulates muscle proteolysis but does not affect protein synthesis. These changes in muscle protein metabolism may play a role in the defense against acidosis by providing amino acid nitrogen to support the glutamine production necessary for renal ammoniagenesis. PMID:3511100

  7. Mechanisms of cellular uptake, intracellular transportation, and degradation of CIGB-300, a Tat-conjugated peptide, in tumor cell lines.

    PubMed

    Benavent Acero, Fernando R; Perera Negrin, Yasser; Alonso, Daniel F; Perea, Silvio E; Gomez, Daniel E; Farina, Hernán G

    2014-06-02

    CIGB-300 is a cyclic synthetic peptide that induces apoptosis in malignant cells, elicits antitumor activity in cancer animal models, and shows tumor reduction signs when assayed in first-in-human phase I trial in patients with cervical tumors. CIGB-300 impairs phosphorylation by casein kinase 2 through targeting the substrate's phosphoacceptor domain. CIGB-300 was linked to the cell penetrating peptide Tat to facilitate the delivery into cells. Previously, we showed that CIGB-300 had a differential antiproliferative behavior in different tumor cell lines. In this work, we studied differential antiproliferative behavior in terms of cellular uptake, intracellular transportation, and degradation in tumor cell lines with dissimilar sensitivity to CIGB-300. The internalization of CIGB-300 was studied in different malignant cell lines. We found that the cell membrane heparan sulfate proteoglycans act as main receptors for extracellular CIGB-300 uptake. The most sensitive tumor cell lines showed higher intracellular incorporation of CIGB-300 in comparison to less sensitive cell lines. Furthermore, CIGB-300 uptake is time- and concentration-dependent in all studied cell lines. It was shown that CIGB-300 has the ability to penetrate cells mainly by direct membrane translocation. However, a minor proportion of the peptide uses an energy-dependent endocytic pathway mechanism to gain access into cells. CIGB-300 is internalized and transported into cells preferentially by caveolae-mediated endocytosis. Lysosomes are involved in CIGB-300 degradation; highly sensitive cell lines showed degradation at earlier times compared to low sensitive cells. Altogether, our data suggests a mechanism of internalization, vesicular transportation, and degradation for CIGB-300 in tumor cells.

  8. Aging, the Central Nervous System, and Mobility in Older Adults: Neural Mechanisms of Mobility Impairment

    PubMed Central

    Cruz-Almeida, Yenisel; Clark, David J.; Viswanathan, Anand; Scherzer, Clemens R.; De Jager, Philip; Csiszar, Anna; Laurienti, Paul J.; Hausdorff, Jeffery M.; Chen, Wen G.; Ferrucci, Luiggi; Rosano, Caterina; Studenski, Stephanie A.; Black, Sandra E.; Lipsitz, Lewis A.

    2015-01-01

    Background. Mobility is crucial for successful aging and is impaired in many older adults. We know very little about the subtle, subclinical age-related changes in the central nervous system (CNS) that mediate mobility impairment. Methods. A conference series focused on aging, the CNS, and mobility was launched. The second conference addressed major age-associated mechanisms of CNS-mediated mobility impairment. Speakers and conference attendees recommended key areas for future research, identified barriers to progress, and proposed strategies to overcome them. Results. Priorities identified for future research include (a) studying interactions among different mechanisms; (b) examining effects of interventions targeting these mechanisms; (c) evaluating the effect of genetic polymorphisms on risks and course of age-related mobility impairment; and (d) examining the effect of age on CNS repair processes, neuroplasticity, and neuronal compensatory mechanisms. Key strategies to promote research include (a) establish standard measures of mobility across species; (b) evaluate the effect of aging in the absence of disease on CNS and mobility; and (c) use advanced computational methods to better evaluate the interactions between CNS and other systems involved in mobility. Conclusions. CNS is a major player in the process, leading to mobility decline with aging. Future research in this area has the potential to prolong independence in older persons. Better interactions among disciplines and shared research paradigms are needed to make progress. Research priorities include the development of innovative approaches to integrate research on aging, cognition, and movement with attention to neurovascular function, neuroplasticity, and neurophysiological reserve. PMID:26386013

  9. Biodegradation of Phenanthrene by Pseudomonas sp. JPN2 and Structure-Based Degrading Mechanism Study.

    PubMed

    Jin, Jingnan; Yao, Jun; Zhang, Qingye

    2016-11-01

    The strain Pseudomonas sp. JPN2 had a high potential to degrade phenanthrene degrading 98.52 % of the initial amount of 100 mg L(-1) after 10 days incubation. The analysis of metabolites demonstrated that the cleavage of phenanthrene started at the C9 and C10 positions on the aromatic ring by the dioxygenation reaction, and then further degraded via a phthalate pathway. To understand the interaction between phenanthrene and the amino acid residues in the active site of the target enzyme, a molecular docking simulation was performed. The results showed that the distances of C9-O1 and C10-O2 atoms were 3.47 and 3.67 Å, respectively. The C9 and C10 positions of the phenanthrene ring are much closer to the dioxygen molecule in the active site relative to the other atoms. Therefore, the C9 and C10 positions are vulnerable to attack in the initial oxygenation process.