Greater Acid Research Articles

Comparison of Quick-Set and Mineral Trioxide Aggregate Root-end Fillings for the Regeneration of Apical Tissues in Dogs

IntroductionQuick-Set (Avalon Biomed Inc, Bradenton, FL) is a calcium aluminosilicate cement that is a potential alternative to mineral trioxide aggregate (MTA) with greater acid resistance and faster setting. The purpose of this study was to compare the regeneration of apical tissues after root-end surgery when the apical tissues were exposed to Quick-Set or White ProRoot MTA (Dentsply Tulsa Dental Specialties, Tulsa, OK) by root-end resection. MethodsThe root canals of 42 mandibular premolars in 7 beagle dogs were accessed, cleaned and shaped, and obturated with Quick-Set or white MTA. Osteotomies and root-end resections were performed immediately. The dogs were sacrificed at 90 days, and the teeth and surrounding tissues were removed and prepared for histologic analysis. The sections of the apical areas were scored for inflammation, new cementum formation, periodontal ligament formation, and bone quality. ResultsAt 90 days, both materials supported some degree of cementum formation on the surface of the material, periodontal ligament regeneration, and excellent bone quality. The only significant difference was greater inflammation found in the Quick-Set group. ConclusionsQuick-Set and White ProRoot MTA had a similar effect on bone quality, cementum formation, and periodontal ligament formation after root-end surgery in dogs. Quick-Set was associated with greater inflammation.

Comparison of the hydrogen-bond patterns in 2-amino-1,3,4-thiadiazolium hydrogen oxalate, 2-amino-1,3,4-thiadiazole-succinic acid (1/2), 2-amino-1,3,4-thiadiazole-glutaric acid (1/1) and 2-amino-1,3,4-thiadiazole-adipic acid (1/1).

The X-ray single-crystal structure determinations of the chemically related compounds 2-amino-1,3,4-thiadiazolium hydrogen oxalate, C2H4N3S(+)·C2HO4(-), (I), 2-amino-1,3,4-thiadiazole-succinic acid (1/2), C2H3N3S·2C4H6O4, (II), 2-amino-1,3,4-thiadiazole-glutaric acid (1/1), C2H3N3S·C5H8O4, (III), and 2-amino-1,3,4-thiadiazole-adipic acid (1/1), C2H3N3S·C6H10O4, (IV), are reported and their hydrogen-bonding patterns are compared. The hydrogen bonds are of the types N-H···O or O-H···N and are of moderate strength. In some cases, weak C-H···O interactions are also present. Compound (II) differs from the others not only in the molar ratio of base and acid (1:2), but also in its hydrogen-bonding pattern, which is based on chain motifs. In (I), (III) and (IV), the most prominent feature is the presence of an R2(2)(8) graph-set motif formed by N-H···O and O-H···N hydrogen bonds, which are present in all structures except for (I), where only a pair of N-H···O hydrogen bonds is present, in agreement with the greater acidity of oxalic acid. There are nonbonding S···O interactions present in all four structures. The difference electron-density maps show a lack of electron density about the S atom along the S···O vector. In all four structures, the carboxylic acid H atoms are present in a rare configuration with a C-C-O-H torsion angle of ∼0°. In the structures of (II)-(IV), the C-C-O-H torsion angle of the second carboxylic acid group has the more common value of ∼|180|°. The dicarboxylic acid molecules are situated on crystallographic inversion centres in (II). The Raman and IR spectra of the title compounds are presented and analysed.

Membrane lipid composition and stress/virulence related gene expression of Salmonella Enteritidis cells adapted to lactic acid and trisodium phosphate and their resistance to lethal heat and acid stress

This study evaluated the acid and heat resistance of Salmonella Enteritidis in simulated gastric fluid (pH2.0) and during thermal treatment (54–60°C), respectively, after adaptation to lactic acid (LA) or trisodium phosphate (TSP) at various pHs (pH5.3–9.0). The changes in membrane lipid composition and expression levels of RpoS and RpoH were examined to elucidate their roles in bacterial stress resistance. Transcriptional profile of several virulence-related genes was also analyzed. Results showed that LA-adapted cells at pH5.3 and 6.3 had higher acid and heat resistance than control cells and cells adapted to TSP at pH8.3 and 9.0. LA-adapted cells had the lowest ratio of unsaturated to saturated fatty acids, indicating that they might possess a less fluid membrane. It was observed that the expression levels of RpoH and RpoS were upregulated in TSP-adapted cells but not in LA-adapted cells. Thus, these results indicate that the increased acid and heat resistance of LA-adapted S. Enteritidis was possibly due to the decreased membrane fluidity instead of the upregulation of RpoS and RpoH. About 6.0, 2.1, and 2.46-fold upregulation of spvR, avrA, and hilA were observed in cells adapted to TSP at pH9.0, except sefA that had its highest expression level in the control cells, indicating that the expression of these virulence genes highly depends on environmental conditions. This is the first study to show that the alteration in the cytoplasmic membrane rather than RpoS and RpoH plays a more crucial role in conferring greater acid and heat resistance on LA-adapted S. Enteritidis, thus providing a better understanding on the bacterial stress response to acidic conditions.

Sterol and Fatty Acid Compositions of Olive Oil as an Indicator of Cultivar and Growing Area

AbstractBecause of the importance of cultivar and growing area on the quality and quantity of extracted olive oil, this study examined the effects of two different growing areas (Qom (subdesertic) and Gorgan (Caspian zone) that have important differences in altitude, latitude, and climatic conditions on the physicochemical characteristics of extracted oils from three common cultivars (Beleydi, Mission and Koroneiki) growing in Iran. Independently of the growing area conditions, Beleydi cultivars showed the lowest values of oil content (16.93 ± 1.55 and 43.54 ± 0.18 % in Qom and Gorgan, respectively) the greatest acidity, even higher than the limits specified by the International Olive Council (IOC) regulations (1.04 and 0.46 % in Qom and Gorgan, respectively), and the lowest oxidative stability (9.0 and 6.7 h in Qom and Gorgan, respectively) among the studied cultivars. All cultivars growing in Qom had lower oil contents, but they had higher oleic acid and β‐sitosterol content and lower PUFA/SFA ratios in comparison with cultivars grown in Gorgan. Therefore, cultivars grown in Qom had higher oxidative stability. Finally, when principal component analysis (PCA) was applied, the fatty acid and sterol profiles could be used to separate olive samples according to their cultivar and growing area, respectively.

Impact of renal medullary three-dimensional architecture on oxygen transport.

We have developed a highly detailed mathematical model of solute transport in the renal medulla of the rat kidney to study the impact of the structured organization of nephrons and vessels revealed in anatomic studies. The model represents the arrangement of tubules around a vascular bundle in the outer medulla and around a collecting duct cluster in the upper inner medulla. Model simulations yield marked gradients in intrabundle and interbundle interstitial fluid oxygen tension (PO2), NaCl concentration, and osmolality in the outer medulla, owing to the vigorous active reabsorption of NaCl by the thick ascending limbs. In the inner medulla, where the thin ascending limbs do not mediate significant active NaCl transport, interstitial fluid composition becomes much more homogeneous with respect to NaCl, urea, and osmolality. Nonetheless, a substantial PO2 gradient remains, owing to the relatively high oxygen demand of the inner medullary collecting ducts. Perhaps more importantly, the model predicts that in the absence of the three-dimensional medullary architecture, oxygen delivery to the inner medulla would drastically decrease, with the terminal inner medulla nearly completely deprived of oxygen. Thus model results suggest that the functional role of the three-dimensional medullary architecture may be to preserve oxygen delivery to the papilla. Additionally, a simulation that represents low medullary blood flow suggests that the separation of thick limbs from the vascular bundles substantially increases the risk of the segments to hypoxic injury. When nephrons and vessels are more homogeneously distributed, luminal PO2 in the thick ascending limb of superficial nephrons increases by 66% in the inner stripe. Furthermore, simulations predict that owing to the Bohr effect, the presumed greater acidity of blood in the interbundle regions, where thick ascending limbs are located, relative to that in the vascular bundles, facilitates the delivery of O2 to support the high metabolic requirements of the thick limbs and raises NaCl reabsorption.

PH-dependent coordination of Pb2+ to metallothionein2: structures and insight into lead detoxification.

Lead is a toxic heavy metal whose detoxification in organisms is mainly carried out by its coordination with some metalloproteins such as metallothioneins (MTs). Two Pb–MT complexes, named as Pb7–MT2(I) and Pb7–MT2(II), form under neutral and weakly acidic conditions, respectively. However, the structures of the two complexes, which are crucial for a better understanding of the detoxification mechanism of Pb–MTs, have not been clearly elucidated. In this Work, coordination of Pb2+ with rabbit liver apo–MT2, as well as with the two individual domains (apo−αMT2 and apo−βMT2) at different pH, were studied by combined spectroscopic (UV–visible, circular dichroism, and NMR) and computational methods. The results showed that in Pb7–MT2(I) the Pb2+ coordination is in the trigonal pyramidal Pb–S3 mode, whereas the Pb7–MT2(II) complex contains mixed trigonal pyramidal Pb–S3, distorted trigonal pyramidal Pb–S2O1, and distorted quadrilateral pyramidal Pb–S3O1 modes. The O-donor ligand in Pb7–MT2(II) was identified as the carboxyl groups of the aspartic acid residues at positions 2 and 56. Our studies also revealed that Pb7–MT2(II) has a greater acid tolerance and coordination stability than Pb7–MT2(I), thereby retaining the Pb2+ coordination at acidic pH. The higher flexibility of Pb7–MT2(II) renders it more accessible to lysosomal proteolysis than Pb7–MT2(I). Similar spectral features were observed in the coordination of Pb2+ by human apo-MT2, suggesting a commonality among mammalian MT2s in the Pb2+ coordination chemistry.

Destabilization of LiBH4dehydrogenation through H+–H−interactions by cooperating with alkali metal hydroxides

Destabilization by the alkali metal hydroxides LiOH, NaOH, and KOH in the solid-state dehydrogenation of LiBH4 is reported. 6.5 wt% of hydrogen was liberated within 10 minutes at 250 °C. Destabilization originated from the interaction between H+ in [OH]− and H− in [BH4]−. A larger Pauling's electronegativity of the alkali metal (Li > Na > K) led to a greater acidity of the proton donor [OH]− site, and thus enhanced destabilization. The temperature of the predominant dehydrogenation was reduced to 207, 221, and 230 °C, for ball milled LiBH4–LiOH, 2LiBH4–NaOH, and 2LiBH4–KOH, respectively. The LiBH4: LiOH stoichiometry greatly affected the destabilization, by providing differing reaction pathways in LiBH4-xLiOH (x = 1, 1.36, 4). The incremental increase in the LiOH content of LiBH4-xLiOH increased the dehydrogenation rate, but the temperature increased from 207 °C (x = 1) to 250 °C (x = 4). 4.1 and 6.5 wt% of hydrogen was liberated within 10 minutes by LiBH4–LiOH and LiBH4–4LiOH, respectively. The incremental increase in dehydrogenation temperature was attributed to differing [BH4]−⋯[OH]− interactions, formed by the differing stoichiometric ratios.

Acid phosphatase activity in mycorrhizal and non-mycorrhizal Scots pine seedlings in relation to nitrogen and phosphorus nutrition

Mycorrhizal and control seedlings of Scots pine (<i>Pinus sylvestris</i> L.) were grown under axenic conditions at various concentrations of nitrogen (0.17 mM, 3.78 mM, 18.92 mM) and phosphorus (0.25 mM, 5.58 mM, 23.5 mM). Enzyme activities of soluble acid phosphatase of excised roots (surface-accessible activity) and of crude enzyme preparations of root tissue (total soluble activity) were analyzed in control and mycorrhizal seedlings. The content of P in pine shoot was also measured. The intermediate supply of nitrogen and phosphorus (N = 3.78 mM, P= 5.58 mM) was optimal for development of ectomycorrhizae. Activity of acid phosphatase was stimulated by higher levels of N in the soil and was higher in mycorrhizal than non-mycorrhizal roots. Pine roots had greater acid phosphatase activity at the reduced than at the higher P concentrations. The presence of mycorrhizae increased the activities of both surface-accessible and total soluble enzyme activities at lower P supply (0.25 mM, 5.58 mM) and decreased it significantly at the highest P concentration (23.5 mM). P content in shoots was higher in mycorrhizal than non-mycorrhizal seedlings.

Infrared spectroscopic characterization of hydrogen-bonded propylene oxide − ethanol and propylene oxide − 2-fluoroethanol complexes isolated in solid neon matrices

The infrared absorption spectra of hydrogen-bonded complexes of propylene oxide with either ethanol or 2-fluoroethanol have been recorded in neon matrices. Mixtures of propylene oxide and ethanol or propylene oxide and 2-fluoroethanol vapors were mixed with an excess of neon gas and deposited onto a KBr substrate at 4.2 K. The results indicate that hydrogen-bonded complexes were formed with propylene oxide as the hydrogen bond acceptor and either ethanol or 2-fluoroethanol as the hydrogen bond donors. The features assigned to the O−H stretch were red-shifted by 175 and 193 cm−1 for the ethanol- and 2-fluoroethanol-containing complexes, respectively. The difference in red shifts can be accounted for due to the greater acidity of 2-fluroethanol. Deuterium isotope experiments were conducted to help confirm the assignment of the O–H stretch for the complexes. As well, structures and infrared spectra were calculated using B3LYP/6-311++G(2d,2p) calculations and were used to compare with the experimental spectra. A “scaling equation” rather than a scaling factor was used and is shown to greatly increase the utility of the calculations when comparing with experimental spectra. An examination of the O–H stretching red shifts for many hydrogen-bound complexes reveals a relationship between the shift and the difference between the acidity of the hydrogen bond donor and the basicity of the hydrogen bond acceptor (the enthalpy of proton transfer). Both hydrogen-bonded complexes and proton-bound complexes appear to have a maximum in the reduced frequency value that corresponds to complexes where the hydrogen/proton are equally shared between the two bases.

자이오머의 산성용액에 대한 산중화능

The aim of this study was to evaluate the acid neutralizing capacity and to observe surface changes of giomer in comparison with composite resin, when it comes in contact with an acidic solution. A packable giomer(Beautifil II) and a flowable giomer(Beautifil Flow F02) were used as experimental groups, while a packable composite resin(FiltekTM Z-250) was used as control group. pH values were measured after mixing the specimens of the disc and powder types with a pH 2.0 hydrochloric acid solution, respectively. Also, in the case of powder type giomers used in the earlier experiment, their pH values were measured again after mixing them with a fresh acid solution. Moreover, surface structure changes of disc type specimens were observed by using a scanning electron microscopy(SEM). In the disc type test, the pH values of packable giomer were significantly increased after 24 hours( p < 0.05). In contrast, in the powder type test, the pH values of packable and flowable giomers were dramatically increased within 30 minutes. The pH value of packable giomer, in particular, was higer than that of flowable giomer(p < 0.05). In the repeated neutralizing test, the degree of pH variation was lower than that of the previous neutralizing test(p < 0.05). Erosive changes on the surface of packable giomer were observed to be more than those on composite resin and flowable giomer as well. In conclusion, giomer has a acid neutralizing capacity, when it comes in contact with an acidic solution. Especially, packable giomer with high filler content has a greater acid neutralizing capacity than flowable giomer.

Spread and change in stress resistance of Shiga toxin‐producing Escherichia coli O157 on fungal colonies

To elucidate the effect of fungal hyphae on the behaviour of Shiga toxin-producing Escherichia coli (STEC) O157, the spread and change in stress resistance of the bacterium were evaluated after coculture with 11 species of food-related fungi including fermentation starters. Spread distances of STEC O157 varied depending on the co-cultured fungal species, and the motile bacterial strain spread for longer distances than the non-motile strain. The population of STEC O157 increased when co-cultured on colonies of nine fungal species but decreased on colonies of Emericella nidulans and Aspergillus ochraceus. Confocal scanning microscopy visualization of green fluorescent protein-tagged STEC O157 on fungal hyphae revealed that the bacterium colonized in the water film that existed on and between hyphae. To investigate the physiological changes in STEC O157 caused by co-culturing with fungi, the bacterium was harvested after 7 days of co-culturing and tested for acid resistance. After co-culture with eight fungal species, STEC O157 showed greater acid resistance compared to those cultured without fungi. Our results indicate that fungal hyphae can spread the contamination of STEC O157 and can also enhance the stress resistance of the bacteria.

Rhizosphere acid and alkaline phosphatase activity as a marker of P nutrition in nodulated Cyclopia and Aspalathus species in the Cape fynbos of South Africa

Cyclopia and Aspalathus species are important economic legumes in the Cape fynbos of South Africa, as they are used for making Honeybush and Rooibos tea, and for trade in the cut wild flower industry. The aim of this study was to assess acid and alkaline phosphatase activity in the rhizosphere of Cyclopia genistoides, Cyclopia subternata, Aspalathus caledonensis and Aspalathus aspalathoides as an indicator of P supply and P nutrition in the nutrient-poor soils of the Cape fynbos. Whether at Kokrivier or Kanetberg, the P enzyme activities were much higher in the rhizospheres of the legumes C. genistoides, C. subternata, A. caledonensis, and A. aspalathoides compared to those of the non-legumes Leucadendron strictum, Elegia thyrsoidea and Mimetes cucullatus, or bulk soil. As a result, plant-available P concentration in the rhizosphere, as well as shoot P levels closely mirrored acid and alkaline phosphatase activity in the rhizosphere of each plant species. Relative to younger plants, older Cyclopia species exhibited, much greater acid and alkaline phosphatase activity in the rhizosphere and this again resulted in much higher plant-available rhizosphere P. C. subternata plants developed from cuttings at Kanetberg showed greater rhizosphere acid and alkaline phosphatase activity than seedlings and bulk soil. As a result, the concentration of plant available-P and organic P were much higher in the rhizosphere of cuttings than seedlings, leading to greater shoot P in cuttings than seedlings. Taken together, these data suggest that rhizosphere P enzyme activity can be used as a good indicator of P supply and P nutrition in Cyclopia cuttings and seedlings, but less so in Aspalathus species in the Cape fynbos. The enhanced P nutrition in plants from cuttings probably accounts for the higher tea yields obtained by farmers when they use cuttings instead of seedlings in their plantations.

A concise review of HPLC, LC‐MS and LC‐MS/MS methods for determination of azithromycin in various biological matrices

Azithromycin is one of the best selling antibiotics in the world. It belongs to the new macrolide family of azalides. It is derived from erythromycin and it differs from erythromycin in having a 15-membered ring and a methyl substituted nitrogen inserted at the 9a position in the aglycone ring. This structural modification confers favourable microbiological and pharmacokinetic characteristics on azithromycin and greater acid stability compared with erythromycin. It is mainly used to treat respiratory infections, sexually transmitted diseases, cutaneous and soft-tissue infections, etc. This review provides a comprehensive overview of various HPLC, LC-MS and LC-MS/MS methods for quantitation of azithromycin in different biological matrices. In addition, it provides general information on extraction steps, internal standard selection, conditions for chromatographic separation, brief validation data and applicable conclusions for reported methods in a defined pattern.

Effects of Temperature and Time on the Morphology, pH, and Buffering Capacity of Bast and Core Kenaf Fibres

This study investigated the effects of heating on the morphology, pH, and buffering capacity of bast and core kenaf fibre. The bast material yielded longer and thinner fibres (with a higher aspect ratio) compared to the core. Changes in fibre morphology were clearly visible when the temperature of pulping was increased. The morphology of the bast fibre displayed significant variations following treatment at different pulping temperature (150, 160, 170, and 180 °C), time (1, 2, and 3 hours), and with the interaction between both parameters. Core fibre also exhibited significant variation in length, width, and wall thickness in all parameters, but lumen diameter and aspect ratio were not significantly affected by the same processing conditions. The pH value of both fibres was reduced as the temperature increased; core fibre was more acidic compared to bast fibre. Bast fibre exhibited greater acid buffering capacity and core fibre greater alkaline buffering capacity.

The postprandial acid pocket does not extend into most distal esophagus: evidence from pH studies performed immediately above the squamocolumnar junction

Objective. The postprandial acid pocket is suggested to be an important factor in the pathogenesis of gastroesophageal reflux disease (GERD) as it according to the theory extends into the distal esophagus. The aim of this study was to test the hypothesis that the acid pocket transverses the squamocolumnar junction (SCJ) and exposes the most distal esophagus to gastric acid for extended periods following a meal. Material and methods. Fifty asymptomatic volunteers and 75 patients with GERD underwent 48-h pH monitoring with the electrode of a pH capsule placed immediately above the SCJ. The characteristics of esophageal acid exposure from the 90-min postprandial periods were compared with those observed during the upright, preprandial periods. Results. In asymptomatic controls, the degree of postprandial esophageal acid exposure was similar to that observed in the preprandial periods (median % time with pH <4, 2.2 vs. 2.6, p = 0.165). In contrast, symptomatic patients had significantly greater acid exposure in the postprandial compared with the preprandial periods (median % time with pH <4, 15.5 vs. 8.5, p < 0.001). The higher degree of acid exposure during the postprandial periods was due to a significantly higher number of short reflux episodes and reflux events with long durations were infrequent. Conclusion. Postprandial acid exposure in the most distal esophagus was characterized by numerous short reflux events, and reflux events of long durations were rare. Our observations suggest that the acid pocket is confined to the stomach, questioning the importance of the acid pocket in GERD.

Pursuit of Lower Critical Dimensional Uniformity in EUV Resists

This paper describes Dow’s efforts toward improved Critical Dimensional Uniformity (CDU) in EUV resists. Many non-material related factors contribute to good CDU, such as aerial image quality. We have focused on fundamental resist properties like intrinsic dissolution contrast and we have found that the photo-decomposable base (PDB) concept can be successfully employed. With the use of a PDB, we can reduce CDU variation at lower exposure energies. For sensitivity, we have focused on more efficient EUV photon capture through increased EUV absorption, as well as more highly efficient PAGs for greater acid generating efficiency. The formulation concepts will be confirmed using Prolith stochastic resist modeling. For the 26nm hp contact holes, we observe excellent overall process window with over 280nm depth of focus for a 10% exposure latitude Process window. The 1σ CDU is 1.1 nm. We also obtain 20nm hp contact resolution in one of our new EUV resists.

Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations.

We identified and quantified abundant iron-oxidizing bacteria (FeOB) at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7), to moderately acidic (R2, pH 4.4), to slightly acidic (R3, pH 6.3) in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U) bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic “Ferrovum myxofaciens” was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and “Ferrovum myxofaciens” revealed that ~72% (R2 sediment) and 37% (R3 sediment) of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.

Enological potential of chestnut wood for aging Tempranillo wines part I: Volatile compounds and sensorial properties

In order to evaluate the potential of chestnut wood for aging purposes, as an alternative to oak wood, the volatile composition and sensorial properties of aged Tempranillo red wines have been studied. Different aging chestnut treatments (chips, barrels, toasted treatment, and aging time) were tested. Time aging and toasting process had a great influence on the volatile composition of aged wines. The use of non-toasted chestnut chips presented some drawbacks such as unpleasant attributes regarded as sawdust, greater acidity and high variability in the volatile composition of aged wines. On the one hand, wines aged by means of toasted chestnut barrels during six months were those most regarded by the panelists due to their excellent sensorial balance between those compounds from wine and toasted chestnut wood. However, based on the result and on the physical properties of chestnut it was advisable not to use chestnut wood barrels for longer aging time to avoid undesirable concentration of 4-ethylphenol and 4-ethylguaiacol which could produce off-flavours.

Comparison of accelerated aging of silicone rubber gasket material with aging in a fuel cell environment

AbstractA polymer electrolyte membrane (PEM) fuel cell stack requires gaskets in each cell to keep the reactant gases within their respective regions. Both sealing and electrochemical performance of the fuel cell depend on the long‐term stability of the gasket materials. In this paper, the change in properties and structure of a silicone rubber gasket brought about by use in a fuel cell was studied and compared to the changes in the same silicone rubber gasket material brought about by accelerated aging. The accelerated aging conditions were chosen to relate to the PEM fuel cell environment, but with more extreme conditions of elevated temperature (140°C) and greater acidity. The dilute sulfuric acid accelerated aging solutions used had pH values of 1, 2, and 4. In an additional test, Nafion® membrane suspended in water was used for accelerated aging, to more closely correspond to a PEM fuel cell environment. The analysis showed that acid hydrolysis was the most likely mechanism of degradation and that similar degradation occurred under both real fuel cell and accelerated aging conditions. It was concluded that the accelerated aging test is a good one for rapidly screening materials for resistance to the acidic environment of the fuel cell. ©2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

The Impact of Substituents on the Transition States of SN2 and E2 Reactions in Aliphatic and Vinylic Systems: Remarkably Facile Vinylic Eliminations

For a series of α and β substituted haloethanes and haloethenes, gas-phase experiments and computational modeling have been used to characterize their nucleophilic substitution and elimination reactions. Despite being less thermodynamically favorable, the vinylic eliminations have rate constants and computed barriers that are similar to those of analogous aliphatic eliminations. This is the result of the vinylic systems shifting to more E1(cb)-like transition states and exploiting the inherent greater acidity of vinylic hydrogens. In general, the α-substituents have a greater impact on the S(N)2 pathways and stabilize the transition states via field and polarizability effects. Substantial stabilization is also provided to the E2 transition states by the α-substituents, but they have surprisingly little impact on the geometries of the transition states of either pathway. The β-substituents generally lead to a strong bias toward elimination and greatly affect the synchronicity of the elimination (more E1(cb)-like) as well as its location on the reaction coordinate (early). The experimental and computational data are in good accord, and the full data set provides a comprehensive picture of substituent effects on solvent-free S(N)2 and E2 processes.