N-mesityl-C-acylketenimines: 1,5-sigmatropic shifts and electrocyclization to quinolines

Flash vacuum thermolysis (FVT) of triazoles 6a-c generates alpha-oxoketenimines 10, the ester 10a being isolable. FVT of pyrroledione 8 generates the isomeric imidoylketene 9a. Ketenes 9 and ketenimines 10 undergo thermal interconversion by 1,3-shifts of methoxy and dimethylamino groups under mild FVT conditions (ca. 350-400 degrees C). Both 9 and 10 are directly observable by IR spectroscopy at either 77 K or on Ar matrix isolation at 12 K. On FVT at temperatures above ca. 400 degrees C, the ketenimines 10 undergo a 1,5-H shift to o-quinoid imines 12/13, followed by electrocyclization to dihydroquinolines 14 (unobserved) and 15 (observed by NMR). The latter are easily oxidized to alkylquinoline-3-carboxylates or quinoline-3-carboxamides 16 by atmospheric oxygen. Ab initio calculations on model compounds 18-23 predict an energy barrier of ca. 38 kcal mol(-1) (161 kJ mol(-1)) for the 1,5-H shift in N-(o-methylphenyl)ketenimines via the transition state TS19 followed by an electrocyclization barrier to dihydroquinoline 23a via TS22a of ca. 16 kcal mol(-1).

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

Role of PGF(2 alpha) and oxytocin in parturition in the brushtail possum (Trichosurus vulpecula)

Maturation of the fetal pituitary and adrenal glands allows the secretion of cortisol, which in turn leads to an increase in prostaglandin and mesotocin production. The production of prostaglandin and mesotocin results in an increase in uterine contractions and initiates birth in marsupials. The major metabolite of PGF(2alpha), 13,14-dihydro-15-keto-prostaglandin F-2alpha (PGFM), has been found in the plasma of the possum at the time of birth and administration of PGF(2alpha) to female possums induced the adoption of the birth position. Evidence that mesotocin is an integral hormone of birth in the tammar wallaby indicates that both PGF(2alpha) and mesotocin or oxytocin are required for marsupial birth. The presence of PGF(2alpha) receptors in the uterus and corpus luteum of the possum, and the in vitro uterine responsiveness to PGF(2alpha) or oxytocin, were examined. PGF(2alpha) receptors were not observed in possum uteri and the inability of PGF(2alpha) to cause contractions indicates that PGF(2alpha) is not involved directly in contraction of the uterus at parturition. The presence of oxytocin and mesotocin receptors in the uterus of possoms and the ability of oxytocin to induce uterine contraction in vitro supports the view that mesotocin is required for expulsion of the young from the uterus. Low numbers of PGF(2alpha) receptors were found in the possum corpus luteum at birth, indicating an involvement of PGF(2alpha) in regression of the corpus luteum.

Resistance development in community-acquired strains of methicillin-resistant Staphylococcus aureus: an in vitro study

This study compares in vitro antimicrobial resistance development between strains of Staphylococcus aureus including newly described community-acquired methicillin-resistant strains (CA-MRSA). High-level resistance developed in all strains of S. aureus after exposure to rifampicin and gentamicin and in some strains after fusidic acid exposure, independent of methicillin resistance phenotype. Resistance did not develop after exposure to clindamycin, cotrimoxazole, ciprofloxacin, linezolid, or vancomycin. These results have important implications for therapy of CA-MRSA infections. (C) 2004 Elsevier B.V. and the International Society of Chemotherapy. All rights reserved.

Dinosaur sanctuary on the Chatham Islands, Southwest Pacific: First record of theropods from the K-T boundary Takatika Grit

Cretaceous-Tertiaty (K-T) boundary (ca. 65 Ma) sections on a Southwest Pacific island containing dinosaurs were unknown until March 2003 when theropod bones were recovered from the Takatika Grit on the remote Chatham Islands (latitude 44 degrees S, longitude 176 degrees W), along the Chatham Rise. Tectonic and palaeontologic evidence support the eastward extension of a ca. 900 km land bridge that connected the islands to what is now New Zealand prior to the K-T boundary. The Chathams terrestrial fauna inhabited coastal, temperate environments along a low-lying, narrow, crustal extension of the New Zealand subcontinent, characterised by a tectonically dynamic, volcanic landscape with eroding hills (horsts) adjacent to flood plains and deltas, all sediments accumulating in grabens. This finger-like tract was blanketed with a conifer and clubmoss (Lycopodiopsida) dominated forest. The Chatham Islands region would have, along with New Zealand, provided a dinosaur island sanctuary after separating from the Gondwana margin ca. 80 Ma. (c) 2005 Elsevier B.V. All rights reserved.

The pearl oysters, Pinctada maxima and P margaritifera, respond in different ways to culture in dissimilar environments

Growth, Condition Index (CI) and survival of the pearl oysters, Pinctada maxima and R margaritifera, were measured in three size groups of oysters over 14 months at two dissimilar environments in the Great Barrier Reef lagoon. These were the Australian Institute of Marine Science (AIMS) in a mainland bay and Orpheus Island Research Station (OIRS) in coral reef waters. Temperature, suspended particulate matter (SPM) and particulate organic matter (POM) were monitored during the study. Temperature at AIMS fluctuated more widely than at OIRS both daily and seasonally, with annual ranges 20-31 degrees C and 22-30 degrees C, respectively. Mean SPM concentration at AIMS (11.1 mg l(-1)) was much higher than at OIRS (1.4 mg l(-1)) and fluctuated widely (2-60 mg l(-1)). Mean POM level was also substantially higher at AIMS, being 2.1 mg l(-1) compared with 0.56 mg l(-1) at OIRS. Von Bertalatiffy growth curve analyses showed that P. maxima grew more rapidly and to larger sizes than P. margaritifera at both sites. For the shell height (SH) of R maxima, growth index phi'=4.31 and 4.24, asymptotic size SHinfinity = 229 and 205 mm, and time to reach 120 mm SH (T-(120))= 1.9 and 2.1 years at AIMS and OIRS, respectively. While for P margaritifera, phi'=4.00 and 4.15, SHinfinity = 136 and 157 mm, and T-(120) = 2.5 and 3.9 years at AIMS and OIRS, respectively. R maxima had significantly lower growth rates and lower survival of small oysters during winter compared with summer. There were, however, no significant differences between the two sites in growth rates of P. maxima and final Cl values. In contrast, P. margaritifiera showed significant differences between sites and not seasons, with lower growth rates, survival of small oysters, final Cl values and asymptotic sizes at AIMS. The winter low temperatures, but not high SPM at AIMS, adversely affected P. maxima. Conversely, the high SPM levels at AIMS, but not temperature, adversely affected P. margaritifera. This was in accordance with earlier laboratory-based energetics studies of the effects of temperature and SPM on these two species. P maxima has potential to be commercially cultured in ca. > 25 degrees C waters with a wide range of SPM levels, including oligotrophic coral reef waters with appropriate particle sizes. It is possible to culture R margaritifera in turbid conditions, but its poor performance in these conditions makes commercial culture unlikely. (c) 2005 Elsevier B.V. All rights reserved.

Effect of pH on Na induced Ca deficiency

Although it is well known that high Na concentrations induce Ca deficiency in acidic conditions, the effect of high pH on this competitive mechanism is not so well understood. The effect of Ca activity ratio (CAR) and pH on the Ca uptake of mungbeans (Vigna radiata (L.) Wilczek cv. Emerald) and Rhodes grass (Chloris gayana cv. Pioneer) in Na dominated solution cultures and in soil was investigated. Changes in pH in the alkaline range were shown not to affect the critical CAR of 0.024 (corresponding to 90 % relative root length) for mungbeans grown in solution culture. Results from soil grown mungbeans confirmed those from solution culture, with a critical CAR of 0.025. A critical CAR of 0.034 was also established for soil grown Rhodes grass. The similarity of critical values established for mungbeans and Rhodes grass in solution culture and soil justifies the use of both solution culture and soil solution measurement as techniques for studying plant growth and limitations across plant species.

Mg induced Ca deficiency under alkaline conditions

Little is known about Mg induced Ca deficiency in alkaline conditions, and the relationship between Mg induced Ca deficiency and Na induced Ca deficiency. Dilute nutrient solutions (dominated by Mg) were used to investigate the effect of Ca activity ratio (CAR) on the growth of mungbeans (Vigna radiata (L.) Wilczek cv. Emerald). At pH 9.0, root growth was reduced below a critical CAR of 0.050 (corresponding to 90 % relative root length). Root growth was found to be limited more in Mg solutions than had been previously observed for Na solutions. Using a CAR equation modified with plasma membrane binding constants (to incorporate the differing antagonistic effects of Mg and Na), new critical CAR values were calculated for both Na (0.56) and Mg (0.44) dominated solutions. This modified CAR equation permits the calculation of CAR irrespective of the dominant salt present.

Effect of ionic strength and clay mineralogy on Na-Ca exchange and the SAR-ESP relationship

The relationship between sodium adsorption ratio (SAR) and exchangeable sodium percentage (ESP) for all soils has traditionally been assumed to be similar to that developed by the United States Salinity Laboratory (USSL) in 1954. However, under certain conditions, this relationship has been shown not to be constant, but to vary with both ionic strength and clay mineralogy. We conducted a detailed experiment to determine the effect of ionic strength on the Na+-Ca2+ exchange of four clay minerals (kaolinite, illite, pyrophyllite, and montmorillonite), with results related to the diffuse double-layer (DDL) model. Clays in which external exchange sites dominated (kaolinite and pyrophyllite) tended to show an overall preference for Na+, with the magnitude of this preference increasing with decreasing ESP. For these external surfaces, increases in ionic strength were found to increase preference for Na+. Although illite (2:1 non-expanding mineral) was expected to be dominated by external surfaces, this clay displayed an overall preference for Ca2+, possibly indicating the opening of quasicrystals and the formation of internal exchange surfaces. For the expanding 2:1 clay, montmorillonite, Na+-Ca2+ exchange varied due to the formation of quasicrystals (and internal exchange surfaces) from individual clay platelets. At small ionic strength and large ESP, the clay platelets dispersed and were dominated by external exchange surfaces (displaying preference for Na+). However, as ionic strength increased and ESP decreased, quasicrystals (and internal exchange surfaces) formed, and preference for Ca2+ increased. Therefore, the relationship between SAR and ESP is not constant and should be determined directly for the soil of interest.

Regulation of the Hsp90-binding immunophilin, cyclophilin 40, is mediated by multiple sites for CA-binding protein (GABP)

Within steroid receptor heterocomplexes the large tetraticopeptide repeat-containing immunophilins, cyclophilin 40 (CyP40), FKBP51, and FKBP52, target a common interaction site in heat shock protein 90 (HspSO) and act coordinately with HspSO to modulate receptor activity. The reversible nature of the interaction between the immunophilins and HspSO suggests that relative cellular abundance might be a key determinant of the immunophilin component within steroid receptor complexes. To investigate CyP40 gene regulation, we have isolated a fi-kilobase (kb) 5 ' -flanking region of the human gene and demonstrated that a similar to 50 base pair (bp) sequence adjacent to the transcription start site is essential for CyP40 basal expression. Three tandemly arranged Ets sites within this critical region were identified as binding elements for the multimeric Ets-related transcription factor, GA binding protein (GABP). Functional studies of this proximal promoter sequence, in combination with mutational analysis, confirmed these sites to be crucial for basal promoter function. Furthermore, overexpression of both GABP alpha and GABP beta subunits in Cos1 cells resulted in increased endogenous CyP40 mRNA levels. Significantly, a parallel increase in FKBP52 mRNA expression was not observed, highlighting an important difference in the mode of regulation of the CyP40 and FKBP52 genes. Our results identify GABP as a key regulator of CyP40 expression. GAFF is a common target of mitogen and stress-activated pathways and may integrate these diverse extracellular signals to regulate CyP40 gene expression.

Phase and microstructural evolution during the heat treatment of Sm-Ca-alpha-sialon ceramics

The phase and microstructural evolution of multi-cation Sm-Ca-alpha-sialon ceramics was investigated. Six samples were prepared, ranging from a pure Sm-sialon to a pure Ca-sialon, with calcium replacing samarium in 20 eq% increments, thus maintaining an equivalent design composition in all samples. After pressureless sintering at 1820 degreesC for 2 It, all samples were subsequently heat treated up to 192 h at 1450 and 1300 degreesC. The amount of grain boundary glass in the samples after sintering was observed to decrease with increasing calcium levels. A M-ss' or M-ss',-gehlenite solid solution was observed to form during the 1450 degreesC heat treatment of all Sm-containing samples, and this phase forms in clusters in the high-Sm samples. The thermal stability of the alpha-sialon phase was improved in the multi-cation systems. Heat treatment at 1300 degreesC produces SmAlO3 in the high-Sm samples, a M-ss',-gehlenite solid solution in the high-Ca samples, and a Sm-Ca-apatite phase in some intermediate samples. (C) 2002 Elsevier Science Ltd. All rights reserved.

Deconvolving the delta O-18 seawater component from subseasonal coral delta O-18 and Sr/Ca at Rarotonga in the southwestern subtropical Pacific for the period 1726 to 1997

To reconstruct oceanographic variations in the subtropical South Pacific, 271-year long subseasonal time series of Sr/Ca and delta(18)O were generated from a coral growing at Rarotonga (21.5degreesS, 159.5degreesW). In this case, coral Sr/Ca appears to be an excellent proxy for sea surface temperature (SST) and coral delta(18)O is a function of both SST and seawater delta(18)O composition (delta(18)O(sw)). Here, we focus on extracting the delta(18)O(sw) signal from these proxy records. A method is presented assuming that coral Sr/Ca is solely a function of SST and that coral delta(18)O is a function of both SST and delta(18)O(sw). This method separates the effects of delta(18)O(sw) from SST by breaking the instantaneous changes of coral delta(18)O into separate contributions by instantaneous SST and delta(18)O(sw) changes, respectively. The results show that on average delta(18)O(sw) at Rarotonga explains similar to39% of the variance in delta(18)O and that variations in SST explains the remaining similar to61% of delta(18)O variance. Reconstructed delta(18)O(sw) shows systematic increases in summer months (December-February) consistent with the regional pattern of variations in precipitation and evaporation. The delta(18)O(sw) also shows a positive linear correlation with satellite-derived estimated salinity for the period 1980 to 1997 (r = 0.72). This linear correlation between reconstructed delta(18)O(sw) and salinity makes it possible to use the reconstructed delta(18)O(sw) to estimate the past interannual and decadal salinity changes in this region. Comparisons of coral delta(18)O and delta(18)O(sw) at Rarotonga with the Pacific decadal oscillation index suggest that the decadal and interdecadal salinity and SST variability at Rarotonga appears to be related to basin-scale decadal variability in the Pacific. Copyright (C) 2002 Elsevier Science Ltd.