Stereoselective Acetate Aldol Reactions From Metal Enolates

This review deals with metal enolate-mediated stereoselective acetate aldol reactions. It summarizes recent advances on aldol additions of unsubstituted metal enolates from chiral auxiliaries, stoichiometric and catalytic Lewis acids, or acting in substrate- controlled reactions, which provide stereocontrolled aldol transformations that allow the efficient synthesis of structurally complex natural products.

A matter of time: delayed mate encounter postpones mating window initiation and reduces the strength of female choosiness

Reproductive success is determined by the presence and timing of encounter of mates. The latter depends on species-specific reproductive characteristics (e.g. initiation/duration of the mating window), season, and reproductive strategies (e.g. intensity of choosiness) that may potentially mitigate constraints imposed by mating windows. Despite their potentially crucial role for fitness and population dynamics, limited evidence exists about mating window initiation, duration and reproductive strategies. Here, we experimentally tested the mechanisms of initiation and the duration of the common lizard's Zootoca vivipara mating window, by manipulating the timing of mate encounter and analyzing its effect on (re-)mating probability. We furthermore tested treatment effects on female reproductive strategies, by measuring female choosiness. The timing of mate encounter and season did not significantly affect mating probability. However, a longer delay until mate encounter reduced female choosiness. Re-mating probability decreased with re-mating delay and was independent of mating delay. This indicates that mating window initiation depends on mate encounter, that its duration is fixed, and that plastic reproductive strategies exist. These findings contrast with previous beliefs and shows that mating windows per se may not necessarily constrain reproductive success, which is congruent with rapid range expansion and absence of positive density-effects on reproductive success (Allee effects). In summary, our results show that predicting the effect of mating windows on reproduction is complex and that experimental evidence is essential for evaluating their effect on reproduction and reproductive strategies, both being important determinants of population dynamics and the colonization of new habitats.

Costs of female reproduction in a conifer tree: a whole-tree level assessment

1. Costs of reproduction lie at the core of basic ecological and evolutionary theories, and their existence is commonly invoked to explain adaptive processes. Despite their sheer importance, empirical evidence for the existence and quantification of costs of reproduction in tree species comes mostly from correlational studies, while more comprehensive approaches remain missing. Manipulative experiments are a preferred approach to study cost of reproduction, as they allow controlling for otherwise inherent confounding factors like size or genetic background. 2. Here, we conducted a manipulative experiment in a Pinus halepensis common garden, removing developing cones from a group of trees and comparing growth and reproduction after treatment with a control group. We also estimated phenotypic and genetic correlations between reproductive and vegetative traits. 3. Manipulated trees grew slightly more than control trees just after treatment, with just a transient, marginally non-significant difference. By contrast, larger differences were observed for the number of female cones initiated 1 year after treatment, with an increase of 70% more cones in the manipulated group. Phenotypic and genetic correlations showed that smaller trees invested a higher proportion of their resources in reproduction, compared with larger trees, which could be interpreted as an indirect evidence for costs of reproduction. 4. Synthesis. This research showed a high impact of current reproduction on reproductive potential, even when not significant on vegetative growth. This has strong implications for how we understand adaptive strategies in forest trees and should encourage further interest on their still poorly known reproductive life-history traits.

Intracellular thiol-mediated modulation of epithelial sodium channel activity.

The epithelial sodium channel ENaC is physiologically important in the kidney for the regulation of the extracellular fluid volume, and in the lungs for the maintenance of the appropriate airway surface liquid volume that lines the pulmonary epithelium. Besides the regulation of ENaC by hormones, intracellular factors such as Na(+) ions, pH, or Ca(2+) are responsible for fast adaptive responses of ENaC activity to changes in the intracellular milieu. In this study, we show that ENaC is rapidly and reversibly inhibited by internal sulfhydryl-reactive molecules such as methanethiosulfonate derivatives of different sizes, the metal cations Cd(2+) and Zn(2+), or copper(II) phenanthroline, a mild oxidizing agent that promotes the formation of disulfide bonds. At the single channel level, these agents applied intracellularly induce the appearance of long channel closures, suggesting an effect on ENaC gating. The intracellular reducing agent dithiothreitol fully reverses the rundown of ENaC activity in inside-out patches. Our observations suggest that changes in intracellular redox potential modulate ENaC activity and may regulate ENaC-mediated Na(+) transport in epithelia. Finally, substitution experiments reveal that multiple cysteine residues in the amino and carboxyl termini of ENaC subunits are responsible for this thiol-mediated inhibition of ENaC.

Survival of zirconia- and metal-supported fixed dental prostheses: a systematic review

Purpose: The aim of this review was to systematically evaluate and compare the frequency of veneer chipping and core fracture of zirconia fixed dental prostheses (FOPS) and porcelain-fused-to-metal (PFM) FDPs and determine possible influencing factors. Materials and Methods: The SCOPUS database and International Association of Dental Research abstracts were searched for clinical studies involving zirconia and PFM FDPs. Furthermore, studies that were integrated into systematic reviews on PFM FDPs were also evaluated. The principle investigators of any clinical studies on zirconia FDPs were contacted to provide additional information. Based on the available information for each FOP, a data file was constructed. Veneer chipping was divided into three grades (grade 1 = polishing, grade 2 = repair, grade 3 = replacement). To assess the frequency of veneer chipping and possible influencing factors, a piecewise exponential model was used to adjust for a study effect. Results: None of the studies on PFM FDPs (reviews and additional searching) sufficiently satisfied the criteria of this review to be included. Thirteen clinical studies on zirconia FDPs and two studies that investigated both zirconia and PFM FDPs were identified. These studies involved 664 zirconia and 134 PFM FDPs at baseline. Follow-up data were available for 595 zirconia and 127 PFM FDPs. The mean observation period was approximately 3 years for both groups. The frequency of core fracture was less than 1% in the zirconia group and 0% in the PFM group. When all studies were included, 142 veneer chippings were recorded for zirconia FDPs (24%) and 43 for PFM FDPs (34%). However, the studies differed extensively with regard to veneer chipping of zirconia: 85% of all chippings occurred in 4 studies, and 43% of all chippings included zirconia FDPs. If only studies that evaluated both types of core materials were included, the frequency of chipping was 54% for the zirconia-supported FDPs and 34% for PFM FDPs. When adjusting the survival rate for the study effect, the difference between zirconia and PFM FDPs was statistically significant for all grades of chippings (P = .001), as well as for chipping grade 3 (P = .02). If all grades of veneer chippings were taken into account, the survival of PFM FDPs was 97%, while the survival rate of the zirconia FDPs was 90% after 3 years for a typical study. For both PFM and zirconia FDPs, the frequency of grades 1 and 2 veneer chippings was considerably higher than grade 3. Veneer chipping was significantly less frequent in pressed materials than in hand-layered materials, both for zirconia and PFM FDPs (P = .04). Conclusions: Since the frequency of veneer chipping was significantly higher in the zirconia FDPs than PFM FDPs, and as refined processing procedures have started to yield better results in the laboratory, new clinical studies with these new procedures must confirm whether the frequency of veneer chipping can be reduced to the level of PFM. Int J Prosthodont 2010;23:493-502

Metal leaching from a limestone quarry minesoil made with thermally-dried sewage sludge

Peer Reviewed

Logistics Management in China's Development Zones - Finnish Metal Industry Perspective

Alikehittynyt infrastruktuuri, tiukat säädökset ja säädösten tulkitseminen, sekä monimutkaiset verotuskäytännöt ovat aiheuttaneet ongelmia suomalaisille Alikehittynyt infrastruktuuri, tiukat säädökset ja säädösten tulkitseminen, sekä monimutkaiset verotuskäytännöt ovat aiheuttaneet ongelmia suomalaisille yrityksille Kiinassa. Tutkimuksen perusteella yritykset eivät pysty vaikuttamaan infrastruktuurin kehittymiseen tai säädösten implementointiin, mutta ylläpitämällä suhteita ja valitsemalla oikeat partnerit yritykset pystyvät hallitsemaan ongelma-alueitaan. Etenkin ulkomaalaisille yrityksille oikean logistiikkaoperaattorin valinta on tärkeätä ja huomioon ottaen palvelutason, kulttuuritaustan sekä kansainväliset operaatiot on ulkomaalaisten yritysten tehokkaampaa käyttää kansainvälisiä operaattoreita kuin paikallisia toimijoita, jotkaovat usein halvempia, mutta eivät pysty toimimaan kansainvälisellä tasolla. Vientiin keskittyneiden yritysten tulisi sijoittua vapaakauppa-alueille tai vientiin painottuneille teollisuusalueille. Kyseisillä alueilla liiketoiminta mannermaahan on rajoitettu, eivätkä alueet täten sovellu yrityksille, jotka ovat keskittyneet Kiinan markkinoille. Paikallisesti operoivien yritysten tulisi sijoittua normaaleihin teollisuuspuistoihin ja käyttää tullin valvomia varastoja tukemaan kansainvälisiä toimintojaan.Tulisi myös muistaa etteivät kiinalaiset teollisuuspuistot täytä kansainvälisiä kriteerejä, joten säädöksiin on tärkeätä tutustua huolella jamielipiteitä kerätä toisilta yrityksiltä. Kiinassa merkittävimmät logistiikkaongelmat ilmenevät tuonnin ja viennin yhteydessä, jolloin säädökset ja toimintamallit ovat kontrolloidumpia. Etenkin tullaus- ja arvonlisävero ongelmat liittyvät kiinteästi tuonti- ja vientiprosessiin. Tutkimuksen tulokset osoittivat, että tullausprosessi tehostuu yhteistyön ja koulutuksen kautta, mutta arvonlisäverosta aiheutuvien kustannusten minimointi vaatii logistiikkapuistojen käyttöä. Mikäli asiakas haluaa tehdä tullauksen kotiprovinssissaan tai yritys tekee kauppaa ALV -vapautettujen yritysten kanssa, tulisi logistiikkapuistojen käyttöä lisätä. Käytettäessä logistiikkapuistoja yritykset välttävät tuotteiden kuljetukset Hongkongiin jatakaisin säästäen huomattavasti kustannuksissa ja toimitusajoissa. Logistiikkapuistoja on myös mahdollista käyttää ratkaisuna kasvaviin ja viivästyviin ALV palautuksiin. Tutkimuksen tulosten mukaan toimintaympäristö ja vientipainotteinen valmistus ohjaavat 3PL yritysten valintaa ja vaihtoehtoisten logistiikkapalvelujen implementointia. Etabloiduttaessavapaakauppa-alueille vientiin ja tuontiin liittyvät ongelmatekijät vahvistuvat sekä rajoitukset kiinan liiketoimintaan kasvavat, mikä tekee yhteistyönkansainvälisten logistiikkaoperaattoreiden kanssa välttämättömäksi ja kannustaa hyödyntämään logistiikkapuistoja.

Fructose Rich Diet-Induced High Plasminogen Activator Inhibitor-1 (PAI-1) Production in the Adult Female Rat: Protective Effect of Progesterone.

The effect of progesterone (P4) on fructose rich diet (FRD) intake-induced metabolic, endocrine and parametrial adipose tissue (PMAT) dysfunctions was studied in the adult female rat. Sixty day-old rats were i.m. treated with oil alone (control, CT) or containing P4 (12 mg/kg). Rats ate Purina chow-diet ad libitum throughout the entire experiment and, between 100 and 120 days of age drank ad libitum tap water alone (normal diet; CT-ND and P4-ND) or containing fructose (10% w/v; CT-FRD and P4-FRD). At age 120 days, animals were subjected to a glucose tolerance test or decapitated. Plasma concentrations of various biomarkers and PMAT gene abundance were monitored. P4-ND (vs. CT-ND) rats showed elevated circulating levels of lipids. CT-FRD rats displayed high (vs. CT-ND) plasma concentrations of lipids, leptin, adiponectin and plasminogen activator inhibitor-1 (PAI-1). Lipidemia and adiponectinemia were high (vs. P4-ND) in P4-FRD rats. Although P4 failed to prevent FRD-induced hyperleptinemia, it was fully protective on FRD-enhanced plasma PAI-1 levels. PMAT leptin and adiponectin mRNAs were high in CT-FRD and P4-FRD rats. While FRD enhanced PMAT PAI-1 mRNA abundance in CT rats, this effect was absent in P4 rats. Our study supports that a preceding P4-enriched milieu prevented the enhanced prothrombotic risk induced by FRD-elicited high PAI-1 production.

A support system for evaluating a suitable joining method in the production of sheet metal goods

This report illustrates a comparative study of various joining methods involved in sheet metal production. In this report it shows the selection of joining methods, which includes comparing the advantages and disadvantages of a method over the other ones and choosing the best method for joining. On the basis of various joining process from references, a table is generated containing set of criterion that helps in evaluation of various sheet metal joining processes and in selecting the most suitable process for a particular product. Three products are selected and a comprehensive study of the joining methods is analyzed with the help of various parameters. The table thus is the main part of the analysis process of this study and can be advanced with the beneficial results. It helps in a better and easy understanding and comparing the various methods, which provides the foundation of this study and analysis. The suitability of the joining method for various types of cases of different sheet metal products can be tested with the help of this table. The sections of the created table display the requirements of manufacturing. The important factor has been considered and given focus in the table, as how the usage of these parameters is important in percentages according to particular or individual case. The analysis of the methods can be extended or altered by changing the parameters according to the constraint. The use of this table is demonstrated by pertaining the cases from sheet metal production.

A female melanin ornament signals offspring fluctuating asymmetry in the barn owl.

Sexual selection theory predicts that males advertise quality by displaying extravagant ornaments. By contrast, whether phenotypic variation in females has a signalling function remains an open question. Here, to our knowledge, we provide the first evidence that a female plumage trait can signal fluctuating asymmetry in the offspring. We experimentally demonstrate in wild barn owls (Tyto alba) that the extent to which females display black spots on their plumage does not only signal offspring parasite resistance as shown in a previous study but also developmental homeostasis in the offspring. A greater number of spotted females produced offspring that had more symmetrical feathers during the period of growth. Males, that pair non-randomly with respect to female plumage spottiness therefore appear to gain substantial benefits by mating with heavily spotted females. Genetic variation in plumage spottiness is nevertheless maintained as the covariation between offspring body mass and mother plumage spottiness varies annually depending on environmental conditions.

Value added logistical support service Part 2. Outsourcing process of spare part logistics in metal industry

The aim of this research study was to find out guidelines for outsourcing of logistics processes. The study was outlined to spare parts and `business-to-business' (B2B) markets in metal industry. This study can be applied as a manual for outsourcing especially warehousing and transportation activities. The study also touches other important areas of spare part logistics like manufacturing, customer service, procurement, quality control, reverse and recycling logistics, logistics technologies and valueadded services. The method of study consisted of three areas. Firstly exchanging views with logistics experts in participating companies, and secondly compiling material based on author's practical experience in logistics business with several international and domestic logistics service providers and vendors. Thirdlythe study includes also references to literature material. Due to the fact thatthe outsourcing of logistics functions can be handled widely and from differentpoint of views, in this study it is concentrated mainly on giving general levelguidelines for defining logistics strategy, hints both for tendering process and implementation project, and not forgetting the aftercare of business partnership.

Freezing Point Depressions of Dilute Solutions of Alkali Metal Chlorides and Bromides

Freezing point depressions (¿Tf) of dilute solutions of several alkali metal chlorides and bromides were calculated by means of the best activity coefficient equations. In the calculations, Hückel, Hamer and Pitzer equationswere used for activity coefficients. The experimental ¿Tf values available in the literature for dilute LiCl, NaCl and KBr solutions can be predicted within experimental error by the Hückel equations used. The experimental ¿Tf values for dilute LiCl and KBr solutions can also be accurately calculated by corresponding Pitzer equations and those for dilute NaCl solutions by the Hamer equation for this salt. Neither Hamer nor Pitzer equations predict accurately the freezing points reported in the literature for LiBr and NaBr solutions. The ¿Tf values available for dilute solutions of RbCl, CsCl or CsBr are not known at the moment accurately because the existing data for these solutions are not precise. The freezing point depressions are tabulated in the present study for LiCl, NaCl and KBr solutions at several rounded molalities. The ¿Tf values in this table can be highly recommended. The activity coefficient equations used in the calculation of these values have been tested with almost allhigh-precision electrochemical data measured at 298.15 K.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Metal surface and subsurface inspection using nondestructive optical methods

This thesis considers nondestructive optical methods for metal surface and subsurface inspection. The main purpose of this thesis was to study some optical methods in order to find out their applicability to industrial measurements. In laboratory testing the simplest light scattering approach, measurement of specular reflectance, was used for surface roughness evaluation. Surface roughness, curvature and finishing process of metal sheets were determined by specular reflectance measurements. Using a fixed angleof incidence, the specular reflectance method might be automated for industrialinspection. For defect detection holographic interferometry and thermography were compared. Using either holographic interferometry or thermography, relativelysmall-size defects in metal plates could be revealed. Holographic techniques have some limitations for industrial measurements. On the contrary, thermography has excellent prospects for on-line inspection, especially with scanning techniques.