Lumettoman maan routaolojen mallintaminen ja ennustettavuus muuttuvassa ilmastossa

Raportissa on arvioitu ilmastonmuutoksen vaikutusta Suomen maaperän talviaikaiseen jäätymiseen lämpösummien perusteella. Laskelmat kuvaavat roudan paksuutta nimenomaisesti lumettomilla alueilla, esimerkiksi teillä, joilta satanut lumi aurataan pois. Luonnossa lämpöä eristävän lumipeitteen alla routaa on ohuemmin kuin tällaisilla lumettomilla alueilla. Toisaalta luonnollisessa ympäristössä paikalliset erot korostuvat johtuen mm. maalajeista ja kasvillisuudesta. Roudan paksuudet laskettiin ensin perusjakson 1971–2000 ilmasto-oloissa talviaikaisten säähavaintotietoihin pohjautuvien lämpötilojen perusteella. Sen jälkeen laskelmat toistettiin kolmelle tulevalle ajanjaksolle (2010–2039, 2040–2069 ja 2070–2099) kohottamalla lämpötiloja ilmastonmuutosmallien ennustamalla tavalla. Laskelman pohjana käytettiin 19 ilmastomallin A1B-skenaarioajojen keskimäärin simuloimaa lämpötilan muutosta. Tulosten herkkyyden arvioimiseksi joitakin laskelmia tehtiin myös tätä selvästi heikompaa ja voimakkaampaa lämpenemisarviota käyttäen. A1B-skenaarion mukaisen lämpötilan nousun toteutuessa nykyisiä mallituloksia vastaavasti routakerros ohenee sadan vuoden aikana Pohjois-Suomessa 30–40 %, suuressa osassa maan keski- ja eteläosissa 50–70 %. Jo lähivuosikymmeninä roudan ennustetaan ohentuvan 10–30 %, saaristossa enemmän. Mikäli lämpeneminen toteutuisi voimakkaimman tarkastellun vaihtoehdon mukaisesti, roudan syvyys pienenisi tätäkin enemmän. Roudan paksuuden vuosienvälistä vaihtelua ja sen muuttumista tulevaisuudessa pyrittiin myös arvioimaan. Leutoina talvina routa ohenee enemmän kuin normaaleina tai ankarina pakkastalvina. Päivittäistä sään vaihtelua simuloineen säägeneraattorin tuottamassa aineistoissa esiintyi kuitenkin liian vähän hyvin alhaisia ja hyvin korkeita lämpötiloja. Siksi näitten lämpötilatietojen pohjalta laskettu roudan paksuuskin ilmeisesti vaihtelee liian vähän vuodesta toiseen. Kelirikkotilanteita voi esiintyä myös kesken routakauden, jos useamman päivän suojasää ja samanaikainen runsas vesisade pääsevät sulattamaan maata. Tällaiset routakauden aikana sattuvat säätilat näyttävätkin yleistyvän lähivuosikymmeninä. Vuosisadan loppua kohti ne sen sijaan maan eteläosissa jälleen vähenevät, koska routakausi lyhenee oleellisesti. Tulevia vuosikymmeniä koskevien ilmastonmuutosennusteiden ohella routaa ja kelirikon esiintymistä on periaatteessa mahdollista ennustaa myös lähiaikojen sääennusteita hyödyntäen. Pitkät, viikkojen tai kuukausien mittaiset sääennusteet eivät tosin ole ainakaan vielä erityisen luotettavia, mutta myös lyhyemmistä ennusteista voisi olla hyötyä mm. tienpitoa suunniteltaessa.

Effect of thiocarbamate, urea, and uracil herbicides on lipid metabolism in groundnut (Arachis hypogaea) leaves

The effect of thiocarbamates (S-ethyldipropylthiocarbamate and diallate), substituted ureas (monuron and diuron), and uracils (bromacil and terbacil) on lipid metabolism in groundnut (Arachis hypogaea) leaves was investigated under nonphotosynthetic conditions. The uptake of [1-14C]acetate by leaf disks was inhibited by the thiocarbamates and marginally by the substituted ureas, but not by the uracil herbicides. The uptake of [methyl-14C]choline was inhibited to a lesser extent by thiocarbamates, while the other herbicides showed a slight stimulation. The thiocarbamates almost completely inhibited uptake of [32P]orthophosphate at 1.0 mM concentration, while diuron and terbacil showed significant inhibition. [1-14C]Acetate incorporation into lipids was inhibited only by diallate. [methyl-14C]Choline incorporation into the choline phosphoglycerides was inhibited by diallate, diuron, and bromacil. The incorporation of [32P]orthophosphate into phospholipids was substantially inhibited (over 90% at 1.0 mM) by the thiocarbamates, but not by the other herbicides. [35S]Sulfate incorporation into sulfoquinovosyl diglycerides was markedly inhibited only by the thiocarbamates. Fatty acid synthesis by isolated chloroplasts was inhibited 40–85% by thiocarbamates, substituted ureas, and bromacil, but not by terbacil. The inhibitory effect of the urea derivatives was reversible, but that of thiocarbamates was irreversible. sn-Glycerol-3-phosphate acyltransferase(s) of the chloroplast and microsomal fractions were profoundly inhibited by thiocarbamates, but not by the other two groups of herbicides. Phosphatidic acid phosphatase was insensitive to all the herbicides tested.

Three Dimensional Line-Clipping by Systematic Enumeration

Three dimensional clipping is a critical component of the 3D graphics pipeline. A new 3D clipping algorithm is presented in this paper. An efficient 2D clipping routine reported earlier has been used as a submodule. This algorithm uses a new classification scheme for lines of all possible orientations with respect to a rectangular parallelopiped view volume. The performance of this algorithm has been evaluated using exact arithmetic operation counts. It is shown that our algorithm requires less arithmetic operations than the Cyrus-Beck 3D clipping algorithm in all cases. It is also shown that for lines that intersect the clipping volume, our algorithm performs better than the Liang-Barsky 3D clipping algorithm.

Role of GDNF and its Cross-Talk with Other Growth Factors in the Dopaminergic System

Parkinson´s Disease (PD) is a neurodegenerative movement disorder resulting from loss of dopaminergic (DA) neurons in substantia nigra (SN). Possible causative treatment strategies for PD include neurotrophic factors, which protect and in some cases restore the function of dopaminergic neurons. Glial cell line-derived neurotrophic factor (GDNF) family of neurotrophic factors have been to date the most promising candidates for treatment of PD, demonstrating both neuroprotective and neurorestorative properties. We have investigated the role of GDNF in the rodent dopaminergic system and its possible crosstalk with other growth factors. We characterized the GDNF-induced gene expression changes by DNA microarray analysis in different neuronal systems, including in vitro cultured Neuro2A cells treated with GDNF, as well as midbrains from GDNF heterozygous (Hz) knockout mice. These microarray experiments, resulted in the identification of GDNF-induced genes, which were also confirmed by other methods. Further analysis of the dopaminergic system of GDNF Hz mice demonstrated about 40% reduction in GDNF levels, revealed increased intracellular dopamine concentrations and FosB/DeltaFosB expression in striatal areas. These animals did not show any significant changes in behavioural analysis of acute and repeated cocaine administration on locomotor activity, nor did they exhibit any changes in dopamine output following treatment with acute cocaine. We further analysed the significance of GDNF receptor RET signalling in dopaminergic system of MEN2B knock-in animals with constitutively active Ret. The MEN2B animals showed a robust increase in extracellular dopamine and its metabolite levels in striatum, increased tyrosine hydroxylase (TH) and dopamine transporter (DAT) protein levels by immunohistochemical staining and Western blotting, as well as increased Th mRNA levels in SN. MEN2B mice had increased number of DA neurons in SN by about 25% and they also exhibited increased sensitivity to the stimulatory effects of cocaine. We also developed a semi-throughput in vitro micro-island assay for the quantification of neuronal survival and TH levels by computer-assisted methodology from limited amounts of tissue. This assay can be applied for the initial screening for dopaminotrophic molecules, as well as chemical drug library screening. It is applicable to any neuronal system for the screening of neurotrophic molecules. Since our microarray experiments revealed possible GDNF-VEGF-C crosstalk we further concentrated on studying the neurotrophic effects of VEGF-C. We showed that VEGF-C acts as a neurotrophic molecule for the DA neurons both in vitro and in vivo, however without additive effect when used together with GDNF. The neuroprotective effect for VEGF-C in vivo in rat 6-OHDA model of PD was demonstrated. The possible signalling mechanisms of VEGF-C in the nervous system were investigated - infusion of VEGF-C to rat brain induced ERK activation, however no direct activation of RET signalling in vitro was found. VEGF-C treatment of rat striatum lead to up-regulation of VEGFR-1-3, indicating that VEGF-C can regulate the expression level of its own receptor. VEGF-C dopaminotrophic activity in vivo was further supported by increased vascular tissue in the neuroprotection experiments.

On The Temperature-Dependence of Regioselectivity in the Amination of Bromobenzotropones

The ipso/cine ratio in the amination of 5-bromo-2,3-benzo- or 2-bromo-4,5-benzotropone shows a dependence upon the temperature at which the reaction is conducted, changing in favour of the ipso-product when the temperature is maintained high, ruling out an aryne-type mechanism. A comparison of independent mechanisms envisaged for the formation of the two isomeric products suggests a two-part reason: (i) at a higher reaction temperature, C-protonation, a step necessary for the formation of the cine-product, could be retarded when a direct internal mode is interfered with by a less efficient external one, and (ii) reketonisation by elimination of bromide, needed to form the ipso-product, is likely to have a high temperature coefficient enabling the rate of its formation to overtake that of the cine-product.

Influence of water and thermal history on ion transport in lithium salt-succinonitrile plastic crystalline electrolytes

Important issues of water and thermal history affecting ion transport in a representative plastic crystalline lithium salt electrolyte: succinonitrile (SN)-lithium perchlorate (LiClO4) are discussed here. Ionic conductivity of electrolytes with high lithium salt amounts (similar to 1 M) in SN at a particular temperature is known to be influenced both by the trans-gauche isomerism and ion association (solvation), the two most important intrinsic parameters of the plastic solvent. In the present study both water and thermal history influence SN and result in enhancement of ionic conductivity of 1 M LiClO4-SN electrolyte. Systematic observations reveal that the presence of water in varying amounts promote ion-pair dissociation in the electrolyte. While trace amounts (approximate to 1-15 ppm) do not affect the trans-gauche isomerism of SN, the presence of water in large amounts (approximate to 5500 ppm) submerges the plasticity of SN. Subjugating the electrolyte to different thermal protocol resulted in enhancement of trans concentration only. This is an interesting observation as it demonstrates a simple and effective procedure involving utilization of an optimized set of external parameters to decouple solvation from trans-gauche isomerism. Observations from the ionic conductivity of various samples were accounted by changes in signature isomer and ion-association bands in the mid-IR regime and also from plastic to normal crystal transition temperature peak obtained from thermal studies. (C) 2010 Elsevier B.V. All rights reserved.

Conformation of polymerizable diacetylenic lecithin, DC8,9PC, by 1H-NMR spectroscopy

Diacetylenic phospholipid, 1,2 bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), forms helices and tubules in addition to liposomes. The diacetylenic moiety responsible for the transformation is probed by 2-D NMR correlated spectroscopy. Chemical shift assignments and the analysis of 2D-COSY measurements were done on the lipid in chloroform-d solution. Based on this analysis, a model for the lipid is proposed. The geometry of the headgroup, glycerol backbone and acyl chains up to three methylenes from glycerol backbone [-(CH2)(3)-] is similar to that of dipalmitoyl phosphatidylcholine. The estimated torsional angle for methylene groups adjacent to diacetylenic moieties suggested an overall tilt of the diacetylenic lipid molecule from the bilayer axis of 25-30 degrees. This tilt could be negative or positive depending on the handedness of the resultant microstructures.

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10(3) cm(-1)) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Omega cm and carrier concentration 1.52 x 10(15) cm(-3). Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices. (C) 2011 Elsevier B.V. All rights reserved.

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

Methanol oxidation on carbon-supported platinum-tin electrodes in sulfuric acid

A study is made of the electrooxidation of methanol in sulfuric acid on carbon-supported electrodes containing platinum-tin bimetal catalysts that are prepared by an in situ potentiometric-characterization route. The catalysts are investigated by employing chemical analyses, X-ray diffraction (XRD), X-ray absorption-near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) data in conjunction with electrochemical measurements. From the electrochemical data, it is inferred that while an electrode with (3:1) Pt-Sn/C catalyst involves a two-electron rate-limiting step akin to platinum-on-carbon electrodes, it is shifted to a one-electron mechanism on electrodes with (3:2)Pt-Sn/C, (3:3)Pt-Sn/C, and (3:4)Pt-Sn/C catalysts. The study suggests that the tin content in the platinum-tin bimetal catalyst produces: (i) a charge transfer from tin to platinum; (ii) an increase in the coverage of adsorbed methanolic residues with increase in the tin content, as indicated by the shift in rest potential of the electrodes towards the reversible value for oxidation of methanol (0.043 V versus SHE), and (iii) a decrease in the overall content of higher valent platinum sites in the catalyst.

High level stable expression of rat brain type IIA sodium channel ?-subunit in CHO cells

The neuronal sodium channels are responsible for the rising phase of action potential and are composed of three subunits, of which the alpha-subunit has been shown to be adequate for most of its functional properties. We have stably expressed the rat brain type IIA sodium channel alpha-subunit in CHO cell tine using a CMV promoter-based vector. The expression was confirmed by detecting a 6.5 kb RNA corresponding to sodium channel alpha-subunit using Northern hybridization. The cells stably expressing the alpha-subunit, yield isolated sodium currents of amplitudes greater than 4nA when studied in whole-cell configuration of the patch-clamp technique. The sodium currents are characterized by activation and inactivation properties similar to neuronal sodium channels, and are blocked by the voltage gated sodium channel blocker tetrodotoxin (TTX).

Methanol oxidation on carbon-supported platinum-tin electrodes in sulfuric acid

A study is made of the electrooxidation of methanol in sulfuric acid on carbon-supported electrodes containing platinum-tin bimetal catalysts that are prepared by an in situ potentiometric-characterization route. The catalysts are investigated by employing chemical analyses, X-ray diffraction (XRD), X-ray absorption-near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) data in conjunction with electrochemical measurements. From the electrochemical data, it is inferred that while an electrode with (3:1) Pt-Sn/C catalyst involves a two-electron rate-limiting step akin to platinum-on-carbon electrodes, it is shifted to a one-electron mechanism on electrodes with (3:2)Pt-Sn/C, (3:3)Pt-Sn/C, and (3:4)Pt-Sn/C catalysts. The study suggests that the tin content in the platinum-tin bimetal catalyst produces: (i) a charge transfer from tin to platinum; (ii) an increase in the coverage of adsorbed methanolic residues with increase in the tin content, as indicated by the shift in rest potential of the electrodes towards the reversible value for oxidation of methanol (0.043 V versus SHE), and (iii) a decrease in the overall content of higher valent platinum sites in the catalyst.

Stereoselections in cyclic β-ketoester alkylations

A hyperconjugative influence may be an additional factor in Z-alkylation being promoted by a syn-axial ester in enolates formed from conformationally immobilised 6-cyclic beta-ketoesters.

Theoretical estimation of the effect of minor elements on the solubility of oxygen in silicon melt

The effect of fourteen minor elements (Al, As, B, Bi, C, Ga, Ge, In, N, P, Pb, S, Sb and Sn) on the solubility of oxygen in silicon melt has been estimated using a recently developed theoretical equation, with only fundamental physical parameters such as hard sphere diameter, atomic volume and molar heat of solution at infinite dilution as inputs. The results are expressed in the form of interaction parameters. Although only limited experimental data are available for comparison, the theoretical approach appears to predict the correct sign, but underestimates the magnitude of the interaction between oxygen and alloying elements. The present theoretical approach is useful in making qualitative predications on the effect of minor elements on the solubility of oxygen in silicon melt, when direct measurements are not available.

Robust/Optimal Temperature Profile Control of a High-Speed Aerospace Vehicle Using Neural Networks

An approximate dynamic programming (ADP)-based suboptimal neurocontroller to obtain desired temperature for a high-speed aerospace vehicle is synthesized in this paper. A I-D distributed parameter model of a fin is developed from basic thermal physics principles. "Snapshot" solutions of the dynamics are generated with a simple dynamic inversion-based feedback controller. Empirical basis functions are designed using the "proper orthogonal decomposition" (POD) technique and the snapshot solutions. A low-order nonlinear lumped parameter system to characterize the infinite dimensional system is obtained by carrying out a Galerkin projection. An ADP-based neurocontroller with a dual heuristic programming (DHP) formulation is obtained with a single-network-adaptive-critic (SNAC) controller for this approximate nonlinear model. Actual control in the original domain is calculated with the same POD basis functions through a reverse mapping. Further contribution of this paper includes development of an online robust neurocontroller to account for unmodeled dynamics and parametric uncertainties inherent in such a complex dynamic system. A neural network (NN) weight update rule that guarantees boundedness of the weights and relaxes the need for persistence of excitation (PE) condition is presented. Simulation studies show that in a fairly extensive but compact domain, any desired temperature profile can be achieved starting from any initial temperature profile. Therefore, the ADP and NN-based controllers appear to have the potential to become controller synthesis tools for nonlinear distributed parameter systems.