Mesospheric temperature response to variations in geomagnetic activity

Temperature data collected over several years from rocket grenade and other experiments at Point Barrow (Alaska), Fort Churchill (Canada) and Wallops Island (Virginia) have been analysed to determine the effect of geomagnetic activity on the neutral temperature in the mesosphere and to study the latitudinal variation of this effect. An analysis carried out has revealed almost certainly significant correlations between the temperature and the geomagnetic indicies Kp and Ap at Fort Churchill and marginally significant correlations at Barrow and Wallops. This has also been substantiated by a linear regression analysis. The results indicate two types of interdependence between mesospheric temperature and geomagnetic field variations. The first type is the direct heating effect, during a geomagnetic disturbance, which has been observed in the present analysis with a time lag of 3–15 hr at the high latitudes and 36 hr at the middle latitudes. The magnitude of this heating effect has been found to decrease at the lower altitudes. The second type of interrelation which has been observed is temperature perturbations preceding geomagnetic field variations, both presumably caused by a disturbance in atmospheric circulation at these levels.

Nonparametric traversability estimation in partially occluded and deformable terrain

Terrain traversability estimation is a fundamental requirement to ensure the safety of autonomous planetary rovers and their ability to conduct long-term missions. This paper addresses two fundamental challenges for terrain traversability estimation techniques. First, representations of terrain data, which are typically built by the rover’s onboard exteroceptive sensors, are often incomplete due to occlusions and sensor limitations. Second, during terrain traversal, the rover-terrain interaction can cause terrain deformation, which may significantly alter the difficulty of traversal. We propose a novel approach built on Gaussian process (GP) regression to learn, and consequently to predict, the rover’s attitude and chassis configuration on unstructured terrain using terrain geometry information only. First, given incomplete terrain data, we make an initial prediction under the assumption that the terrain is rigid, using a learnt kernel function. Then, we refine this initial estimate to account for the effects of potential terrain deformation, using a near-to-far learning approach based on multitask GP regression. We present an extensive experimental validation of the proposed approach on terrain that is mostly rocky and whose geometry changes as a result of loads from rover traversals. This demonstrates the ability of the proposed approach to accurately predict the rover’s attitude and configuration in partially occluded and deformable terrain.

Analysis and computation of the oil film thickness between the piston ring and cylinder liner of an internal combustion engine

A study of the essential features of piston rings in the cylinder liner of an internal combustion engine reveals that the lubrication problem posed by it is basically that of a slider bearing. According to steady-flow-hydrodynamics, viz. Image the oil film thickness becomes zero at the dead centre positions as the velocity, U = 0. In practice, however, such a phenomenon cannot be supported by consideration of the wear rates of pistion rings and cylinder liners. This can be explained by including the “squeeze” action term in the

Rates of oxidation of thioketones by singlet oxygen

Rate constants for the quenching of singlet oxygen by a series of thioketones were measured by monitoring the inhibition of the self-sensitized photooxidation of rubrene. A correlation of the quenching rate with the nature of the substituents on the aromatic rings for the diarylthioketones and arylalkylthioketones was found, whereas correlation with the n orbital ionization potential was observed for the dialkylthioketones.

Structure of pentacyclo[7.4.2.02,6.06,15.011,14]pentadec-4-ene-7,13-dione, a novel pentacyclic C15 quinane system

C 15H 1602 (a synthetic precursor to dodecahedrane), monoclinic, P21/n, a = 12.171 (5), b = 6.976(5), c = 13.868 (3) A, B = 102.56 (3) ° , Z = 4, D m = 1.30, D c = 1.318 g cm -3, F(000) = 488, g(Mo K¢t) = 0.92 cm- 1. Intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.077 (R w = 0.076) for 1337 observed reflections. All the five-membered rings are cis fused and have envelope (C s symmetry) conformations.

The sensitivity of the northern hemisphere summer mean meridional circulation to changes in the large scale eddy forcing

A zonally averaged version of the Goddard Laboratory for Atmospheric Sciences (GLAS) climate model is used to study the sensitivity of the northern hemisphere (NH) summer mean meridional circulation to changes in the large scale eddy forcing. A standard solution is obtained by prescribing the latent heating field and climatological horizontal transports of heat and momentum by the eddies. The radiative heating and surface fluxes are calculated by model parameterizations. This standard solution is compared with the results of several sensitivity studies. When the eddy forcing is reduced to 0.5 times or increased to 1.5 times the climatological values, the strength of the Ferrel cells decrease or increase proportionally. It is also seen that such changes in the eddy forcing can influence the strength of theNH Hadley cell significantly. Possible impact of such changes in the large scale eddy forcing on the monsoon circulation via changes in the Hadley circulation is discussed. Sensitivity experiments including only one component of eddy forcing at a time show that the eddy momentum fluxes seem to be more important in maintaining the Ferrel cells than the eddy heat fluxes. In the absence of the eddy heat fluxes, the observed eddy momentum fluxes alone produce subtropical westerly jets which are weaker than those in the standard solution. On the other hand, the observed eddy heat fluxes alone produce subtropical westerly jets which are stronger than those in the standard solution.

Computational Studies on Bimetallic Clusters

The chemical and physical properties of bimetallic clusters have attracted considerable attention due to the potential technological applications of mixed-metal systems. It is of fundamental interests to study clusters because they are the link between atomic surface and bulk properties. More information of metal-metal bond in small clusters can be hence released. The studies in my thesis mainly focus on the two different kinds of bimetallic clusters: the clusters consisting of extraordinary shaped all metal four-membered rings and a series of sodium auride clusters. As described in most general organic chemistry books nowadays, a group of compounds are classified as aromatic compounds because of their remarkable stabilities, particular geometrical and energetic properties and so on. The notation of aromaticity is essentially qualitative. More recently, the connection has been made between aromaticity and energetic and magnetic properties. Also, the discussions of the aromatic nature of molecular rings are no longer limited to organic compounds obeying the Hückel’s rule. In our research, we mainly applied the GIMIC method to several bimetallic clusters at the CCSD level, and compared the results with those obtained by using chemical shift based methods. The magnetically induced ring currents can be generated easily by employing GIMIC method, and the nature of aromaticity for each system can be therefore clarified. We performed intensive quantum chemical calculations to explore the characters of the anionic sodium auride clusters and the corresponding neutral clusters since it has been fascinating in investigating molecules with gold atom involved due to its distinctive physical and chemical properties. As small gold clusters, the sodium auride clusters seem to form planar structures. With the addition of a negative charge, the gold atom in anionic clusters prefers to carry the charge and orients itself away from other gold atoms. As a result, the energetically lowest isomer for an anionic cluster is distinguished from the one for the corresponding neutral cluster. Mostly importantly, we presented a comprehensive strategy of ab initio applications to computationally implement the experimental photoelectron spectra.

Spatial and temporal variability in midge (Nematocera) assemblages in shallow Finnish lakes (60−70 °N) : community-based modelling of past environmental change

Multi- and intralake datasets of fossil midge assemblages in surface sediments of small shallow lakes in Finland were studied to determine the most important environmental factors explaining trends in midge distribution and abundance. The aim was to develop palaeoenvironmental calibration models for the most important environmental variables for the purpose of reconstructing past environmental conditions. The developed models were applied to three high-resolution fossil midge stratigraphies from southern and eastern Finland to interpret environmental variability over the past 2000 years, with special focus on the Medieval Climate Anomaly (MCA), the Little Ice Age (LIA) and recent anthropogenic changes. The midge-based results were compared with physical properties of the sediment, historical evidence and environmental reconstructions based on diatoms (Bacillariophyta), cladocerans (Crustacea: Cladocera) and tree rings. The results showed that the most important environmental factor controlling midge distribution and abundance along a latitudinal gradient in Finland was the mean July air temperature (TJul). However, when the dataset was environmentally screened to include only pristine lakes, water depth at the sampling site became more important. Furthermore, when the dataset was geographically scaled to southern Finland, hypolimnetic oxygen conditions became the dominant environmental factor. The results from an intralake dataset from eastern Finland showed that the most important environmental factors controlling midge distribution within a lake basin were river contribution, water depth and submerged vegetation patterns. In addition, the results of the intralake dataset showed that the fossil midge assemblages represent fauna that lived in close proximity to the sampling sites, thus enabling the exploration of within-lake gradients in midge assemblages. Importantly, this within-lake heterogeneity in midge assemblages may have effects on midge-based temperature estimations, because samples taken from the deepest point of a lake basin may infer considerably colder temperatures than expected, as shown by the present test results. Therefore, it is suggested here that the samples in fossil midge studies involving shallow boreal lakes should be taken from the sublittoral, where the assemblages are most representative of the whole lake fauna. Transfer functions between midge assemblages and the environmental forcing factors that were significantly related with the assemblages, including mean air TJul, water depth, hypolimnetic oxygen, stream flow and distance to littoral vegetation, were developed using weighted averaging (WA) and weighted averaging-partial least squares (WA-PLS) techniques, which outperformed all the other tested numerical approaches. Application of the models in downcore studies showed mostly consistent trends. Based on the present results, which agreed with previous studies and historical evidence, the Medieval Climate Anomaly between ca. 800 and 1300 AD in eastern Finland was characterized by warm temperature conditions and dry summers, but probably humid winters. The Little Ice Age (LIA) prevailed in southern Finland from ca. 1550 to 1850 AD, with the coldest conditions occurring at ca. 1700 AD, whereas in eastern Finland the cold conditions prevailed over a longer time period, from ca. 1300 until 1900 AD. The recent climatic warming was clearly represented in all of the temperature reconstructions. In the terms of long-term climatology, the present results provide support for the concept that the North Atlantic Oscillation (NAO) index has a positive correlation with winter precipitation and annual temperature and a negative correlation with summer precipitation in eastern Finland. In general, the results indicate a relatively warm climate with dry summers but snowy winters during the MCA and a cool climate with rainy summers and dry winters during the LIA. The results of the present reconstructions and the forthcoming applications of the models can be used in assessments of long-term environmental dynamics to refine the understanding of past environmental reference conditions and natural variability required by environmental scientists, ecologists and policy makers to make decisions concerning the presently occurring global, regional and local changes. The developed midge-based models for temperature, hypolimnetic oxygen, water depth, littoral vegetation shift and stream flow, presented in this thesis, are open for scientific use on request.

Reconstructions of past climates from documentary and natural sources in Finland since the 18th century

In this paper both documentary and natural proxy data have been used to improve the accuracy of palaeoclimatic knowledge in Finland since the 18th century. Early meteorological observations from Turku (1748-1800) were analyzed first as a potential source of climate variability. The reliability of the calculated mean temperatures was evaluated by comparing them with those of contemporary temperature records from Stockholm, St. Petersburg and Uppsala. The resulting monthly, seasonal and yearly mean temperatures from 1748 to 1800 were compared with the present day mean values (1961-1990): the comparison suggests that the winters of the period 1749-1800 were 0.8 ºC colder than today, while the summers were 0.4 ºC warmer. Over the same period, springs were 0.9 ºC and autumns 0.1 ºC colder than today. Despite their uncertainties when compared with modern meteorological data, early temperature measurements offer direct and daily information about the weather for all months of the year, in contrast with other proxies. Secondly, early meteorological observations from Tornio (1737-1749) and Ylitornio (1792-1838) were used to study the temporal behaviour of the climate-tree growth relationship during the past three centuries in northern Finland. Analyses showed that the correlations between ring widths and mid-summer (July) temperatures did not vary significantly as a function of time. Early (June) and late summer (August) mean temperatures were secondary to mid-summer temperatures in controlling the radial growth. According the dataset used, there was no clear signature of temporally reduced sensitivity of Scots pine ring widths to mid-summer temperatures over the periods of early and modern meteorological observations. Thirdly, plant phenological data with tree-rings from south-west Finland since 1750 were examined as a palaeoclimate indicator. The information from the fragmentary, partly overlapping, partly nonsystematically biased plant phenological records of 14 different phenomena were combined into one continuous time series of phenological indices. The indices were found to be reliable indicators of the February to June temperature variations. In contrast, there was no correlation between the phenological indices and the precipitation data. Moreover, the correlations between the studied tree-rings and spring temperatures varied as a function of time and hence, their use in palaeoclimate reconstruction is questionable. The use of present tree-ring datasets for palaeoclimate purposes may become possible after the application of more sophisticated calibration methods. Climate variability since the 18th century is perhaps best seen in the fourth paper study of the multiproxy spring temperature reconstruction of south-west Finland. With the help of transfer functions, an attempt has been made to utilize both documentary and natural proxies. The reconstruction was verified with statistics showing a high degree of validity between the reconstructed and observed temperatures. According to the proxies and modern meteorological observations from Turku, springs have become warmer and have featured a warming trend since around the 1850s. Over the period of 1750 to around 1850, springs featured larger multidecadal low-frequency variability, as well as a smaller range of annual temperature variations. The coldest springtimes occurred around the 1840s and 1850s and the first decade of the 19th century. Particularly warm periods occurred in the 1760s, 1790s, 1820s, 1930s, 1970s and from 1987 onwards, although in this period cold springs occurred, such as the springs of 1994 and 1996. On the basis of the available material, long-term temperature changes have been related to changes in the atmospheric circulation, such as the North Atlantic Oscillation (February-June).

Structure of a new crystal form of 2-{[3-(trifluoromethyl)phenyl]amino}benzoic acid (flufenamic acid)

C14Ht0F3NO2, P2.Jc, a = 12.523 (4), b = 7.868(6), c = 12.874 (3)A, fl = 95.2 (2) ° , O,,, = 1.47 (4), D e = 1.47 Mg m -3, Z = 4. Final R = 0.074 for 2255 observed reflections. The carboxyl group and the phenyl ring bearing the carboxyl group are nearly coplanar whereas the two phenyl rings are inclined with respect to each other at 52.8 ° . The difference between the two polymorphs of flufenamic acid lies in the geometrical disposition of the [3-(trifluoromethyl)- phenyl]amino moiety with respect to the benzoic acid moiety. As in other fenamate structures, the carboxyl group and the imino N atom are connected through an intramolecular hydrogen bond; also, pairs of centrosymmetrically related molecules are connected through hydrogen bonds involving carboxyl groups.

A novel use of near infrared spectroscopy: ageing deepwater sharks

To age sharks, the growth bands in the shark vertebrae (like the rings in a tree) or on the spines in front of each dorsal fin (which only some sharks have) are manually counted using a microscope. This is time-consuming and is only possible on dead animals. NIR spectroscopy is shown to be able to detect age in dorsal fin spines of sharks and hand-held NIR spectroscopy units could potentially be used for ageing of sharks in the field, at sea, using a hand-held unit to scan the fin spine on a live animal.

3,3',5,5'-Tetrabromophenolsulfonphthalein (bromphenol blue), C19H10Br4O5S

M r=670.02, monoclinic, C2/c, a= 31.003(4), b=11.037(2), c=21.183(3)A, fl= 143.7 (1) °, V= 4291.2/k 3, D,n = 2.06, D x = 2.07Mgm -3, Z=8, MoKa, 2=0.7107/k, /~=7.45 mm -1, F(000) = 2560, T= 293 K, R = 0.061 for 1697 observed reflections. The bromphenol blue molecule consists essentially of three planar groupings: the sulfonphthalein ring system and two dibromophenol rings attached to the tetrahedral C atom of the five-membered ring of the sulfonphthalein system. The dibromophenol rings are inclined with resPect to each other at 73 ° whereas they make angles of 85 and 68 ° with respect to the sulfonphthalein system. The molecules aggregate into helical columns with the non-polar regions of the molecules in the interior and the polar regions on the surface. The columns are held together by a network of hydrogen bonds.

4-Biphenylyl phenyl thioketone (I), C19H14S, and 1-naphthyl phenyl thioketone (II), C17H12S

(I): Mr=274"39, orthorhombic, Pbca, a = 7.443 (1), b= 32.691 (3), c= 11.828 (2)A, V= 2877.98A 3, Z=8, Din= 1.216 (flotation in KI), D x = 1.266 g cm -3, /~(Cu Ka, 2 = 1.5418 A) = 17.55 cm -1, F(000) = li52.0, T= 293 K, R = 6.8%, 1378 significant reflections. (II): M r = 248.35, orthorhombic, P212~21, a = 5.873 (3), b = 13.677 (3), c = 15-668 (5) A, V = 1260.14 A 3, Z = 4, D,n = 1.297 (flotation in KI), Dx= 1.308 g cm -a, /t(CuKa, 2=1.5418 A) = 19.55 cm -~, F(000) = 520.0, T= 293 K, R = 6.9%, 751 significant reflections. Crystals of (I) and (II) undergo photo-oxidation in the crystallinestate. In (I) the dihedral angle between the phenyl rings of the biphenyl moiety is 46 (1) °. The C=S bond length is 1.611(5) A in (I) and 1.630 (9)/~ in (II). The correlation between molecular packing and reactivity is discussed.

Molecular structure of nicotinamide adenine dinucleotide

NICOTINAMIDE adenine dinucleotide (NAD) has a fundamental role in metabolic processes as an electron transport molecule. Although its chemical structure was elucidated1 in 1934, its detailed conformation remains still to be established in spite of numerous physicochemical applications2. NAD analogues with a variety of substitutions on the bases are known to retain considerable activity of the natural coenzyme as long as the pyrophosphate diester group has been retained3,4. The geometry of this backbone moiety is therefore indispensable to our understanding of the conformation and function of the coenzyme. We have so far no experimental evidence on this in NAD or any other nucleotide coenzyme molecule. X-ray studies have been possible only on those analogues5,6 where the nicotinamide and adenine rings are linked by a trimethylene bridge. The results are conflicting and it is difficult to use them to provide a structural basis for the NAD molecule itself, particularly as the phosphate backbone is absent from these analogues.

Eru Ilúvatar : Jumala J.R.R. Tolkienin legendariumissa

The purpose of my research is to inquire into the essence and activity of God in the legendarium of the English philologist and writer J.R.R. Tolkien (1892-1973). The legendarium, composed of Tolkien’s writings related to Middle-earth, was begun when he created two Elvish languages, Quenya based on Finnish, Sindarin based on Welsh. Tolkien developed his mythology inspired by Germanic myths and The Kalevala. It is a fictional ancient history set in our world. The legendarium is monotheistic: God is called Eru ‘The One’ and Ilúvatar ‘Father of All’. Eru is the same as the Christian God, for Tolkien wanted to keep his tales consistent with his faith. He said his works were Christian by nature, with the religious element absorbed into the story and the symbolism. In The Silmarillion, set in the primeval ages of Middle-earth, the theological aspects are more conspicuous, while in The Lord of the Rings, which brings the stories to an end, they are mostly limited to symbolic references. The legendarium is unified by its realistic outlook on creaturely abilities and hope expressing itself as humbly defiant resistance. ”The possibility of complexity or of distinctions in the nature of Eru” is a part of the legendarium. Eru Ilúvatar is Trinitarian, as per Tolkien’s faith. Without contextual qualifiers, Eru seems to refer to God the Father, like God in the Bible. Being the creator who dwells outside the world is attributed to Him. The Holy Spirit is the only Person of the Trinity bestown with names: the Flame Imperishable and the Secret Fire. When Eru creates the material world with His word, He sends the Flame Imperishable to burn at the heart of the world. The Secret Fire signifies the Creative Power that belongs to God alone, and is a part of Him. The Son, the Word, is not directly mentioned, but according to one writing Eru must step inside the world in order to save it from corruption, yet remain outside it at the same time. The inner structure of the legendarium refers to the need for a future salvation. The creative word of Eru, “Eä! Let these things Be!”, probably has a connection with the Logos in Christianity. Thus we can find three “distinctions” in Eru: a Creator who dwells outside the world, a Sustainer who dwells inside it and a Redeemer who shall step inside it. Some studies of Tolkien have claimed that Eru is distant and remote. This seems to hold water only partially. Ilúvatar, the Father of All, has a special relation with the Eruhíni, His Children, the immortal Elves and the mortal Men. He communicates with them directly only through the Valar, who resemble archangels. Nevertheless, only the Children of Eru can fight against evil, because their tragic fortunes turn evil into good. Even though religious activities are scarce among them, the fundamental faith and ultimate hope of the “Free Peoples” is directed towards Eru. He is present in the drama of history as the “Author of the Story”, who at times also interferes with its course through catastrophes and eucatastrophes, ‘good catastrophes’. Eru brings about a catastrophe when evil would otherwise bring good to an end, and He brings about a eucatasrophe when creaturely strength is not sufficent for victory. Victory over corruption is especially connected with mortal Men, of whom the most (or least) insignificant people are the Hobbits. However, because of the “primeval disaster” (that is, fall) of Mankind, ultimate salvation can only remain open, a hope for the far future.