Molecular complexes of metallo tetraphenyl porphyrins with 2,4,5,7-tetranitro fluorenone

The interactions of mesotetraphenyl porphyrin and its metallo derivatives with 2,4,5,7-tetra nitrofluorenone have been studied using spectroscopic methods. The association constants (K) for 1:1 complexes in Ch2Cl2Cl2 follow the order Pd+2>Co+2> Cu+2>VO+2>Ni+2>Zn+2. The values of K are accounted in terms of stereochemistry of MTPPs and the electronic configuration of the metal ions. The magnitude and direction of the proton NMR shifts of the acceptor and donor in the complexes and their ESR parameter furnish information as to the possible structures of these complexes in solution.

Conformational analysis of small disulfide loops. Spectroscopic and theoretical studies on a synthetic cyclic tetrapeptide containing cystine

The conformational analysis of the synthetic peptide Boc-Cys-Pro-Val-Cys-NHMe has been carried out, as a model for small disulfide loops, in biologically active polypeptides. 'H NMR studies (270 MHz) establish that the Val(3) and Cys(4) NH groups are solvent shielded, while 13C studies establish an all-trans peptide backbone. Circular dichroism and Raman spectroscopy provide evidence for a right-handed twist of the disulfide bond. Analysis of the vicinal (JaB)c oupling constants for the two Cys residues establishes that XI - *60° for Cys(4), while some flexibility is suggested at Cys( 1). Conformational energy calculations, imposing intramolecular hydrogen bonding constraints, favor a P-turn (type I) structure with Pro(2)-Va1(3) as the corner residues. Theoretical and spectroscopic results are consistent with the presence of a transannular 4 - 1 hydrogen bond between Cys( 1) CO and Cys(4) NH groups, with the Val NH being sterically shielded from the solvent environment.

Adsorption isitherms for neutral organic compounds-A hierarchy in modelling: Part IV. Charge of maximum adsorption-Statistical mechanical basis

The charge at which adsorption of orgamc compounds attains a maximum ( \sigma MAX M) at an electrochenucal interface is analysed using several multi-state models in a hierarchical manner The analysis is based on statistical mechamcal results for the following models (A) two-state site parity, (B) two-state muhl-slte, and (C) three-state site parity The coulombic interactions due to permanent and reduced dipole effects (using mean field approximation), electrostatic field effects and specific substrate interactions have been taken into account. The simplest model in the hierarchy (two-state site parity) yields the exphcit dependence of ( \sigma MAX M) on the permanent dipole moment, polarizability of the solvent and the adsorbate, lattice spacing, effective coordination number, etc Other models in the baerarchy bring to hght the influence of the solvent structure and the role of substrate interactions, etc As a result of this approach, the "composition" of oM.x m terms of the fundamental molecular constants becomes clear. With a view to use these molecular results to maxamum advantage, the derived results for ( \sigma MAX M) have been converted into those involving experimentally observable parameters lake Co, C 1, E N, etc Wherever possible, some of the earlier phenomenologlcal relations reported for ( \sigma MAX M), notably by Parsons, Damaskm and Frumkln, and Trasattl, are shown to have a certain molecular basis, vlz a simple two-state sate panty model.As a corollary to the hxerarcbacal modelling, \sigma MAX M and the potential corresponding to at (Emax) are shown to be constants independent of 0max or Corg for all models The lmphcatlon of our analysis f o r OmMa x with respect to that predicted by the generalized surface layer equation (which postulates Om~ and Ema x varlaUon with 0) is discussed in detail Finally we discuss an passing o M. and the electrosorptlon valency an this context.

Adsorption isotherms for neutral organic compounds - A hierarchy in modelling: Part V. Models for the inner layer potential difference in the presence of dipolar adsorption

The relations for the inner layer potential &fference (E) in the presence of adsorbed orgamc molecules are derived for three hterarchlcal models, m terms of molecular constants like permanent &pole moments, polarlzablhtles, etc It is shown how the experimentally observed patterns of the E vs 0 plots (hnear m all ranges of $\sigma^M$, non-linear in one or both regions of o M, etc ) can be understood in a serm-quantltatlve manner from the simplest model in our hierarchy, viz the two-state site panty version Two-state multi-site and three-state (sxte panty) models are also analysed and the slope (3E/80),,M tabulated for these also The results for the Esm-Markov effect are denved for all the models and compared with the earlier result of Parsons. A comparison with the GSL phenomenologlcal equation is presented and its molecular basis, as well as the hmltatlons, is analysed. In partxcular, two-state multa-slte and three-state (site panty) models yield E-o M relations that are more general than the "umfied" GSL equation The posslblhty of vaewlng the compact layer as a "composite medium" with an "effective dlelectnc constant" and obtaimng novel phenomenological descnptions IS also indicated.

Dielectric Relaxation in SrLiB9O15 Glasses

Transparent SrLiB9O15 (SLBO) glasses were fabricated via the conventional melt-quenching technique. X-ray powder diffraction and differential thermal analysis carried out on the as-quenched samples confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 100 Hz to 10 MHz frequency range for SLBO glasses were measured as a function of temperature (300–1023 K). The dielectric relaxation characteristics were rationalized using the electric modulus formalism. The electrode polarization effect was subtracted from the low-frequency dielectric constant to have an insight into the intrinsic dielectric behavior of SLBO glasses. The imaginary part of electric modulus spectra was modeled using an approximate solution of Kohlrausch–Williams–Watts relation. The dielectric constant for the as-quenched glass increased with increasing temperature and exhibited anomalies in the vicinity of the glass transition and crystallization temperatures.

Synthesis and structure of mixed ligand isonitroso-β-ketoiminenickel(II) complexes. Crystal structure of (1-ethoxycarbonyl-2-npropylimino-1-propanoneoximato) (1-methoxycarbonyl-2-imino-1-propanoneoximato)nickel(II)

Mixed ligand complexes of the type Ni(R-AB)(AC') and Ni(R-AC)(AB') where AB/AC denote N-bonded isonitroso- [3-ketoimino ligands, AB'/AC' denote the corresponding Obonded ligands and R = Me, Et, n-Pr are synthesised and characterised. The complexes are neutral with square planar geometry around nickel(II). The bonding isomerism of the isonitroso group is discussed on the basis of i.r. and 1H n.m.r. studies. The crystal structure of the title complex, Ni(n-Pr-IEAI)(IMAI') has been determined from diffractometer data by Patterson and Fourier methods and refined by least squares to R = 0.088 for 2209 observed reflections. Unit cell constants are: a = 11.945(2), b = 22.436(7), c = 13.248(5) ~, [3 = 95.13(2) ~ The space group is P2Jc with Z = 8. Niekel(II) has a square planar coordination of two imine nitrogens, an isonitroso-nitrogen (from n-Pr-IEAI) and another isonitrosooxygen (from IMAI').

Determination of chemical shift anisotropy without a reference and of direct and indirect spin-spin couplings between heteronuclei

A method employing two liquid crystals of opposite diamagnetic anisotropies to determine chemical shift anisotropy without using any reference compound is described. It also provides individual values of the direct and the indirect spin-spin coupling constants between heteronuclei. The parameters for acetonitrile are reported.

The Milky Way's Dark Matter Halo Appears To Be Lopsided

The atomic hydrogen gas (H I) disk in the outer region (beyond similar to 10 kpc from the center) of Milky Way can provide valuable information about the structure of the dark matter halo. The recent three-dimensional thickness map of the outer H I disk from the all sky 21 cm line Leiden/Argentine/Bonn survey, gives us a unique opportunity to investigate the structure of the dark matter halo of Milky Way in great detail. A striking feature of this new survey is the north-south (N-S) asymmetry in the thickness map of the atomic hydrogen gas. Assuming vertical hydrostatic equilibrium under the total potential of the Galaxy, we derive the model thickness map of the H I gas. We show that simple axisymmetric halo models, such as softened isothermal halo (producing a flat rotation curve with V-c similar to 220 km s(-1)) or any halo with density falling faster than the isothermal one, are not able to explain the observed radial variation of the gas thickness. We also show that such axisymmetric halos along with different H I velocity dispersion in the two halves, cannot explain the observed asymmetry in the thickness map. Amongst the nonaxisymmetric models, it is shown that a purely lopsided (m = 1, first harmonic) dark matter halo with reasonable H I velocity dispersion fails to explain the N-S asymmetry satisfactorily. However, we show that by superposing a second harmonic (m = 2) out of phase onto a purely lopsided halo, e. g., our best fit and more acceptable model A (with parameters epsilon(1)(h) = 0.2, epsilon(2)(h) = 0.18, and sigma(H I) = 8.5 km s(-1)) can provide an excellent fit to the observation and reproduce the N-S asymmetry naturally. The emerging picture of the asymmetric dark matter halo is supported by the. cold dark matter halos formed in the cosmological N-body simulation.

Donor properties of metallomacrocyclic tetrapyrrole pigments with sym-trinitrobenzene

The interactions of metallo derivatives of macrocyclic tetrapyrrole pigments, pheophytin a (pheo), phthalocyanin (phth), and tetraphenylporphyrin (TPP) with sym-trinitrobenzene (TNB) have been studied with use of spectroscopic methods. These macrocyles form 1:l molecular complexw with the acceptor. The association constants (K) for the interactions follow the decreasing order of binding as pheo > phth > TPP. The divalent metal ions influence the values of K for the various metallo TPP derivatives, and the relative order of stabilities decrease as Co > Cu = VO > Ni > Zn. The stereochemistry of M(TPP) and the electronic configuration of the metal ions are shown to contribute to the magnitudes of K. The acceptor strongly quenches the fluorescence of the metallo macrocycles, and the quenching constant decreases as pheo > phth > TPP. The formation of exciplexes is postulated on the basis of the rate of bimolecular quenching constants and solvent effects.

Suomen rautakautiset kulkuset, kellot ja kelloriipukset : äänimaiseman arkeologiaa

The thesis addresses the problem of Finnish Iron Age bells, pellet bells and bell pendants, previously unexplored musical artefacts from 400–1300 AD. The study, which contributes to the field of music archaeology, aims to provide a gateway to ancient soundworlds and ideas of music making. The research questions include: Where did these metal artefacts come from? How did they sound? How were they used? What did their sound mean to the people of the Iron Age? The data collected at the National Museum of Finland and at several provincial museums covers a total of 486 bells, pellet bells and bell pendants. By means of a cluster analysis, each category was divided into several subgroups. The subgroups, which all seem to have a different dating and geographical distribution, represent a spread of both local and international manufacturing traditions. According to an elemental analysis, the material varies from iron to copper-tin, copper-lead and copper-tin-lead alloys. Clappers, pellets and pebbles prove that the bells and pellet bells were indisputably instruments intended for sound production. Clusters of small bell pendants, however, probably produced sound by jingling against each other. Spectrogram plots reveal that the partials of the still audible sounds range from 1 000 to 19 850 Hz. On the basis of 129 inhumation graves, hoards, barrows and stray finds, it seems evident that the bells, pellet bells and bell pendants were fastened to dresses and horse harnesses or carried in pouches and boxes. The resulting acoustic spaces could have been employed in constructing social hierarchies, since the instruments usually appear in richly furnished graves. Furthermore, the instruments repeatedly occur with crosses, edge tools and zoomorphic pendants that in the later Finnish-Karelian culture were regarded as prophylactic amulets. In the Iron Age as well as in later folk culture, the bell sounds seem to have expressed territorial, social and cosmological boundaries.

Logic as the Universal Science : Bertrand Russell's Early Conception of Logic and Its Philosophical Context

Bertrand Russell (1872 1970) introduced the English-speaking philosophical world to modern, mathematical logic and foundational study of mathematics. The present study concerns the conception of logic that underlies his early logicist philosophy of mathematics, formulated in The Principles of Mathematics (1903). In 1967, Jean van Heijenoort published a paper, Logic as Language and Logic as Calculus, in which he argued that the early development of modern logic (roughly the period 1879 1930) can be understood, when considered in the light of a distinction between two essentially different perspectives on logic. According to the view of logic as language, logic constitutes the general framework for all rational discourse, or meaningful use of language, whereas the conception of logic as calculus regards logic more as a symbolism which is subject to reinterpretation. The calculus-view paves the way for systematic metatheory, where logic itself becomes a subject of mathematical study (model-theory). Several scholars have interpreted Russell s views on logic with the help of the interpretative tool introduced by van Heijenoort,. They have commonly argued that Russell s is a clear-cut case of the view of logic as language. In the present study a detailed reconstruction of the view and its implications is provided, and it is argued that the interpretation is seriously misleading as to what he really thought about logic. I argue that Russell s conception is best understood by setting it in its proper philosophical context. This is constituted by Immanuel Kant s theory of mathematics. Kant had argued that purely conceptual thought basically, the logical forms recognised in Aristotelian logic cannot capture the content of mathematical judgments and reasonings. Mathematical cognition is not grounded in logic but in space and time as the pure forms of intuition. As against this view, Russell argued that once logic is developed into a proper tool which can be applied to mathematical theories, Kant s views turn out to be completely wrong. In the present work the view is defended that Russell s logicist philosophy of mathematics, or the view that mathematics is really only logic, is based on what I term the Bolzanian account of logic . According to this conception, (i) the distinction between form and content is not explanatory in logic; (ii) the propositions of logic have genuine content; (iii) this content is conferred upon them by special entities, logical constants . The Bolzanian account, it is argued, is both historically important and throws genuine light on Russell s conception of logic.

Wipert von Blücher und Finnland : Alternativpolitik und Diplomatie im 'Dritten Reich'

This dissertation explores the role of the German minister to Helsinki, Wipert von Blücher (1883-1963), within the German-Finnish relations of the late 1930s and the Second World War. Blücher was a key figure – and certainly one of the constants – within German Finland policy and the complex international diplomacy surrounding Finland. Despite representing Hitler’s Germany, he was not a National Socialist in the narrower sense of the term, but a conservative civil servant in the Wilhelmine tradition of the German foreign service. Along with a significant number of career diplomats, Blücher attempted to restrict National Socialist influence on the exercise of German foreign policy, whilst successfully negotiating a modus vivendi with the new regime. The study of his political biography in the Third Reich hence provides a highly representative example of how the traditional élites of Germany were caught in an cycle of conformity and, albeit tacit, opposition. Above all, however, the biographical study of Blücher and his behaviour offers an hitherto unexplored approach to the history of the German-Finnish relations. His unusually long tenure in Helsinki covered the period leading up to the so-called Winter War, which left Blücher severely distraught by Berlin’s effectively pro-Soviet neutrality and brought him close to resigning his post. It further extended to the German-Finnish rapprochement of 1940/41 and the military cooperation of both countries from mid-1941 to 1944. Throughout, Blücher developed a diverse and ambitious set of policy schemes, largely rooted in the tradition of Wilhelmine foreign policy. In their moderation and commonsensical realism, his designs – indeed his entire conception of foreign policy – clashed with the foreign political and ideological premises of the National Socialist regime. In its theoretical grounding, the analysis of Blücher’s political schemes is built on the concept of alternative policy and indebted to A.J.P. Taylor’s definition of dissent in foreign policy. It furthermore rests upon the assumption, introduced by Wolfgang Michalka, that National Socialist foreign policy was dominated by a plurality of rival conceptions, players, and institutions competing for Hitler’s favour (‘Konzeptionen-Pluralismus’). Although primarily a study in the history of international relations, my research has substantially benefited from more recent developments within cultural history, particularly research on nobility and élites, and the renewed focus on autobiography and conceptions of the self. On an abstract level, the thesis touches upon some of the basic components of German politics, political culture, and foreign policy in the first half of the 20th century: national belonging and conflicting loyalties, self-perception and representation, élites and their management of power, the modern history of German conservatism, the nature and practice of diplomacy, and, finally, the intricate relationship between the ethics of the professional civil service and absolute moral principles. Against this backdrop, the examination of Blücher’s role both within Finnish politics and the foreign policy of the Third Reich highlights the biographical dimension of the German-Finnish relationships, while fathoming the determinants of individual human agency in the process.

1H and 13C NMR study of pyridylamides and thionamides

1H and 13C NMR spectra are reported for several pyridylamides and thionamides. Complete analyses of the 13C spectra have yielded the chemical shifts and the direct and long range (13C, 1H) coupling constants. 13C chemical shifts show linear relationship with charge densities computed by the CNDO method. The variations in the chemical shifts are discussed.

Contribution from normal and starburst galaxies to the extragalactic gamma-ray background (EGRB)

The extragalactic diffuse emission at gamma-ray energies has interesting cosmological implications since these photons suffer little or no attenuation during their propagation from the site of origin. The emission could originate from either truly diffuse processes or from unresolved point sources such as AGNs, normal galaxies and starburst galaxies. Here, we examine the unresolved point source origin of the extragalactic gamma-ray background emission from normal galaxies and starburst galaxies. gamma-ray emission from normal galaxies is primarily coming from cosmic-ray interactions with interstellar matter and radiation (similar to 90%) along with a small contribution from discrete point sources (similar to 10%). Starburst galaxies are expected to have enhanced supernovae activity which leads to higher cosmic-ray densities, making starburst galaxies sufficiently luminous at gamma-ray energies to be detected by the current gamma-ray mission(Fermi Gamma-ray Space Telescope).

Cation-induced crown porphyrin dimers of oxovanadium(IV)

Oxovanadium(1V) porphyrins appended with crown ether (benzo-15-crown-5) at the 5 (mono), the 5 and 10115 (cis/trans bis), the 5, 10, and 15 (tris), and the 5, 10, 15, and 20 (tetrakis) positions have been synthesized. The cation complexation behavior of these cavity-bearing porphyrins has been studied by using optical aborption and ESR spectral methods. The cations K+, Cs+, NH4+, and Ba2+, which require two crown ether cavities for complexation, induce dimerization of the porphyrins. The cation-induced dimerization constants for a representative tetrasubstituted porphyrin vary as K+ > Ba2+ > Cs+ - NH4+, and the relative stabilities of the dimers are dependent on the type of the substitution, tetrakis > tris > cis bis. ESR spectra recorded at a sample temperature of 77 K have low-field components attributed to Ah& = f 2 transitions, providing further evidence for the existence of dimers in solutions. The eclipsed sandwich dimers have V-V distances in the range 4.70 A. The relative distributions of oxovanadium crown porphyrins in terms of monomeric and dimeric forms rest on the geometric dispositions of the crown ether appendages.