Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II) complexes (1-5) of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Crystal structures of a nonapeptide helix containing alpha,alpha-di-n-butylglycine (Dbg), Boc-Gly-Dbg-Ala-Val-Ala-Leu-Aib-Val-Leu-OMe

Two crystals structures of a nonapeptide (anhydrous and hydrated) containing the amino acid residue alpha, alpha-di-n-butylglycyl, reveal a mixed 3(10)/alpha-helical conformation. Residues 1-7 adopt phi, psi values in the helical region, with Val(8) being appreciably distorted. The Dbg residue has phi, psi values of -40, -37 degrees and -46, -40 degrees in two crystals with the two butyl side chains mostly extended in each. Peptide molecules in the crystals pack into helical columns. The crystal parameters are C50H91N9O12, space group P2(1), with a = 9.789(1) Angstrom, b = 20.240(2) Angstrom, c = 15.998(3) Angstrom, beta = 103.27(1); Z = 2, R = 10.3% for 1945 data observed >3 sigma(F) and C50H91N9O12. 3H(2)O, space group P2(1), with a = 9.747(3) Angstrom, b = 21.002(8) Angstrom, c = 15.885(6) Angstrom, beta = 102.22(3)degrees, Z = 2, R = 13.6% for 2535 data observed >3 sigma(F). The observation of a helical conformation at Dbg suggests that the higher homologs in the alpha, alpha-dialkylated glycine series also have a tendency to stabilize peptide helices. (C) Munksgaard 1996.

Conformation of di-n-propylglycine residues (Dpg) in peptides: crystal structures of a type I 'beta-turn forming tetrapeptide and an alpha-helical tetradecapeptide

The crystal structures of two oligopeptides containing di-n-propylglycine (Dpg) residues, Boc-Gly-Dpg-Gly-Leu-OMe (1) and Boc-Val-Ala-Leu-Dpg-Val-Ala-Leu-Val-Ala-Leu-Dpg-Val-Ala-Leu-OMe (2) are presented. Peptide 1 adopts a type I' beta-turn conformation with Dpg(2)-Gly(3) at the corner positions. The 14-residue peptide 2 crystallizes with two molecules in the asymmetric unit, both of which adopt alpha-helical conformations stabilized by 11 successive 5 -> 1 hydrogen bonds. In addition, a single 4 -> 1 hydrogen bond is also observed at the N-terminus. All live Dpg residues adopt backbone torsion angles (phi, psi) in the helical region of conformational space. Evaluation of the available structural data on Dpg peptides confirm the correlation between backbone bond angle N-C-alpha-C' (tau) and the observed backbone phi,psi values. For tau > 106 degrees, helices are observed, while fully extended structures are characterized by tau < 106 degrees. The mean r values for extended and folded conformations for the Dpg residue are 103.6 degrees +/- 1.7 degrees and 109.9 degrees +/- 2.6 degrees, respectively. Copyright (C) 2007 European Peptide Society and John Wiley & Sons, Ltd.

Kuviteltu aatelismies : Aateluus viholliskuvana ja itseymmärryksenä 1800-luvun Suomessa

An imagined nobleman Nobility as an enemy image and in-group identity in nineteenth-century Finland The focal point of this study is the difficult relationship between two seemingly very different 19th-century elite groups, the upwardly mobile bourgeois intelligentsia and the slowly declining traditional nobility. In the thinking of the bourgeois contender the two emerged as exact opposites, styled as conflicting ideal types: an outdated, exclusive, degenerate hereditary aristocracy versus a dynamic and progressive new force in society, recruited solely on the basis of personal merit, originating from the common people and representing the nation. The appearance of an important 19th-century novelty, print publicity, coincided with the emergence of the bourgeois intelligentsia. The institutions of the developing publishing industry were manned by the aspiring new group. The strengthening flow of progressive, democratic, nationalist ideas distributed via the printing presses carried an undercurrent of self-promotion. It transmitted to the developing readership the self-image of the new cultural bourgeoisie as the defender and benevolent educator of the nation. Having won the contest over the media, the intelligentsia was free to present its predecessor and rival as an enemy of the people. In its politics the nobility emerged as an ideal scapegoat, represented as the source for existing social evils, all if which would promptly go away after its disappearance. It also served as a black backcloth, against which the democratic, national, progressive bourgeois intelligentsia would shine more brightly. In order to shed light on the 19th-century process of (re)modelling the image of nobility as a public enemy I have used four different types of source materials. These include three genres of print publicity, ranging from popular historical and contemporary fiction to nonfictional presentations of national history and the news and political commentaries of the daily papers, complemented by another, originally oral type of publicity, the discussion protocols of the Finnish four-estate parliament. To counterpoint these I also analysed the public self-image of the nobility, particularly vis-à-vis the nationalist and democratic ethos of the modernising politics.

Solution conformation of a tetradecapeptide stabilized by two di-n-propyl glycine residues

The solution conformation of a designed tetradecapeptide Boc-Val-Ala-Leu-Dpg-Val-Ala-Leu-Val-Ala-Leu-Dpg-Val-Ala-Leu-OMe (Dpg-14) containing two di-n-propyl glycine (Dpg) residues has been investigated by H-1 NMR and circular dichroism in organic solvents. The peptide aggregates formed at a concentration of 3 mm in the apolar solvent CDCl3 were broken by the addition of 12% v/v of the more polar solvent DMSO-d(6). Successive NiH <-> Ni+1H NOEs observed over the entire length of the sequence in this solvent mixture together with the observation of several characteristic medium-range NOEs support a major population of continuous helical conformations for Dpg-14. Majority of the observed coupling constants ((3)(alpha)(JNHC)(H)) also support phi values in the helical conformation. Circular dichroism spectra recorded in methanol and propan-2-ol give further support in favor of helical conformation for Dpg-14 and the stability of the helix at higher temperature. Copyright (C) 2010 European Peptide Society and John Wiley & Sons, Ltd.

Structural and spectral perspectives of a novel thiosemicarbazone synthesized from di-2-pyridyl ketone and 4-phenyl-3-thiosemicarbazide

A new thiosemicarbazone, HL is synthesized from di-2-pyridyl ketone and 4-phenyl-3-thiosemicarbazide and structurally and spectrochemically characterized. H-1 NMR, C-13 NMR, COSY, HMQC and IR spectra of the compound are studied and the proton magnetic resonance spectrum reveals some unprecedented observations. The thione form is predominant in the solid state, as supported by the crystal structure and IR data, while a thiol-thione equilibrium is proposed in the solution state by NMR studies. The compound crystallizes into a monoclinic lattice with space group C2/c and the ZE conformation is exhibited by the thiosemicarbazone. Intra- and intermolecular hydrogen-bonding interactions give rise to a two-dimensional packing in the crystal lattice

Suomen suuriruhtinaskunnan virkamiehistön yksityiskirjastot ja sensuurin kieltämä kirjallisuus niissä 1800-luvun alkuvuosikymmeninä

Tutkimus luotaa 1800-luvun alkuvuosikymmenten Suomen suuriruhtinaskunnan virkamiehistön poliittisia asenteita sensuuri-ja painovapauskysymysten valossa. Sadan virkamiehistöön kuuluneen henkilön yksityiskirjastot ja niiden sisältämät mahdolliset sensuurin kieltämät nimikkeet on seulottu Kansalliskirjaston kokoelmissa olevista 1800- luvun kirjahuutokauppaluetteloista vertailemalla niitä Kansallisarkistossa säilytettäviin sensuuriviranomaisten kiellettyjen teosten listoihin. Tutkimuksen keskeisimmiksi teemoiksi nousevat näin poliittis- sekä kirjahistorialliset, kirjallista kulttuuria koskettelevat ulottuvuudet. Virkamiehistön yksityiskirjastot mahdollisine kiellettyine nimikkeineen on esitelty tilastollisen taulukoinnin avulla kirjastojen koon, virkamiehistön hallintoalan, rankiluokan sekä alueellisen identiteetin mukaan jaoteltuina. Vaikka lähdeaineiston perusteella on tämänkaltaisen poliittisväritteisen kirjallisen kulttuurin tavoittaminen osaksi ongelmallista, ovat huutokauppaluettelot systemaattisesta ja säännöllisestä luonteestaan johtuen merkittävää ja satunnaisten inventaarioluetteloiden ohella lähestulkoon ainoaa käsillä olevaa yksityiskirjastoja koskevaa lähdeaineistoa. Suomen 1800-luvun valtiolliseen asemaan liittyviä historiantulkintoja on tutkimuksen edetessä pyritty kuljettamaan rinnakkain; niitä ovat toisaalta suomalaisten käsitykset maansa perustuslaillisesta asemasta ja toisaalta venäläisten viranomaisten tulkinnat Suomen asemasta yleisvaltakunnallisessa viitekehyksessä. Tämän ohella tutkimusaihetta on lähestytty sen ajalliseeen kontekstiin olennaisesti kytkeytyvien yhteiskunta-ja historianfilosofisten teorioiden avulla. Ne ovat olleet myös tutkimuksen kohteena olleille aikalaisille relevantti henkinen ulottuvuus. Tämä on perusteltua, koska filosofista ja valtiotieteellistä kirjallisuutta on ollut kirjastoissa paljon. Etiikasta ja moraalista lähtevä vapauden ongelma on ollut yksi tämänkaltainen yhteiskuntafilosofinen kysymys. Tutkimuksessa aika ajoin esiin nouseva aatteellinen vertailu muiden Euroopan maiden oloihin laajentaa tutkimuksen historiallisen viitekehyksen osaksi 1800-luvun eurooppalaisen henkisen aatemaailman maisemaa. Tutkimuksen varovaiset johtopäätökset juontuvat erilaisista näkökulmista. Kiellettyjä nimikkeitä löytyi hieman yli 30 % kaikista virkamiehistön yksityiskirjastoista, mutta kiellettyjen nimikkeiden määrät osoittautuivat kirjastokohtaisesti laskettuna pienehköiksi. Ilmiön voi näin väittää olleen toisaalta marginaalista, mutta toisaalta konkreettinen osoitus poliittiseen vakaumukseen viittaavasta asennoitumisesta; sensuuria esimerkiksi saatettiin tulkita perustuslaillisuutta ja Aleksanteri I:n antaman hallitsijanvakuutuksen taustaa vasten. Kielletyn kirjallisuuden hankkiminen sensuurilaeista piittaamatta saattoi myös olla kamppailua hyvänä pidetyn yhteiskuntajärjestyksen puolesta järjestelmän epäkohtia vastaan. Keisaria kohtaan tunnettiin lojaalisuutta, mutta hänen hallitsemaansa järjestelmää edustavia sensuuriviranomaisia kohtaan välttämättä ei. Tässä kohdin Suomen tilanteella oli vastaavuutta Saksan oloihin, j o s s a nuorhegeliläiset halusivat muuttaa yhteiskuntaa ideaalimpaan suuntaan. Venäjän keisarikuntaan kuuluminen toi mukanaan maallista hyvää, mutta henkisen kulttuurin puolella orientoiduttiin pääasiassa länteen, ja pitäydyttiin Ruotsin ajan luomassa perinnössä. Yksi keskeinen tästä kummunnut valistusaatteen traditionaalinen arvo oli itsensä vapaa kehittäminen, joten sensuurikysymyksissä ajauduttiin väistämättä törmäyskurssille valtiopoliittisen ja kulttuurisen identiteetin ristipaineessa. Vaikka valtiopoliittinen identiteetti vaihtui vuoden 1809 jälkeen, ei kulttuurisen identiteetin kohdalla näin käynyt. Tätä kautta vahvistuu kokonaiskuva 1700-luvun historian ja Ruotsin ajan perinnön tärkeydestä 1800-luvun henkiselle kehitykselle etenkin kirjallisen kulttuurin saralla.

Jac. Ahrenberg ja historian perintö : Restaurointisuunnitelmat Viipurin ja Turun linnoihin 1800-luvun lopussa

Jac. Ahrenberg and Patrimony Restoration Plans for Viipuri and Turku Castles at the End of the 19th Century This dissertation examines the unrealized restoration plans for two castles in the Grand Duchy of Finland one located at Viipuri (Vyborg, nowadays in Russia), the other at Turku (in Swedish, Åbo) during the last decades of the 19th century. Both castles were used as prisons, barracks and warehouses. From the middle of the 19th century on, their restoration and transformation into museums and "national monuments" were demanded in the newspapers. The prison reform in the 1860s stimulated the documentation and debate concerning their future, but it was only at the beginning of the 1880s when their restoration became an official state-run project. The undertaking was carried out by Johan Jacob (Jac.) Ahrenberg (1847 1914), architect of the National Board of Public Buildings. By combining written sources with drawings and photographs, this dissertation examines the restoration projects, the two castles' significance and the ways in which they were investigated by scholars. The plans are analyzed in connection with restoration practices in France and Sweden and in the context of contemporary discussions concerning national art and patrimony. The thesis argues that these former castles of the Swedish crown were used to manifest the western roots of Finnish law and order, the lineage of power and the capacity of the nation to defend itself. However, because of their symbolism, their restoration became a politically delicate question concerning the role of the Swedish heritage in Finland's nation-building process. According to Jac. Ahrenberg's plans, the two castles were to be restored to their assumed appearance at the time of the Vasa dynasty. Consequently, the structures would have resembled castles in Sweden. It is suggested that one aim of the restoration plans was to transform the two buildings into monuments testifying to the common history of Sweden and Finland. They were meant to consolidate the Swedish basis of Finnish culture and autonomy and thus to secure them against the threatening implications of Russian imperialism. It seems that along with the changing ideals of architectural restoration and the need for an original Finnish architectural heritage, the political connotations associated with the castles were one reason why Jac. Ahrenberg's restoration plans were never realized.