Mossbauer effect studies of the thermal decomposition of iron(II) oxalate in hydrogen

Mössbauer-effect and X-ray studies were carried out on the product samples of the thermogravimetric analysis (TGA) and of the isothermal decomposition of iron(II) oxalate in flowing H2. Two types of sample configurations were employed for isothermal studies between 280 to 420°C for various periods of heating. Low temperature Mossbauer measurements at liquid nitrogen temperature were carried out to examine the superparamagnetic (SPM) contributions. From the spectra of samples decomposed at 340°C, in vertical experiments, the percentage SPM and percentage ferromagnetic (FM) area of Fe3O4 were estimated and an average size (˜167Å) for Fe3O4 was derived. Mossbauer measurements (at high temperatures) were carried out on Fe3C formed in horizontal experiments, for two samples decomposed at ˜320°C for 1 hr and 2 hr. An estimate of SPM and FM Fe3C was obtained by calculating KV, the anisotropy energy for the Fe3C in these two samples and values of 5.07 × 10−16 and 7.02 × 10−16 erg/sec, respectively, were obtained.

Electron spin resonance study of copper(II) doped ferroelectric ammonium sulphate

Single crystal electron spin resonance studies of Cu2+ doped ferroelectric ammonium sulphate ((NH4)2SO4, Tc = 223 K) are reported at 300 and 77 K. The Cu2+ ion is found to enter the lattice interstitially with a trigonal bipyramidal coordination. Proton superhyperfine interaction is found for magnetic field directions close to the a-axis. Changes are observed in the 77 K recordings indicating a distortion of the trigonal bipyramid consistent with crystal structure data. An increase of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding. The Cu2+ ion doped as an impurity in a trigonal bipyramid environment in a diamagnetic host lattice is reported for the first time.

Kummisetien katolinen kirkko : Kummisetä-trilogian ja Sopranos-televisiosarjan välittämä kuva roomalaiskatolisesta kirkosta

Tässä tutkielmassa tutkin millaisen kuvan Francis Ford Coppolan ohjaamat kolme Kummisetä-elokuvaa ja David Chasen luoman Sopranos-televisiosarjan kaksi ensimmäistä tuotantokautta antavat roomalaiskatolisesta kirkosta ja erityisesti Amerikassa toimivasta roomalaiskatolisesta kirkosta. Kummisetä-elokuvat valmistuivat vuosina 1972, 1974 ja 1990, Sopranos-sarjan kaksi ensimmäistä tuotantokautta taas esitettiin HBO-kanavalla ensimmäisen kerran vuosina 1999 ja 2000. Lähteet kattavat Amerikan katolisen kirkon historian 1900-luvun alusta aina 2000-luvun alkuun asti. Pyrin vastaamaan tutkielmassani siihen, millaisena lähteet kuvaavat katolisen ja onko kuvaukselle löydettävissä jotain syitä. Kummisetä-elokuvien kohdalla on paradoksaalista se, että ne kaikki kuvaavat menneisyyden eivätkä tekohetkensä tapahtumia, mikä mahdollisesti näkyy myös niiden tavassa kuvata katolista kirkkoa. Vaikuttaisi siltä, että varsinkin kahden ensimmäisen Kummisetä-elokuvan tapa kuvata Amerikan katolista kirkkoa pohjautuu pitkälti elokuvan tekohetken tunnelmiin. Elokuvien ohjaaja Francis Ford Coppola on myöntänyt käyttäneensä Kummisetä-elokuvien päähenkilöinä olevaa Corleone-perhettä Amerikan vertauskuvana. Elokuvien yksi kattava teema on eräänlainen maallistumiskehitys, jossa vanhan polven edustajan, don Vito Corleonen, arvot syrjäytyvät ja tilalle nousee uusi johtajapolvi Viton nuorimman pojan don Michael Corleonen hahmossa. Michael Corleone edustaa huomattavasti armottomampaa polvea kuin Vito eikä uskonto ja katolinen kirkko näy hänen elämässään juuri lainkaan. Michaelin kyyninen ja kylmäkin hahmo on mitä todennäköisemmin vertauskuva elokuvien tekohetken yleisistä tunnelmia, jolloin Watergate-skandaali kansallisella tasolla ja Vatikaanin II konsiili ja paavin kiertokirje Humanae Vitae muokkasivat rajusti perinteisen katolisuuden ja amerikkalaisuuden identiteettiä. Kolmas Kummisetä-elokuva käsittelee lähes kokonaan paavi Johannes Paavali I:n lyhyeksi jäänyttä paaviuskautta vuodelta 1978 osittain fiktioin keinoin. Elokuvan yhtäläisyydet rikoskirjailija David Yallopin menestyskirjaan In Gods Name. An Investigation into the Murder of Pope John Paul I, jossa kirjailija esittää paavin tulleen kuurian virkamiesten ja mafiosoiden murhaamaksi, ovat selkeät. Kirkosta luodaan kuva toisaalta armottomona valtakoneistona, mutta toisaalta myös hengellisenä yhteisönä, josta katuvan ihmisen on mahdollisuus löytää apua. Sopranos-televisiosarja jatkaa kahdella ensimmäisellä tuotantokaudellaan saman maallistumiskehityksen kulkua kuin kaksi ensimmäistä Kummisetä-elokuvaakin. Päähenkilö Tony Soprano perheineen on lähes täysin irrallaan katolisesta perinteestä eivätkä he enää tunne sen oppejakaan kunnolla. Silti he mieltävät itsensä katolilaisiksi. Tämä vastaa joiltain osin tutkimustuloksia todellisista amerikkalaisista katolilaisista. Kaiken kaikkiaan Kummisetä-elokuvatrilogia ja Sopranos-televisiosarja antavat katolisesta kirkosta hyvin monipuolisen ja joissain asioissa totuudenmukaisenkin kuvan, joskin tekijöiden oma henkilöhistoria ja ajan skandaalit ovat väistämättä värittäneet kirkkokuvausta. Siten ne muodostavat värikkään läpileikkauksen Amerikan katolisen kirkon kehityksestä amerikanitalialaisessa yhteisössä 1900-luvun alusta 2000-luvun alkuun.

Bromination of Intermolecular Chelate Linkage Isomers of 3-Oximino-4,9-Dimethyl (or 4,7,9-Trimethyl)-5,8-Diazadodeca-4,8-Diene-2,11-Dionato Nickel(II)

The reaction of the title complexes (FIG. 1) with N-bromosuccinimide or bromine in chloroform yields isomeric bromo complexes on substitution of the γ-CH carbon proton by bromine. The brominated products have been characterised by ir, pmr, electronic absorption spectra, conductivity and magnetic susceptibility measurements. The linkage isomerisation of the brominated products in chloroform has been shown to depend on the diamine residue.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 mu m

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mu m up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5)(Sigma(+)(u) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

Linkage isomerism in nickel(II) I-isonitroso-imine ligand complexes

I-isonitroso-imine ligand complexes of nickel(II), namely, bis(isonitrosomethylacetoacetate-imino)Ni(II), Ni(IMI)(IMI); bis(isonitrosobenzoylacetoneimino)Ni(II), Ni(IBI)(IBI) and bis(isonitrosoacetoacetanilideimino)Ni(II), Ni(IANI)(IANI), have been prepared and characterized. On the basis of their spectroscopic and magnetic properties, these complexes are suggested to have a square-planar stereochemistry around the metal ion with both nitrogen (ligand denoted without prime) and oxygen (ligand denoted with prime) coordinated isonitroso groups. The i.r. and NMR spectra of these and other similar complexes are discussed.

X-ray studies of crystalline complexes involving amino acids. II. The crystal structure of L-arginine L-glutamate

Abstract is not available.

Interaction of palladium (II) with DNA

The nature of interaction of palladium(II) with calf thymus DNA was studied using viscometry, ultraviolet, visible and infrared spectrophotometry and optical rotatory disperison and circular dichroism measurements. The results indicate that Pd(II) interacts with both the phosphate and bases of DNA. The ORD/CD data indicate that the binding of Pd(II) to DNA brings about considerable conformational changes in DNA.

Preparation of Palladium(II) Complexes of Isonitrosoacetylacetoneimines Having O- and N-Coordinated Isonitroso Groups

Methods for the preparation of palladium(II) complexes of the type Pd(R-IAI)(IAI'), where IAI' is the anion of isonitrosoacetylacetoneimine and R-IAI, its N-alkyl or N-aryl derivative, are given.

Metal chelates in vinyl polymerization. II. Mechanism of initiation by Fe(DPM)3

The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)3, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction.

New ternary copper(II) complexes of L-alanine and heterocyclic bases: DNA binding and oxidative DNA cleavage activity

Four new ternary copper(II) complexes of alpha-amino acid having polypyridyl bases of general formulation [Cu(L-ala)(B)(H2O)](X)(1-4), where L-ala is L-alanine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) and 5,6-phenanthroline dione (dione, 3), dipyrido[3,2:2',3'-f] quinoxaline (dpq, 4), and X = ClO4-/NO3- are synthesized, characterized by various spectroscopic and X-ray crystallographic methods. The complexes show a distorted square-pyramidal (4 + 1) CuN3O2 coordination geometry. The one-electron paramagnetic complexes (1-4) display a low energy d-d band near 600 nm in aqueous medium and show a quasi-reversible cyclic voltammetric response due to one-electron Cu(II)/Cu(I) reduction near - 100 mV (versus SCE) in DMF-0.1 M TBAP. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. All the complexes barring the complexes 1 and 3 are avid binder to the CT-DNA in the DNA minor groove giving an order: 4 > 2 >>>1, 3. The complexes 2 and 4 show appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA) as a reducing agent. Hydroxyl radical was investigated to be the DNA cleavage active species. Control experiments in the presence of distamycin-A show primarily minor groove-binding propensity for the complexes 2 and 4 to the DNA.

X-ray crystal structure of a ternary copper(II) vitamin B6 complex, hydroxo(2,2'-bipyridyl)(pyridoxinato) copper(II) monohydrate. A rare example of monodentate coordination of copper(II) by the hydroxyl ion

A ternary metal complex involving Vitamin B6 with the formula [Cu(bipy)(pn) (OH)]H2O (bipy = 2,2'²-bipyridine, PN = anionic pyridoxine) has been synthesized and studied in the solid state by means of spectroscopy and X-ray crystallography. The geometry around copper(II) is distorted square pyramidal, two oxygens from phenolic and 4-(hydroxymethyl) groups of pn, two nitrogens from bipy and an axial OH- ion forming the coordination sphere. In this structure pn exists in a new anionic form with deprotonation of the phenolic group. The structure also provides a rare example of monodentate hydroxyl coordination to copper.

A novel amino acid racemization in vitamin b6-amino acid schiff base copper complexes: crystal structures of aquo (5'-phosphopyridoxylidene-dl-tyrosinato) copper(II) 3.5H2O and aquo (5'-phosphopyridoxylidene-dl-phenylalaninato) copper(II) 2.5H2O

A novel racemization observed in the Vitamin B6-amino acid Schiff base complexes, aquo (5'-phosphopyridoxylidene-l-tyrosinato) copper(II) and aquo (5'-phosphopyridoxylidene-l-phenylalaninato) copper(II) is described. The racemization taking place in solution under mild acidic conditions (pH 5-6) was confirmed by CD studies and the products were characterized by single crystal X-ray diffraction. The structures of both complexes show almost parallel orientation of the aromatic side chain and the pyridoxal II-system. The activation of the αCsingle bondH group due to the intermolecular II- interaction is probably the reason for the unusual racemization observed.