Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Studies in the polarography of metal-amino acid complexes -Part II. Lead

1. The polarographic behaviour of glycine, α-alanine, β-alanine, valine, aspartic acid, glutamic acid and asparagine complexes of lead has been studied at various pH values and in presence of (1) NaOH, (2) Na2CO3 and (3) NH4 NO3+NH4OH. All the polarographic waves have been found to be reversible. 2. Experiments conducted on the effect of variation of pH, i.e., 7A2. The data have been analysed employing the equations developed by DeFord and Hume as modified by McKenzie and Mellor. 3. Only pure complexes are produced below pH 11·2 in the case of aspartic acid, glutamic acid and glycine, while mono hydroxy complexes are produced in α-alanine, valine and asparagine systems. 4. It has been found that no mixed hydroxy and mixed ammonia complexes are produced in presence of sodium hydroxide and ammonia-ammonium nitrate, respectively. However evidence is obtained for the formation of mixed carbonate complexes in glycine and aspartic acid systems in presence of sodium carbonate. 5. Thermodynamic data have been calculated from polarographic measurements for 18 complexes. 6. The suitability of incorporating amino acids in base solutions for the polarographic estimation of lead has been tested.

Vibrational analysis of the (B2P{cyrillic}→X2P{cyrillic}) system of NS

A few red degraded bands attributable to NS have been reported earlier by Fowler and Barker, Dressler and Barrow et al, and they occur in the same region (2300 to 2700 Å) as the bands of the known systems (C2∑+-X2P{cyrillic}) and (A2Δ-X2P{cyrillic}). Measurements made on the heads of some of these weak bands led Barrow et al. to believe that these bands may form a system analogous to the β-system of NO and be due to a2P{cyrillic}-2P{cyrillic} transition. The spectrum of NS has now been studied in a little more detail by means of an uncondensed discharge through dry nitrogen and sulphur vapour in the presence of argon and thirty three bands belonging to this system have been recorded in the region 2280 to 2760 Å. It has been found possible to represent the band heads by means of the equation {Mathematical expression}. Taking the lower state doublet interval as 223 cm-1, it is shown that the separation in the upper state is 94 cm-1. The ratio of the force constants in the upper and the ground states is found to be 0·39 and is nearly the same as that in the β-system of NO (0·30). The present vibrational analysis therefore supports the view that these new red degraded bands of NS arise from a (B2P{cyrillic}→X2P{cyrillic}) transition and the observed intensity distribution in the form of a wide parabola is also in qualitative agreement with what is expected from the moderately large Δ re (∼0·12Å) value.

Assessing the mitigation potential of forestry activities in a changing climate: A case study for Karnataka

The Clean Development Mechanism (CDM), Article 12 of the Kyoto Protocol allows Afforestation and Reforestation (A/R) projects as mitigation activities to offset the CO2 in the atmosphere whilst simultaneously seeking to ensure sustainable development for the host country. The Kyoto Protocol was ratified by the Government of India in August 2002 and one of India's objectives in acceding to the Protocol was to fulfil the prerequisites for implementation of projects under the CDM in accordance with national sustainable priorities. The objective of this paper is to assess the effectiveness of using large-scale forestry projects under the CDM in achieving its twin goals using Karnataka State as a case study. The Generalized Comprehensive Mitigation Assessment Process (GCOMAP) Model is used to observe the effect of varying carbon prices on the land available for A/R projects. The model is coupled with outputs from the Lund-Potsdam-Jena (LPJ) Dynamic Global Vegetation Model to incorporate the impacts of temperature rise due to climate change under the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) A2, A1B and B1. With rising temperatures and CO2, vegetation productivity is increased under A2 and A1B scenarios and reduced under B1. Results indicate that higher carbon price paths produce higher gains in carbon credits and accelerate the rate at which available land hits maximum capacity thus acting as either an incentive or disincentive for landowners to commit their lands to forestry mitigation projects. (C) 2009 Elsevier B.V. All rights reserved.

Distribution of products around a burning droplet: an analytical approach

A knowledge of the concentration distribution around a burning droplet is essential if accurate estimates are to be made of the transport coefficients in that region which influence the burning rate. There are two aspects of this paper; (1) determination of the concentration profiles, using the simple assumption of constant binary diffusion coefficients for all species, and comparison with experiments; and (2) postulation of a new relation for the therinal conductivity, which takes into account the variations of both temperature and concentrations of various species. First, the theoretical concentration profiles are evaluated and compared with experimental results reported elsewhere [5]. It is found that the agreement between the theory and experiment is fairly satisfactory. Then, by the use of these profiles and the relations proposed in the literature for the thermal conductivity of a mixture of nonpolar gases, a new relation for thermal conductivity: K = (A1 + B1 T) + (A2 + B2 T) xr (21). is suggested for analytical solutions of droplet combustion problems. Equations are presented to evaluate A1, A2, B1, and B2, and values of these terms for a few hydrocarbons are tabulated.

Ultra-violet bands of mercury iodide

The ultraviolet bands of mercury iodide have been excited in uncondensed discharge and photographed with a quartz Littrow spectrograph. The bands in the region λ 2658 to 2530 Å have been analysed into two systems which may form the two components of a2Π-2∑ electronic transition with a2Π interval equal to 858·9 cm-1. These systems and the systems in the region λ 3095 to 2647 Å have the same lower state.

Structural, dielectric and ferroelectric properties of four-layer Aurivillius phase Na0.5La0.5Bi4Ti4O15

Monophasic Na0.5La0.5Bi4Ti4O15 powders were synthesized via the conventional solid-state reaction route. The X-ray powder diffraction (XRD), selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) studies carried out on the as synthesized powdered samples confirmed the phase to be a four-layer Aurivillius that crystallizes in an orthorhombic A2(1)am space group. The microstructure and the chemical composition of the sintered sample were examined by scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). The dielectric properties of the ceramics have been studied in the 27-700 degrees C temperature range at various frequencies (100 Hz to 1 MHz). A sharp dielectric anomaly was observed at 580 degrees C for all the frequencies corresponding to the ferroelectric to paraelectric phase transition. Saturated ferroelectric hysteresis loops were observed at 200 degrees C and the associated remnant polarization (P-r) and coercive field (E-c) were found to be 7.4 mu C/cm(2) and 34.8 kV/cm, respectively. AC conductivity analysis confirmed the existence of two different conduction mechanisms in the ferroelectric region. Activation energies calculated from the Arrhenius plots were similar to 0.24 eV and similar to 0.84 eV in the 300-450 degrees C and 450-580 degrees C temperature ranges, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Die mündliche Sprachkompetenz finnischer Deutschlernender aus Sicht der grammatikalischen Korrektheit : Eine Fehleranalyse im Rahmen des HY-TALK-Projekts

Tutkielman päätavoitteena on analysoida suomalaisten, saksaa opiskelevien lukiolaisten suullisen testin suorituksia kielen oikeellisuuden näkökulmasta virheanalyysin avulla. Aineistona on osa Helsingin yliopiston HY-TALK-hankkeen saksan kielen tutkimusaineistosta: videoinnit suullisen kielitaidon testeistä sekä asiantuntijaraadin arvioinnit suorituksista. Koska aineisto on suullinen, tutkielmassa tarkastellaan aluksi suullisen kielen piirteitä. Virheanalyysin pohjana ovat muun muassa Corderin, Nickelin, Kleppinin ja Jamesin esittämät teoriat. Tutkielmassa analysoidaan kolmentoista, selkeästi joko A1.3- tai A2.2-taitotasolle arvioidun opiskelijan suoritukset. Virheanalyysin tavoitteena on saada selville kielioppivirheiden määrät, kullekin taitotasolle tyypilliset kielioppivirheet sekä selvittää tasojen välisiä eroja. Virheanalyysissä ei huomioida leksikaalisia eikä ääntämisvirheitä, vaan keskitytään morfologisiin ja syntaktisiin virheisiin. Virheet jaotellaan eri virheluokkiin (nominaalilausekkeiden deklinaatio, pronomini, taipumattomat sanaluokat, kysymyssanat, kieltoilmaukset, verbit ja lauserakenne) ja ne tilastoidaan taulukoihin. Lisäksi pohditaan virheiden syitä sekä virheiden vaikutusta kielen ymmärrettävyyteen. Jälkimmäistä selvitetään saksaa äidinkielenään puhuvan, kolmihenkisen raadin avulla. Raadin sekä numeeriset että verbaaliset arvioinnit ovat myös osa tutkielman aineistoa. Toinen tutkielman päätavoite on opetussuunnitelman taitotasoasteikon validointi. Tarkoituksena on selvittää oikeellisuuden taitotasokuvausten toimivuutta arvioinnissa A1.3- ja A2.2-tasojen osalta. Tätä tavoitetta varten selvitetään myös kielitaidon arvioinnin taustalla olevia teorioita. HY-TALK-asiantuntijaraadin arviointeja verrataan virheanalyysin tuloksiin korrelaatiokertoimen ja regressiosuoran avulla. Virheanalyysin perusteella voidaan todeta, että molemmilla tasoilla olevat opiskelijat tekevät eniten virheitä nominaalilausekkeiden deklinaatiossa (A2.2-tasolla 60,0 prosenttia kaikista virheistä ja A1.3-tasolla 42,2 prosenttia). A1.3-tasolle arvioidut opiskelijat tekevät paljon virheitä myös verbeissä ja lauserakenteissa, kun taas A2.2-tason opiskelijat hallitsevat nämä rakenteet paremmin. A1.3-tasolle arvioidut opiskelijat tekevät enemmän virheitä (22,10 virhettä sataa sanaa kohden) kuin A2.2-tasolle arvioidut (9,80 virhettä sataa sanaa kohden). Virheiden syitä ovat muun muassa testitilanne, puhekumppanin vaikutus ja interferenssi. Kielen ymmärrettävyyteen vaikuttavat saksalaisen raadin mukaan kielioppivirheiden lisäksi muun muassa puheen sujuvuus ja leksikaaliset ongelmat. Vakavimpina virheinä pidetään virheitä lauserakenteessa, sillä ne haittaavat usein ymmärrettävyyttä. Deklinaatiovirheitä puolestaan ei yleensä pidetä vakavina virheinä. Taitotasokuvaukset toimivat A1.3- ja A2.2-tasojen osalta hyvin, sillä virheanalyysin virhemäärät ja HY-TALK-raadin arvioinnit korreloivat keskenään, kun otetaan huomioon molemmat tasot A1.3 ja A2.2. Kielioppivirheiden määrä siis vaikuttaa kielen oikeellisuuden arviointiin. Taitotasokuvauksia olisi kuitenkin joiltain osin syytä tarkentaa ja yhtenäistää esimerkiksi konkreettisten esimerkkien avulla (esim. mikä on peruskielioppivirhe?) ja kuvaamalla myös kielen ymmärrettävyyttä joka tasolla.

Visualisation of a 2′-5′ parallel stranded double helix at atomic resolution: crystal structure of cytidylyl-2′,5′-adenosine

X-ray crystallographlc studies on 3′–5′ ollgomers have provided a great deal of information on the stereochemistry and conformational flexibility of nucleic acids and polynucleotides. In contrast, there is very little Information available on 2′–5′ polynucleotides. We have now obtained the crystal structure of Cytidylyl-2′,5′-Adenoslne (C2′p5′A) at atomic resolution to establish the conformational differences between these two classes of polymers. The dlnucleoside phosphate crystallises in the monocllnlc space group C2, with a = 33.912(4)Å, b =16.824(4)Å, c = 12.898(2)Å and 0 = 112.35(1) with two molecules in the asymmetric unit. Spectacularly, the two independent C2′p5′A molecules in the asymmetric unit form right handed miniature parallel stranded double helices with their respective crystallographic two fold (b axis) symmetry mates. Remarkably, the two mini duplexes are almost indistinguishable. The cytosines and adenines form self-pairs with three and two hydrogen bonds respectively. The conformation of the C and A residues about the glycosyl bond is anti same as in the 3′–5′ analog but contrasts the anti and syn geometry of C and A residues in A2′p5′C. The furanose ring conformation is C3′endo, C2′endo mixed puckering as in the C3′p5′A-proflavine complex. A comparison of the backbone torsion angles with other 2′–5′ dinucleoside structures reveals that the major deviations occur in the torsion angles about the C3′–C2′ and C4′-C3′ bonds. A right-handed 2′–5′ parallel stranded double helix having eight base pairs per turn and 45° turn angle between them has been constructed using this dinucleoside phosphate as repeat unit. A discussion on 2′–5′ parallel stranded double helix and its relevance to biological systems is presented.

Critical resistivity in impurity doped binary liquid mixtures

The electrical resistance of the critical binary liquid system C6H12+(CH3CO)2O is measured both in the pure form and when the system is doped with small amounts (≈ 100 ppm) of H2O impurities. Near Tc, the resistance varies as dR/dT = A1+A2 (T-Tc)-b with b ≈ 0.35. Neither the critical exponent b nor the amplitude ratio A1/A2 are affected by the impurities. A sign reversal of dR/dT is noticed at high temperatures T much greater-than Tc.

Dilute solution properties of methyl methacrylate—acrylonitrile copolymer (MA2)

This article deals with studies of the dilute solution properties of methyl methacrylate-acrylonitrile (MMA-AN) copolymer of 0.415 mole fraction (mf) of acrylonitrile composition. Mark—Houwink parameters for this copolymer have been evaluated in acetonitrile (MeCN), 2-butanone (MEK), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL). The Mark-Houwink exponent a in all four solvents at all temperatures is larger than the corresponding values of the parent homopolymers. The solvent power is in the order of DMF < γ–BL < MEK < MeCN; [η] decreases with an increase in temperature, which is behavior characteristic of polymers in good solvent. The unperturbed dimensions (K0) values, obtained by the Stockmayer–Fixman method, are lower than those for the parent homopolymers and depend on solvent as well as temperature. The solute—solvent interaction parameter X1 values are close to 0.5; X1 is independent of temperature. The excess interaction parameter XABvalues are negative. The results for this copolymer system in regard to low second virial coefficient A2, large X1, and high a values suggest that the large extension of these copolymer chains is due to the unusual short-range interactions.