Anaerobic DNA cleavage activity in red light and photocytotoxicity of (pyridine-2-thiol)cobalt(III) complexes of phenanthroline bases

Cobalt(III) complexes [Co(pnt)(B)(2)](NO3)(2) (1-3) of pyridine-2-thiol (pnt) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d: 2',3'-f]quinoxaline (dpq in 2) and dipyrido[3,2-a:2',3'-c] phenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The crystal structure of 1a as mixed ClO4- and PF6- salt of 1 shows a (CoN5S)-N-III coordination geometry in which the pnt and phen showed N,S- and N,N-donor binding modes, respectively. The complexes exhibit Co(III)/Co(II) redox couple near -0.3 V (vs. SCE) in 20% DMF-Tris-HCl buffer having 0.1 M TBAP. The complexes show binding propensity to calf thymus DNA giving K-b values within 2.2 x 10(4)-7.3 x 10(5) M-1. Thermal melting and viscosity data suggest DNA surface and/or groove binding of the complexes. The complexes show significant anaerobic DNA cleavage activity in red light under argon atmosphere possibly involving sulfide anion radical or thiyl radical species. The DNA cleavage reaction under aerobic medium in red light is found to involve both singlet oxygen and hydroxyl radical pathways. The dppz complex 3 shows non-specific BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via both hydroxyl and singlet oxygen pathways. The dppz complex 3 exhibits photocytotoxicity in HeLa cervical cancer cells giving IC50 values of 767 nM and 19.38 mu M in UV-A light of 365 nm and in the dark, respectively. A significant reduction of the dark toxicity of the dppz base (IC50 = 8.34 mu M in dark) is observed on binding to the cobalt(III) center.

Scopophobia/Scopophilia: electric light and the anxiety of the gaze in postwar American architecture

In the years of reconstruction and economic boom that followed the Second World War, the domestic sphere encountered new expectations regarding social behaviour, modes of living, and forms of dwelling. This book brings together an international group of scholars from architecture, design, urban planning, and interior design to reappraise mid-twentieth century modern life, offering a timely reassessment of culture and the economic and political effects on civilian life. This collection contains essays that examine the material of art, objects, and spaces in the context of practices of dwelling over the long span of the postwar period. It asks what role material objects, interior spaces, and architecture played in quelling or fanning the anxieties of modernism’s ordinary denizens, and how this role informs their legacy today. Table of Contents [Book] Introduction Robin Schuldenfrei Part 1: Psychological Constructions: Anxiety of Isolation and Exposure 1. Taking Comfort in the Age of Anxiety: Eero Saarinen’s Womb Chair Cammie McAtee 2. The Future is Possibly Past: The Anxious Spaces of Gaetano Pesce Jane Pavitt 3. Scopophobia/Scopophilia: Electric Light and the Anxiety of the Gaze in American Postwar Domestic Architecture Margaret Petty Part 2: Ideological Objects: Design and Representation 4. The Allegory of the Socialist Lifestyle: The Czechoslovak Pavilion at the Brussels Expo, its Gold Medal and the Politburo Ana Miljacki 5. Assimilating Unease: Moholy-Nagy and the Wartime-Postwar Bauhaus in Chicago Robin Schuldenfrei 6. The Anxieties of Autonomy: Peter Eisenman from Cambridge to House VI Sean Keller Part 3: Societies of Consumers: Materialist Ideologies and Postwar Goods 7. "But a home is not a laboratory": The Anxieties of Designing for the Socialist Home in the German Democratic Republic 1950—1965 Katharina Pfützner 8. Architect-designed Interiors for a Culturally Progressive Upper-Middle Class: The Implicit Political Presence of Knoll International in Belgium Fredie Floré 9. Domestic Environment: Italian Neo-Avant-Garde Design and the Politics of Post-Materialism Mary Louise Lobsinger Part 4: Class Concerns and Conflict: Dwelling and Politics 10. Dirt and Disorder: Taste and Anxiety in the Working Class Home Christine Atha 11. Upper West Side Stories: Race, Liberalism, and Narratives of Urban Renewal in Postwar New York Jennifer Hock 12. Pawns or Prophets? Postwar Architects and Utopian Designs for Southern Italy Anne Parmly Toxey. Coda: From Homelessness to Homelessness David Crowley

Search for a Light Higgs Boson in Central Exclusive Diffraction: Method and Detectors

By detecting leading protons produced in the Central Exclusive Diffractive process, p+p → p+X+p, one can measure the missing mass, and scan for possible new particle states such as the Higgs boson. This process augments - in a model independent way - the standard methods for new particle searches at the Large Hadron Collider (LHC) and will allow detailed analyses of the produced central system, such as the spin-parity properties of the Higgs boson. The exclusive central diffractive process makes possible precision studies of gluons at the LHC and complements the physics scenarios foreseen at the next e+e− linear collider. This thesis first presents the conclusions of the first systematic analysis of the expected precision measurement of the leading proton momentum and the accuracy of the reconstructed missing mass. In this initial analysis, the scattered protons are tracked along the LHC beam line and the uncertainties expected in beam transport and detection of the scattered leading protons are accounted for. The main focus of the thesis is in developing the necessary radiation hard precision detector technology for coping with the extremely demanding experimental environment of the LHC. This will be achieved by using a 3D silicon detector design, which in addition to the radiation hardness of up to 5×10^15 neutrons/cm2, offers properties such as a high signal-to- noise ratio, fast signal response to radiation and sensitivity close to the very edge of the detector. This work reports on the development of a novel semi-3D detector design that simplifies the 3D fabrication process, but conserves the necessary properties of the 3D detector design required in the LHC and in other imaging applications.

Discursive Matrixes of Motherhood : Cultivating Decency and Emotion in Finnish and French Mother-talk

Discursive Matrixes of Motherhood examines women's discourse on their experiences of new motherhood in Finland and France. It sets out from two culturally prevalent turns of speech observed in different social forums: in conversations amongst mothers with tertiary education and in the print media. The pool of data includes: 30 interviews, 8 autobiographically inspired novels and 80 items from women's magazines. With instruments loaned from the toolbox of rhetorical analysis, the recurrence of certain expressions or clichés is analyzed with regard to the national, cultural, biographical, political and daily contexts and settings in which the speaking subjects are immersed. "Staying at home is such a short and special time", the first expression under scrutiny, caught the sociological eye because of its salience in Finland and because it appeared as contradictory with a core characteristic of the Finnish context:long family leave. The cliché was found to function as a discursive micromechanism which swept mothers' 'complaints' under the proverbial carpet. Proper emotions and decency in mother-talk thereby appear as collective achievements. An opposite phenomenon - that of the scaling up of rewards procured by children - was also discerned in the data. Indeed, the French expression "Profiter de mon enfant" ["making the most of my child"/"enjoying my child"] is interpreted as a crystallization of a hedonist ethos of motherhood in everyday language. Secondly, the recurrence of this utterance is analyzed in the light of a requisite located in child-rearing expert literature: that of pleasure that women should take in mothering. Hence, one of the rules found to structure the discursive matrixes of motherhood is the laudability and audibility of enjoyment and conversely the discretion and discouragement of 'complaints'. The cultivation of decent matches between certain categories of emotions and certain categories of individuals also appears as a characteristic of discursive matrixes. One of the methodological findings relates to the fact that such matches may be constituted as sociological objects through the identification of recurrent discursive crystallizations in a given culture. Ideal matches may crystallize in turns of speech and mismatches can be managed through clichés. Becoming a mother entails an immersion in such a particular economy of speech. Key words: mothers, motherhood, transition to parenthood, family, emotions, morality, bonds, rhetorical analysis, discourse analysis, media analysis, France, Finland, comparative sociology

On Using Projective Relations for Calibration and Estimation in a Structured-Light Scanner

For structured-light scanners, the projective geometry between a projector-camera pair is identical to that of a camera-camera pair. Consequently, in conjunction with calibration, a variety of geometric relations are available for three-dimensional Euclidean reconstruction. In this paper, we use projector-camera epipolar properties and the projective invariance of the cross-ratio to solve for 3D geometry. A key contribution of our approach is the use of homographies induced by reference planes, along with a calibrated camera, resulting in a simple parametric representation for projector and system calibration. Compared to existing solutions that require an elaborate calibration process, our method is simple while ensuring geometric consistency. Our formulation using the invariance of the cross-ratio is also extensible to multiple estimates of 3D geometry that can be analysed in a statistical sense. The performance of our system is demonstrated on some cultural artifacts and geometric surfaces.

Subject Teacher Training and Teaching in English

The purpose of this Master s thesis is on one hand to find out how CLIL (Content and Language Integrated Learning) teachers and English teachers perceive English and its use in teaching, and on the other hand, what they consider important in subject teacher education in English that is being planned and piloted in STEP Project at the University of Helsinki Department of Teacher Education. One research question is also what kind of language requirements teachers think CLIL teachers should have. The research results are viewed in light of previous research and literature on CLIL education. Six teachers participate in this study. Two of them are English teachers in the comprehensive school, two are class teachers in bilingual elementary education, and two are subject teachers in bilingual education, one of whom teaches in a lower secondary school and the other in an upper secondary school. One English teacher and one bilingual class teacher have graduated from a pilot class teacher program in English that started at the University of Helsinki in the middle of the 1990 s. The bilingual subject teachers are not trained in English but they have learned English elsewhere, which is a particular focus of interest in this study because it is expected that a great number of CLIL teachers in Finland do not have actual studies in English philology. The research method is interview and this is a qualitative case study. The interviews are recorded and transcribed for the ease of analysis. The English teachers do not always use English in their lessons and they would not feel confident in teaching another subject completely in English. All of the CLIL teachers trust their English skills in teaching, but the bilingual class teachers also use Finnish during lessons either because some teaching material is in Finnish, or they feel that rules and instructions are understood better in mother tongue or students English skills are not strong enough. One of the bilingual subject teachers is the only one who consciously uses only English in teaching and in discussions with students. Although teachers good English skills are generally considered important, only the teachers who have graduated from the class teacher education in English consider it important that CLIL teachers would have studies in English philology. Regarding the subject teacher education program in English, the respondents hope that its teachers will have strong enough English skills and that it will deliver what it promises. Having student teachers of different subjects studying together is considered beneficial. The results of the study show that acquiring teaching material in English continues to be the teachers own responsibility and a huge burden for the teachers, and there has, in fact, not been much progress in the matter since the beginning of CLIL education. The bilingual subject teachers think, however, that using one s own material can give new inspiration to teaching and enable the use of various pedagogical methods. Although it is questionable if the language competence requirements set for CLIL teachers by the Finnish Ministry of Education are not adhered to, it becomes apparent in the study that studies in English philology do not necessarily guarantee strong enough language skills for CLIL teaching, but teachers own personality and self-confidence have significance. Keywords: CLIL, bilingual education, English, subject teacher training, subject teacher education in English, STEP

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases Co(L)(2)](ClO4)(2) (1-3), where L is 4'-phenyl-2,2':6',2''-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2''-terpyridine (an-tpy in 2) and 4'-(1-pyrenyl)-2,2':6',2''-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1 : 2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H2O (2 : 1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K-b value of similar to 10(6) M-1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC50 values of 24.2 and 7.6 mu M, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.

Analysis of light‐induced processes in bacteriorhodopsin and its application for spatial light modulation

A simplified energy‐level scheme is proposed for the photochemical cycle of the bacteriorhodopsin molecule. Rate equations are solved for the detailed light‐induced processes based on this model and the intensity‐induced population densities in various states of the molecule at steady state are computed which are used to obtain an analytic expression for the absorption coefficient of the modulation beam. Modulation of the probe laser‐beam transmission by the modulation‐laser‐beam intensity‐induced population changes is analyzed. It is predicted that for a probe beam at 412 nm up to 82% modulation can be achieved using a laser beam intensity of 3.2 W/cm2 at 570 nm. For temperatures ∼77 K, the transmission at 610 nm can be switched from zero to 81% for modulating laser intensity of 11 W/cm2. Construction of a spatial light modulator based on bacteriorhodopsin molecules is proposed and some of its features are discussed.

Remarkable photocytotoxicity of curcumin in HeLa cells in visible light and arresting its degradation on oxovanadium(IV) complex formation

Curcumin (Hcur) as a cellular imaging and PDT agent shows remarkable photocytotoxicity in HeLa cells in visible light of 400-700 nm giving IC50 = 8.2 +/- 0.2 mu M and its degradation is arrested on formation of photocytotoxic dipyridophenazine (dppz) complex VO(cur)(dppz)Cl] (IC50 = 3.3 +/- 0.4 mu M), while both are less toxic in the dark.

Iron(III) benzhydroxamates of dipicolylamines for photocytotoxicity in red light and cellular imaging

Benzhydroxamate (BHA) iron(III) complexes Fe(BHA)(L)ClICI (I, 2)], where L is (phenyl)dipicolylamine (phdpa in I) and (pyrenyl)dipicolylamine (pydpa in 2), were prepared and their photocytotoxicity in visible (400-700 nm) and red (600-720 nm) light was studied. Complex 1 was structurally characterized by X-ray crystallography. The complexes have high-spin iron(III) centers. Complex 2, with a pyrenyl fluorophore, was used for cellular imaging, showing both mitochondrial and nuclear localization in the fluorescence microscopic study. The complex exhibited photocytotoxicity in red light in HeLa cancer cells, giving IC50 value of 24.4(+/- 0.4) pM, but remained essentially non-toxic in the dark. The involvement of reactive oxygen species and an apoptotic nature of cell death were observed from the cellular studies. (C) 2014 Elsevier Ltd. All rights reserved.

Oxovanadium(IV) catecholates of terpyridine bases for cellular imaging and photocytotoxicity in red light

Oxovanadium(IV) catecholates of terpyridyl bases, viz. VO(cat)(L)] (L - phtpy, 1; stpy, 2) and VO(dopa-NBD)(L)] (L = phtpy, 3; stpy, 4), where cat is benzene-1,2-diolate, dopa-NBD is 4-(2-(4-nitrobenzoc]1,2,5]oxadiazol-7-ylamino)ethyl)benzene-1,2-di olate, phtpy is (4'-phenyl)-2,2':6',2 `'-terpyridine and stpy is (2,2':6',2 `'-terpyridin-4'-oxy)ethyl-beta-D-glucopyranoside, were prepared and characterized, and their DNA binding, DNA photo-cleavage activity, photocytotoxicity in red light (600-720 nm), cellular uptake and intracellular localization behaviour were studied. The complexes showed an intense ligand-to-metal charge transfer (LMCT) band at similar to 500 nm. The sugar appended complexes 2 and 4 showed significant uptake into the cancer cells. The dopa-NBD complexes 3 and 4 showing green emission were used for cellular imaging. The complexes showed diffused cellular localization mainly in the cytosol and to a lesser extent into the nucleus as evidenced from the confocal microscopy study. Complexes 1-4 showed significant photocytotoxicity in the PDT spectral window giving low IC50 values, while remaining relatively non-toxic in dark.

Iron(III) Catecholates for Cellular Imaging and Photocytotoxicity in Red Light

Iron(III) complexes Fe(L)(L') (NO3)]-in which L is phenyl-N, N-bis(pyridin-2-yl) methyl]methanamine (1), (anthracen-9-yl)N, N-bis(pyridin-2-yl) methyl] methanamine (2), (pyreny-1-yl)-N, N-bis(pyridin- 2-yl) methyl] methanamine (3-5), and L' is catecholate (1-3), 4-tert-butyl catecholate (4), and 4-(2-aminoethyl)benzene- 1,2-diolate (5)-were synthesized and their photocytotoxic proper-ties examined. The five electron-paramagnetic complexes displayed a FeIII/ Fe-II redox couple near similar to 0.4 V versus a saturated calomel electrode (SCE) in DMF/0.1m tetrabutylammonium perchlorate (TBAP). They showed unpre-cedented photocytotoxicity in red light (600-720 nm) to give IC50-15 mm in various cell lines by means of apoptosis to generate reactive oxygen species. They were ingested in the nucleus of HeLa and HaCaT cells in 4 h, thereby interacting favorably with calf thymus (ct)-DNA and photocleaving pUC19 DNA in red light of 785 nm to form hydroxyl radicals.

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.