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.

The effect of exercise and light on mood

The aim of the study was to compare the effect physical exercise and bright light has on mood in healthy, working-age subjects with varying degrees of depressive symptoms. Previous research suggests that exercise may have beneficial effects on mood at least in subjects with depression. Bright light exposure is an effective treatment of winter depression, and possibly of non-seasonal depression as well. Limited data exist on the effect of exercise and bright light on mood in non-clinical populations, and no research has been done on the combination of these interventions. Working-age subjects were recruited through occupational health centres and 244 subjects were randomized into intervention groups: exercise, either in bright light or normal lighting, and relaxation / stretching sessions, either in bright light or normal gym lighting. During the eight-week intervention in midwinter, subjects rated their mood using a self-rating version of the Hamilton Depression Scale with additional questions for atypical depressive symptoms. The main finding of the study was that both exercise and bright-light exposure were effective in treating depressive symptoms. When the interventions were combined, the relative reduction in the Hamilton Depression Scale was 40 to 66%, and in atypical depressive symptoms even higher, 45 to 85%. Bright light exposure was more effective than exercise in treating atypical depressive symptoms. No single factor could be found that would predict a good response to these interventions. In conclusion, aerobic physical exercise twice a week during wintertime was effective in treating depressive symptoms. Adding bright light exposure to exercise increased the benefit, especially by reducing atypical depressive symptoms. Since this is so, this treatment could prevent subsequent major depressive episodes among the population generally.

DNA cleavage in red light promoted by copper(II) complexes of -amino acids and photoactive phenanthroline bases

Ternary copper(II) complexes [Cu(L-trp)(B)(H2O)](NO3) ( 1–3) and [Cu(L-phe)(B)(H2O)](NO3) ( 4–6) of L-tryptophan (L-trp) and L-phenylalanine (L-phe) having phenanthroline bases (B), viz. 1,10-phenanthroline (phen, 1 and 4), dipyrido[3,2-d:2,3-f]quinoxaline (dpq, 2 and 5) and dipyrido[3,2-a:2,3-c]phenazine (dppz, 3 and 6), were prepared and characterized by physico-chemical techniques. Complexes 3 and 6 were structurally characterized by X-ray crystallography and show the presence of a square pyramidal (4 + 1) CuN3O2 coordination geometry in which the N,O-donor amino acid (L-trp or L-phe) and N,N-donor phenanthroline base bind at the equatorial plane with an aqua ligand coordinated at the elongated axial site. Complex 3 shows significant distortion from the square pyramidal geometry and a strong intramolecular – stacking interaction between the pendant indole ring of L-trp and the planar dppz aromatic moiety. All the complexes display good binding propensity to the calf thymus DNA giving an order: 3, 6 (dppz) > 2, 5 (dpq) > 1, 4 (phen). The binding constant (Kb) values are in the range of 2.1 × 104–1.1 × 106 mol-1 with the binding site size (s) values of 0.17–0.63. The phen and dpq complexes are minor groove binders while the dppz analogues bind at the DNA major groove. Theoretical DNA docking studies on 2 and 3 show the close proximity of two photosensitizers, viz. the indole moiety of L-trp and the quinoxaline/phenazine of the dpq/dppz bases, to the complementary DNA strands. Complexes 2 and 3 show oxidative DNA double strand breaks (dsb) of supercoiled (SC) DNA forming a significant quantity of linear DNA along with the nicked circular (NC) form on photoexposure to UV-A light of 365 nm and red light of 647.1 nm (Ar–Kr laser). Complexes 1, 5 and 6 show only single strand breaks (ssb) forming NC DNA. The red light induced DNA cleavage involves metal-assisted photosensitization of L-trp and dpq/dppz base resulting in the formation of a reactive singlet oxygen (1O2) species.

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

Cities of Light: Two Centuries of Urban Illumination

Cities of Light is the first global overview of modern urban illumination, a development that allows human wakefulness to colonize the night, doubling the hours available for purposeful and industrious activities. Urban lighting is undergoing a revolution due to recent developments in lighting technology, and increased focus on sustainability and human-scaled environments. Cities of Light is expansive in coverage, spanning two centuries and touching on developments on six continents, without diluting its central focus on architectural and urban lighting. Covering history, geography, theory, and speculation in urban lighting, readers will have numerous points of entry into the book, finding it easy to navigate for a quick reference and or a coherent narrative if read straight through. With chapters written by respected scholars and highly-regarded contemporary practitioners, this book will delight students and practitioners of architectural and urban history, area and cultural studies, and lighting design professionals and the institutional and municipal authorities they serve. At a moment when the entire world is being reshaped by new lighting technologies and new design attitudes, the longer history of urban lighting remains fragmentary. Cities of Light aims to provide a global framework for historical studies of urban lighting and to offer a new perspective on the fast-moving developments of lighting today.

Edge of Danger: electric light and the negotiation of public and private domestic space in Philip Johnson's Glass and Guest House

In the first half of the twentieth century the dematerializing of boundaries between enclosure and exposure problematized traditional expectations of the domestic environment. At the same time, as a space of escalating technological control, the modern domestic interior also offered new potential to redefine the meaning and means of habitation. The inherent tension between these opposing forces is particularly evident in the introduction of new electric lighting technology and applications into the modern domestic interior in the mid-twentieth century. Addressing this nexus of technology and domestic psychology, this article examines the critical role of electric lighting in regulating and framing both the public and private occupation of Philip Johnson's New Canaan estate. Exploring the dialectically paired transparent Glass House and opaque Guest House, this study illustrates how Johnson employed electric light to negotiate the visual environment of the estate as well as to help sustain a highly aestheticized domestic lifestyle. Contextualized within the existing literature, this analysis provides a more nuanced understanding of the New Canaan estate as an expression of Johnson's interests as a designer as well as a subversion of traditional suburban conventions.

Influences on sleep-wake behaviour in older adults and community dementia care: Light exposure and partner impact

This project described sleep-wake behaviour in community-dwelling older adults and in community dementia care. It examined the applicability of a newly presented conceptual model (the Multifactorial Influences on Sleep Health model) to evaluate factors influencing sleep in ageing, with a particular focus on the importance of daytime light exposure and the impact of partners.

The Science and Art of Light

Architecture today often is praised for its tectonics, floating volumes, and sensational, gravity-defying stunts of “starchitecture.” Yet, very so often there is a building that inspires descriptions of the sublime, the experiential, and the power of light and architecture to transcend our expectations. The new Meinel Optical Sciences Research Building, designed by Phoenix-based Richärd+Bauer for the University of Arizona, Tucson, is one of these architectural rarities. Already drawing comparisons to Louis Kahn's 1965 Salk Institute for Biological Studies in La Jolla, California, the indescribable quality of light that characterizes the best of Kahn's work also resonates in Richärd+Bauer's new building. Both an expansion and renovation of the existing College of Optical Sciences facilities, the Meinel building includes teaching and research laboratories, six floors of offices, discussion areas, conference rooms, and an auditorium. The new 47,000 square-foot cast-in-place concrete structure, wrapped on three-sides in copper-alloy panels, harmonizes with the largely brick vocabulary of the campus while reflecting the ethereal quality of the wide Arizona sky. The façade, however, is merely a prelude for what awaits inside—where light and architecture seamlessly combine to create moments of pure awe.

Light and the Urban Nightscape

The design of nighttime environments that instill feelings of both safety and enjoyment is of critical importance to the economic and cultural vitality of urban centers around the world. This has been broadly recognized in Europe for several decades, but has only recently been seriously addressed in North America. The following considers lighting design for the urban nightscape through the examination of two progressive urban lighting projects, organizations like the Lighting Urban Community International (LUCI), the City-People-Light program, and the role of lighting festivals and workshops in advancing urban lighting design.

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.

Characterizing Physical Properties of Wetting Paper by Air Coupled Ultrasound and Light

This thesis reports investigations into the paper wetting process and its effects on the surface roughness and the out-of-plane (ZD) stiffness of machine-made paper. The aim of this work was to test the feasibility of employing air-borne ultrasound methods to determine surface roughness (by reflection) and ZD stiffness (by through transmission) of paper during penetration of distilled water, isopropanol and their mixtures. Air-borne ultrasound provides a non-contacting way to evaluate sample structure and mechanics during the liquid penetration event. Contrary to liquid immersion techniques, an air-borne measurement allows studying partial wetting of paper. In addition, two optical methods were developed to reveal the liquid location in paper during wetting. The laser light through transmission method was developed to monitor the liquid location in partially wetted paper. The white light reflection method was primarily used to monitor the penetration of the liquid front in the thickness direction. In the latter experiment the paper was fully wetted. The main results of the thesis were: 1) Liquid penetration induced surface roughening was quantified by monitoring the ultrasound reflection from the paper surface. 2) Liquid penetration induced stiffness alteration in the ZD of paper could be followed by measuring the change in the ultrasound ZD resonance in paper. 3) Through transmitted light revealed the liquid location in the partially wetted paper. 4) Liquid movement in the ZD of the paper could be observed by light reflection. The results imply that the presented ultrasonic means can without contact measure the alteration of paper roughness and stiffness during liquid transport. These methods can help avoiding over engineering the paper which reduces raw material and energy consumption in paper manufacturing. The presented optical means can estimate paper specific wetting properties, such as liquid penetration speed, transport mechanisms and liquid location within the paper structure. In process monitoring, these methods allow process tuning and manufacturing of paper with engineered liquid transport characteristics. With such knowledge the paper behaviour during printing can be predicted. These findings provide new methods for paper printing, surface sizing, and paper coating research.

Primordial Isocurvature Perturbation in Light of CMB and LSS Data

The increased accuracy in the cosmological observations, especially in the measurements of the comic microwave background, allow us to study the primordial perturbations in grater detail. In this thesis, we allow the possibility for a correlated isocurvature perturbations alongside the usual adiabatic perturbations. Thus far the simplest six parameter \Lambda CDM model has been able to accommodate all the observational data rather well. However, we find that the 3-year WMAP data and the 2006 Boomerang data favour a nonzero nonadiabatic contribution to the CMB angular power sprctrum. This is primordial isocurvature perturbation that is positively correlated with the primordial curvature perturbation. Compared with the adiabatic \Lambda CMD model we have four additional parameters describing the increased complexity if the primordial perturbations. Our best-fit model has a 4% nonadiabatic contribution to the CMB temperature variance and the fit is improved by \Delta\chi^2 = 9.7. We can attribute this preference for isocurvature to a feature in the peak structure of the angular power spectrum, namely, the widths of the second and third acoustic peak. Along the way, we have improved our analysis methods by identifying some issues with the parametrisation of the primordial perturbation spectra and suggesting ways to handle these. Due to the improvements, the convergence of our Markov chains is improved. The change of parametrisation has an effect on the MCMC analysis because of the change in priors. We have checked our results against this and find only marginal differences between our parametrisation.