Faculty of Natural Sciences and Mathematics

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The status of women in the region of Golo Brdo, Republic of Albania
(New Europe College, Букурешт, Република Романија, 2007)
Ines Crvenkovska Risteska
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NARRATIVES AND SELF-DETERMINATION: HISTORIES ON PERSONAL SEXUALITY AND THE SEXUALITY OF THE OTHER
(Časopis Centra za etnološka istraživanja (CEAI) Filozofskog fakulteta Univerziteta u Beogradu, 2009)
Ines Crvenkovska Risteska
This research deals with the sexuality of young males based upon their narratives. Through their memories, they create a history of their personal sexuality. This is how a periodization of experiences related to same sex sexual relations is formed. Personal perception on one's own sexuality is reflected upon the continuous process of construction of one's own gender.
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Topochemical limits for solid-state photoreactivity by fine tuning of the pi-pi interactions
(2009-06-03)
Yang, Shi-Yao
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Naumov, Pance
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Fukuzumi, Shunichi
The limiting topochemical criteria for photodimerization were studied by modulation of the pi-pi stacking interactions between self-templating planar molecules with hydrogen bonding. The product yield and composition can be controlled predominantly by the distance between the reactive bonds.
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Hybrid hard- and soft-modelling applied to analyze ultrafast processes by femtosecond transient absorption spectroscopy: study of the photochromism of salicylidene anilines
(Elsevier BV, 2009-05-29)
Ruckebusch, C
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Sliwa, M
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Réhault, J
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Naumov, P
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Huvenne, J P
Multivariate curve resolution-alternating least squares (MCR-ALS) of multi-experiment data analysis was successfully applied to elucidate the photodynamics of the N-(3-methylsalicylidene)-3-methylaniline by analyzing UV-vis femtosecond transient absorption spectra. The two-way data obtained present some specific difficulties linked to the nature of the transient spectra collected and to the overlapping of the photodynamics of the solvent and other contributions at short time scale (below 1 ps). Advantage was taken from the flexibility of the hybrid hard-soft multivariate curve resolution (HS-MCR) approach to consider a non-absorbing contribution in the kinetic model and to provide a functional description of the solvent in soft-modelling. The results obtained confirm the existence of an intermediate excited state in the process, which is created just after the ESIPT. It was observed that this intermediate relaxes in a few hundreds of femtosecond to the S(1) fluorescent cis-keto excited state and a decay time constant of 219 fs was found. These results confirm other femtosecond time-resolved fluorescence studies on salicylidene aniline molecules. Previous hypothesis on the formation of the trans-keto photoproduct from the S(1) fluorescent cis-keto state (time constant 14 ps) is also confirmed.
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Structure and spectroscopy of oxyluciferin, the light emitter of the firefly bioluminescence
(American Chemical Society (ACS), 2009-08-19)
Naumov, Pance
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Ozawa, Yutaka
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Ohkubo, Kei
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Fukuzumi, Shunichi
The crystal structures of the pure, unsubstituted firefly emitter oxyluciferin (OxyLH(2)) and its 5-methyl analogue (MOxyLH(2)) were determined for the first time to reveal that both molecules exist as pure trans-enol forms, enol-OxyLH(2) and enol-MOxyLH(2), assembled as head-to-tail hydrogen-bonded dimers. Their steady-state absorption and emission spectra (in solution and in the solid state) and nanosecond time-resolved fluorescence decays (in solution) were recorded and assigned to the six possible trans chemical forms of the emitter and its anions. The spectra of the pure emitter were compared to its bioluminescence and fluorescence spectra when it is complexed with luciferase from the Japanese firefly (Luciola cruciata) and interpreted in terms of the intermolecular interactions based on the structure of the emitter in the luciferase active site. The wavelengths of the emission spectral maxima of the six chemical forms of OxyLH(2) are generally in good agreement with the theoretically predicted energies of the S(0)-S(1) transitions and range from the blue to the red regions, while the respective absorption maxima range from the ultraviolet to the green regions. It was confirmed that both neutral forms, phenol-enol and phenol-keto, are blue emitters, whereas the phenolate-enol form is yellow-green emitter. The phenol-enolate form, which probably only exists as a mixture with other species, and the phenolate-enolate dianion are yellow or orange emitters with close position of their emission bands. The phenolate-keto form always emits in the red region. The concentration ratio of the different chemical species in solutions of OxyLH(2) is determined by several factors which affect the intricate triple chemical equilibrium, most notably the pH, solvent polarity, hydrogen bonding, presence of additional ions, and pi-pi stacking. Due to the stabilization of the enol group of the 4-hydroxythiazole ring by hydrogen bonding to the proximate adenosine monophosphate, which according to the density functional calculations is similar to that due to the dimerization of two enol molecules observed in the crystal, the phenolate ion of the enol tautomer, which is the predominant ground-state species within the narrow pH interval 7.44-8.14 in buffered aqueous solutions, is the most probable emitter of the yellow-green bioluminescence common for most wild-type luciferases. This conclusion is supported by the bioluminescence/fluorescence spectra and the NMR data, as well the crystal structures of OxyLH(2) and MOxyLH(2), where the conjugated acid (phenol) of the emitter exists as pure enol tautomer.
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New type of dual solid-state thermochromism: modulation of intramolecular charge transfer by intermolecular pi-pi interactions, kinetic trapping of the aci-nitro group, and reversible molecular locking
(American Chemical Society (ACS), 2009-10-22)
Naumov, Pance
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Lee, Sang Cheol
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Ishizawa, Nobuo
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Jeong, Young Gyu
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Chung, Ihn Hee
When heated above room temperature, some crystalline polymorphs of the 1,3-bis(hydroxyalkylamino)-4,6-dinitrobenzenes (BDBn, n = 2-5), bis(hydroxyalkyl) analogues of the intramolecular charge-transfer molecule 1,3-diamino-4,6-dinitrobenzene, exhibit "dual" thermochromism: gradual color change from yellow to orange at lower temperatures, and sharp color change from orange to red at higher temperatures. These two thermochromic changes are related to different solid-state processes. When allowed to cool to room temperature, the yellow color of the thermochromic molecules with different alkyl length (n) is recovered with unexpectedly different kinetics, the order of the respective rate constants ranging from 10(-7)-10(-6) s(-1) for BDB2 to about 0.1 s(-1) in the case of BDB3. The thermochromic mechanism and the reasons behind the different kinetics were clarified on the basis of detailed crystallographic characterization, kinetic thermoanalysis, and spectroscopic study of eight crystalline forms (seven polymorphs and one solvate). It was found that the polymorphism is due to the possibility of "locking" and "unlocking" of the alkyl arms by formation of a strong intramolecular hydrogen bond between the hydroxyl groups at their hydroxyl termini. The locking of BDB2, with shortest alkyl arms, is reversible and it can be controlled thermally; either of the two conformations can be obtained in the solid state by proper thermal treatment. By use of high temperature in situ single crystal X-ray diffraction analysis of BDB3, direct evidence was obtained that the gradual thermochromic change is related to increased distance and weakened pi-pi interactions between the stacked benzene rings: the lattice expands preferably in the stacking direction, causing enhanced oscillator strength and red shift of the absorption edge of the intramolecular charge transfer transition. The second, sharp thermochromic change had been assigned previously to solid-solid phase transition triggered by intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular pi-pi interactions and thermal intramolecular proton transfer to aromatic nitro group.
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On the short carbonyl bond in bis[mu-1,2-benzisothiazol-3(2H)-one 1,1-dioxido-kappa2N:O]bis[[1,2-benzisothiazol-3(2H)-one 1,1-dioxido-kappaN]bis(imidazole)copper(II)]
(International Union of Crystallography (IUCr), 2001-09)
Naumov, P
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Jovanovski, G
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Hu, S Z
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Suh, I H
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Razak, I A
The short carbonyl bond in the title compound, [Cu(2)(C(7)H(4)NO(3)S)(4)(C(3)H(4)N(2))(4)] [Liu, Huang, Li & Lin (1991). Acta Cryst. C47, 41-43], is an artifact of disorder in the isothiazol-3(2H)-one 1,1-dioxide part of the 1,2-benzisothiazol-3(2H)-one entity. In the present redetermination, all bond dimensions in the centrosymmetric dinuclear molecule are normal. The five-coordinate Cu atom shows trigonal-bipyramidal coordination. Hydrogen bonds from the imidazole donor ligand link adjacent molecules into a two-dimensional layer structure.
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Digitoxin metabolism by rat liver microsomes
(1975-09-01)
Schmoldt, A
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Benthe, H F
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Haberland, G
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Relativistic addition of parallel velocities from Lorentz contraction and time dilation
(American Association of Physics Teachers (AAPT), 2006-09)
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Aberration of light in a uniformly moving optical medium
(American Association of Physics Teachers (AAPT), 2004-07)

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