Synthesis,characterization, and photophysical studies of new bichromophoric ruthenium(II) complexes

The photophysical properties of a series of prepared ruthenium tris(bipyridine) complexes, covalently linked to aromatic species, of type [Ru(bpy)(2)-(4-methyl-4'-(arylaminocarbonyl)-2,2'-bipyridine)](2+) ([Ru(bpy)(2)(mbpy-L)](2+), where bpy = 2,2'-bipyridine; mbpy = 4-methyl-4'-carbonyl-2,2'-bipyridine; and L = 2-aminonaphthyl (naph), 9-aminoanthryl (anth), 1-aminopyrenyl (pyr), or 9-aminoacridinyl (acrd)) were studied by electronic absorption spectroscopy and steady state and time resolved luminescence spectroscopies. The absorption spectra of the MLCT electronic transition of the complexes are similar, which is in agreement with a practically constant redox potential of Ru(III/II) close to 1.28 V versus Ag/AgCl. However, the luminescence spectra of the new complexes are red shifted compared to Ru(bpy)(3)(2+), and this effect is ascribed to solvation and inductive effects of the amide group which enhance the symmetry breakdown among the three bipyridyl ligands. The energy stabilization of the (3)MLCT state is in the range 2.1-8.4 kJ/mol. The triplet-triplet energy transfer between the Ru complex and the aromatic species linked by an amide spacer is a slow process with rate constants of 2.6 x 10(4), 3.6 x 10(4), and 4.9 x 10(4) s(-)(1) for anthracene, acridine, and pyrene as acceptors in methanol, respectively. The energy transfer rate constant increases with decreasing polarity of the solvent. In dichloromethane, the rate constants for anthracene, acridine, and pyrene acceptors are 2.6 x 10(5), 1.5 x 10(5), and 2.9 x 10(5) s(-)(1), respectively. The low efficiency of energy transfer is due to the small difference in triplet energy between donor and acceptor species, weak electronic coupling, and unfavorable Franck-Condon factors, despite the short separation distance between donor and acceptor species in an amide bridge.     

Adsorption of Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) from aqueous solutions on a 2-mercaptobenzimidazole-modified silica gel

The chemically modified silica, obtained by reacting 2-mercaptobenz-imidazole with 3-chloropropyl silica gel, was used to adsorb Cu(II), Zn(II), Cd(II) and Pb(II) from aqueous solutions at various pH. Between pH 3–5, the order of selectivity was Hg(II) > Cd(II) Cu(II) Zn(II) Pb(II). Under batch conditions retentions of 100% were achieved for all metals except for Pb(II) where 93% was attained. Under column conditions recoveries of 100% were obtained for all metals.     

MoCalc: a new graphical user interface for molecular calculations

A new computer program called MoCalc (Molecular Calculations) has been designed to help the computational chemistry practitioner in the task of performing and analyzing molecular calculations. MoCalc is a graphical user interface for the MO calculation programs Gamess and Mopac, and uses Rasmol and Babel for molecule display and file conversion, respectively. In its initial version, MoCalc can execute the following operations: (a) create and handle Gamess and Mopac input files; (b) import any kind of molecular geometry supported by Babel and paste it as Cartesian, internal, or Gaussian-type coordinates on the input file; (c) convert Gamess and Mopac output files to inputs of both programs; (d) edit and validate the keywords that control the Gamess and Mopac calculation procedure; (e) display the input (Mopac) and output (Gamess and Mopac) molecular geometries; (f) run single or multiple (batch) calculations, either interactively or in background; (g) automatically open the output files as soon as the calculation finishes; (h) extract results from the output files, such as energy, charges, dipole, population analysis, wave function, bond orders, and valence analysis, and display them in spreadsheets; (i) calculate reactivity indices derived from the frontier orbital theory and the root-mean-square (rms) deviation of input and output geometries. All the results generated by MoCalc can be promptly transferred to text editors and electronic spreadsheets, which facilitate a detailed subsequent analysis and the publication of the results. MoCalc can also perform graphical and numerical comparative analysis of the some results when more than one output file is loaded. The program was coded in Visual Basic and runs in Windows 95/98/NT4/ME/2000/XP environments.     

Particle-Like Description for FRW Cosmologies

We show that the dynamical behavior of the scale factor in FRW cosmologies with equation of state p = ( - 1) is formally equivalent to a classical particle under the action of a homogeneous potential V(q) = qⁿ, where and n are constants. The relations (n) and (E,n), where is the curvature parameter and E is the total energy of the test particle, are established. It is shown that the same approach can be generalized to include a nonvanishing cosmological constant as well as to describe viscous models. A comparison is made between the Lagrangian and general relativistic possibilities.     

Semiclassical backreaction around a nearly spinning cosmic string

This Letter investigates semiclassical backreaction of a conformally coupled massless scalar field on the geometrical background of a nearly spinning cosmic string — the spin density is smaller than, but arbitrarily close to, the dislocation parameter. As the spin density approaches the dislocation parameter, it is shown that an ergoregion spreads indefinitely around the cosmic string, boosting along the string axis the once static observers. Considering that the geometrical background contains closed timelike curves when the spin density exceeds the dislocation parameter, it is argued that the appearance of the ergoregion may be part of a chronology protection mechanism that takes place in related non-stationary geometries.     

Specific heat spectra of non-interacting fermions in a quasiperiodic ladder sequence

We compute the specific heat spectra of non-interacting fermions whose energy spectrum was obtained from a quasiperiodic ladder sequence (Fibonacci and Rudin-Shapiro type), mimicking a DNA molecule model. The specific heat is calculated from their underlying multi-fractal energy spectrum, considering several values of energy densities. Comparisons are made with a real DNA sequence, namely the human chromosome 22 (Ch22).     

Edgeworth expansion for an estimator of the adjustment coefficient

We establish an Edgeworth expansion for an estimator of the adjustment coefficient R, directly related to the geometric-type estimator for general exponential tail coefficients, proposed in [Brito, M., Freitas, A.C.M., 2003. Limiting behaviour of a geometric-type estimator for tail indices. Insurance Math. Econom. 33, 211-226].Using the first term of the expansion, we construct improved confidence bounds for R. The accuracy of the approximation is illustrated using an example from insurance (cf. [Schultze, J., Steinebach, J., 1996. On least squares estimates of an exponential tail coefficient. Statist. Dec. 14, 353-372]).     

Nitroso group transfer from substituted N-methyl-N-nitrosobenzenesulfonamides to amines. Intrinsic and apparent reactivity.

We have studied the nitroso group transfer from substituted N-methyl-N-nitrosobenzenesulfonamides to primary and secondary amines, observing that the rate of the reaction increases as a consequence of the presence of electron withdrawing groups on the aromatic ring of the nitrosating agents. The rate constants determined for the nitroso group transfer, ktr, give good Bronsted-type relationships between log ktr (rate constant for nitroso group transfer) and pKaR2NH2+ and pKaleaving group. The study of the nitrosation processes of secondary amines catalyzed by ONSCN and denitrosation catalyzed by SCN-, in combination with the formation equilibrium of ONSCN, has enabled us to calculate the value of the equilibrium constant for the loss of the NO+ group from a protonated N-nitrosamine (pKNOR2N+HNO), which can be defined by analogy with pKaR2NH2+. The value of pKNOX-NO for the loss of the NO+ group from an N-methyl-N-nitrosobenzenesulfonamide was obtained in a similar way. By using values of delta pKNO = pKNOR2N+HNO - pKNOX-NO, we were able to calculate the equilibrium constant for the nitroso group transfer and characterize the transition state. On the basis of Bronsted-type correlations, we have obtained values of beta nuclnorm and alpha lgnorm approximately equal to 0.55, showing a perfectly balanced transition state. In terms of the Marcus theory, the calculation of the intrinsic barriers for the nitroso group transfer reaction shows that the presence of electron withdrawing groups on the aromatic ring of the N-methyl-N-nitrosobenzenesulfonamides does not cause these barriers to vary.     

Photosensitive Materials for Integrated Optic Applications

This article presents results of device fabrication using UV processing of materials and integrated optic components produced by flame hydrolysis deposition and hybrid sol-gel technology. Photosensitive materials were employed in the fabrication of channel waveguides and channel photo-imprinted waveguides incorporating Bragg gratings through single and double-step exposure.     

Time-Dependent Dephasing and Quantum Transport

The investigation of the phenomenon of dephasing assisted quantum transport, which happens when the presence of dephasing benefits the efficiency of this process, has been mainly focused on Markovian scenarios associated with constant and positive dephasing rates in their respective Lindblad master equations. What happens if we consider a more general framework, where time-dependent dephasing rates are allowed, thereby, permitting the possibility of non-Markovian scenarios? Does dephasing-assisted transport still manifest for non-Markovian dephasing? Here, we address these open questions in a setup of coupled two-level systems. Our results show that the manifestation of non-Markovian dephasing-assisted transport depends on the way in which the incoherent energy sources are locally coupled to the chain. This is illustrated with two different configurations, namely non-symmetric and symmetric. Specifically, we verify that non-Markovian dephasing-assisted transport manifested only in the non-symmetric configuration. This allows us to draw a parallel with the conditions in which time-independent Markovian dephasing-assisted transport manifests. Finally, we find similar results by considering a controllable and experimentally implementable system, which highlights the significance of our findings for quantum technologies.