Tunable Linear and Nonlinear Optical Properties from Room Temperature Phosphorescent Cyclic Triimidazole-Pyrene Bio-Probe

Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation-dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different species has been followed by thermal and X-ray diffraction analyses and the emissive features interpreted through structural results and DFT/TDDFT calculations. Particularly intriguing is the polymorph TTPyr(HT), serendipitously obtained at high temperature but stable also at room temperature, whose non-centrosymmetric structure guarantees an SHG efficiency 10 times higher than that of standard urea. Its crystal packing, where only the TT units are strongly rigidified by π-π stacking interactions while the Pyr moieties possess partial conformational freedom, is responsible for the observed dual fluorescence. The potentialities of TTPyr for bioimaging have been successfully established.     

Smooth solutions to a class of free boundary parabolic problems

We establish existence, uniqueness, and regularity results for solutions to a class of free boundary parabolic problems, including the free boundary heat equation which arises in the so-called ``focusing problem' in the mathematical theory of combustion. Such solutions are proved to be smooth with respect to time for positive , if the data are smooth.

     

Ionization and Partitioning Profiles of Zwitterions: The case of the anti-inflammatory drug azapropazone

Azapropazone ( 1 ) is a non-steroidal anti-inflammatory drug (NSAID) whose chemical structure is markedly different from that of other agents in this class and challenges our understanding of structure-activity and structure-permeation relationships. Using a variety of experimental and computational techniques, we studied 1 for its molecular structure in the gas phase and non-protic polar solvents, protonation/deprotonation equilibra, tautomerism, and pH-lipophilicity profiles (octan-1-ol/H₂O and dodecane/H₂O). Other NSAIDs and model compounds were also examined for comparison. Due to its very low acidic pK_a1, 1 exists in the physiological pH range as a zwitterion and as an anion. Some pharmacological implications of these findings are discussed.     

Effect of support on the synergy in HDS of thiophene and HDN of pyridine over Mo sulfide catalysts promoted by Rh

The effect of support (SiO₂-Al₂O₃, Al₂O₃,MgO) of the Rh-Mo(S) sulfide catalysts on the synergy in hydrodesulfurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyridine was studied. The synergy in HDS was between 7–10 regardless of the kind of support used. The synergy in HDN varied from none over the MgO supported sample to about 3 over SiO₂-Al₂O₃ supported catalyst, in accord with the positive effect of increasing support acidities. This revised version was published online in June 2006 with corrections to the Cover Date.     

Incorporating the effect of ionic strength in free energy calculations using explicit ions

The incorporation of explicit ions to mimic the effect of ionic strength or to neutralize the overall charge on a system in free energy calculations using molecular dynamics simulations is investigated. The difference in the free energy of hydration between two triosephosphate isomerase inhibitors calculated at five different ion concentrations is used as an example. We show that the free energy difference can be highly sensitive to the presence of explicit ions even in cases where the mutation itself does not involve a change in the overall charge. The effect is most significant if the molecule carries a net charge close to the site mutated. Furthermore, it is shown that the introduction of a small number of ions can lead to very severe sampling problems suggesting that in practical calculations convergence can best be achieved by incorporating either no counterions or by simulating at high ionic strength to ensure sufficient sampling of the ion distribution.     

Hydrolytic protein cleavage mediated by unusual mononuclear copper(II) complexes: X-ray structures and solution studies

The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes.     

Jensen’s functional equation on the symmetric group S<Subscript>n</Subscript>

Two natural extensions of Jensen’s functional equation on the real line are the equations f(xy) + f(xy ⁻¹) =  2f(x) and f(xy) + f(y ⁻¹ x) =  2f(x), where f is a map from a multiplicative group G into an abelian additive group H. In a series of papers (see Ng in Aequationes Math 39:85–99, 1990; Ng in Aequationes Math 58:311–320, 1999; Ng in Aequationes Math 62:143–159, 2001), Ng solved these functional equations for the case where G is a free group and the linear group GL_n(R), R=\mathbbZ,\mathbbR{{GL_n(R), R=\mathbb{Z},\mathbb{R}}} , is a quadratically closed field or a finite field. He also mentioned, without a detailed proof, in the above papers and in (see Ng in Aequationes Math 70:131–153, 2005) that when G is the symmetric group S _n , the group of all solutions of these functional equations coincides with the group of all homomorphisms from (S _n , ·) to (H, + ). The aim of this paper is to give an elementary and direct proof of this fact.