Effects of potassium on the supramolecular structure and electronic properties of eumelanin thin films

The role of potassium in the formation of synthetic eumelanin aggregates is investigated by atomic force microscopy and soft-X-ray spectroscopy. Control over the thin film granularity is achieved by using K salts, in both drop casting and electrodeposition of eumelanin thin films. Further control over orientation is made possible by a suitable choice of the substrate: evidence of self-assembly is found for thin films deposited on gold. Finally, it is shown that the potassium content affects not only the samples morphology, but also the low-lying states in the valence band, where a transfer of spectral weight across the HOMO-LUMO gap is observed, disclosing possible applications of this multifunctional biomacromolecule.     

The Role of Ion Pairs in the Second‐Order NLO Response of 4‐X‐1‐Methylpiridinium Salts

A series of 4‐X‐1‐methylpyridinium cationic nonlinear optical (NLO) chromophores (X=(E)‐CH?CHC₆H₅; (E)‐CH?CHC₆H₄‐4′‐C(CH₃)₃; (E)‐CH?CHC₆H₄‐4′‐N(CH₃)₂; (E)‐CH?CHC₆H₄‐4′‐N(C₄H₉)₂; (E,E)‐(CH?CH)₂C₆H₄‐4′‐N(CH₃)₂) with various organic (CF₃SO₃^?, p‐CH₃C₆H₄SO₃^?), inorganic (I^?, ClO₄^?, SCN^?, [Hg₂I₆]^2?) and organometallic (cis‐[Ir(CO)₂I₂]^?) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second‐order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second‐order NLO response, investigated by the electric‐field‐induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10^?3 M , and their dipole moments were determined. Generally, below 5×10^?4 M , ion pairs start to dissociate into ions with parallel increase of the second‐order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10^?3 M , some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second‐order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self‐aggregate.     

Integration of spore-based genetically engineered whole-cell sensing systems into portable centrifugal microfluidic platforms

Bacterial whole-cell biosensing systems provide important information about the bioavailable amount of target analytes. They are characterized by high sensitivity and specificity/selectivity along with rapid response times and amenability to miniaturization as well as high-throughput analysis. Accordingly, they have been employed in various environmental and clinical applications. The use of spore-based sensing systems offers the unique advantage of long-term preservation of the sensing cells by taking advantage of the environmental resistance and ruggedness of bacterial spores. In this work, we have incorporated spore-based whole-cell sensing systems into centrifugal compact disk (CD) microfluidic platforms in order to develop a portable sensing system, which should enable the use of these hardy sensors for fast on-field analysis of compounds of interest. For that, we have employed two spore-based sensing systems for the detection of arsenite and zinc, respectively, and evaluated their analytical performance in the miniaturized microfluidic format. Furthermore, we have tested environmental and clinical samples on the CD microfluidic platforms using the spore-based sensors. Germination of spores and quantitative response to the analyte could be obtained in 2.5–3 h, depending on the sensing system, with detection limits of 1 × 10⁻⁷ M for arsenite and 1 × 10⁻⁶ M for zinc in both serum and fresh water samples. Incorporation of spore-based whole-cell biosensing systems on microfluidic platforms enabled the rapid and sensitive detection of the analytes and is expected to facilitate the on-site use of such sensing systems.     

Variation of the ultrafast fluorescence quenching in 2,6-sulfanyl-core-substituted naphthalenediimides by electron transfer

The ultrafast fluorescence quenching of 2,6-sulfanyl-core-substituted naphthalenediimides was investigated by transient spectroscopy. We find a strong dependence of the relaxation on the chemical structure of the substituent. Direct linking of an aryl rest to the sulfur atom leads to a strong red shift of the fluorescence in 1 ps and the disappearance of the emission in 5-7 ps depending on the polarity and viscosity of the solvent. This complex behavior is interpreted with the help of quantum chemical calculations. The calculations suggest that the initial relaxation corresponds to a planarization of the substituents and an associated partial electron transfer. This is followed by a twisting of the phenylsulfanyl substituents out of the molecular plane that allows a complete localization of the electron-donating orbital on the aryl group. Finally the back transfer happens in another 5-7 ps. For an additional methylene spacer group between the sulfur and the aryl, this sequence of relaxation steps is not possible and a simple exponential decay, slower by about 1 order of magnitude, is found.     

New organotin(IV) complexes with l-Arginine, Nα-t-Boc-l-Arginine and l-Alanyl-l-Arginine: Synthesis, structural investigations and cytotoxic activity

Novel diorganotin(IV) derivatives of l-Arginine (HArg), N_α-(tert-Butoxycarbonyl)-l-Arginine (Boc-Arg-OH) and l-Ala-l-Arg (H₂Ala-Arg), H₂NC(NH)NH(CH₂)₃CH(NHR′)CO₂H, where R′ = H in HArg, R′ = C(O)OC(CH₃)₃ in Boc-Arg-OH, R′ = H₂NCH(CH₃)CO in H₂Ala-Arg and triorganotin(IV) derivatives of Boc-Arg-OH have been synthesized and structurally characterized. The complexes were investigated by FT-IR and ¹¹⁹Sn Mössbauer in the solid state and by ¹H, ¹³C, ¹¹⁹Sn and ¹H-¹H COSY NMR spectroscopy, in solution. The spectroscopic characterization leading to the proposed molecular structures was accomplished on the basis of these experiments. l-Arginine appears to behave as a chelating ligand through carboxylate and -NH₂ groups in Me₂Sn(Arg)₂, while in N_α-t-Boc-l-Arginine complex, the N_α-protected amino group being exempted from coordination, only the carboxylate groups are effectors of bonding to the organometallic moieties. FT-IR spectra give a clear indication that guanidino groups in all the complexes are not involved in coordination, since ν(CN-H) frequency of the terminal guanidino group is fairly constant and unshifted relative to the free ligand. The biological activity of organotin(IV)-complexes was also investigated by use of human HT29 colorectal carcinoma cells. The cytotoxic activity of the compounds was determined by the MTT quantitative colorimetric assay, capable of detecting viable cells in comparison with that exerted by cisplatin. A marked cytotoxic activity for nearly all complexes, is evident being higher than that exerted by cisplatin, while no significant improvement of activity was observed for Me₂Sn(Arg)₂ and Me₂Sn(Ala-Arg), which was confirmed by IC₅₀ values. Then, we assessed whether the cytotoxicity induced by organotin(IV) complexes was associated with the induction of apoptosis. Light microscopy analysis, performed to study the morphological changes induced in HT29 cells, confirmed the results obtained with MTT test. No significant morphological alterations were observed in HT29 cells after treatment with Me₂Sn(Ala-Arg) and Me₂Sn(l-Arg)₂. Cells treated with ⁿBu₂Sn(Boc-Arg)₂, ⁿBu₂Sn(Ala-Arg), ⁿBu₃Sn(Boc-Arg) and Me₃Sn(Boc-Arg), appeared rounded, isolated and detached from culture substrate, indicating the commitment to apoptotic cell death.     

Hydrogen abstraction from H‐donor substrates by the 6‐CF3‐benzotriazol‐N‐oxyl radical (TFNO)

The aminoxyl radical 6‐trifluoromethyl‐benzotriazol‐N‐oxyl (TFNO) has been generated from the parent hydroxylamine 6‐CF₃‐1‐hydroxy‐benzotriazole (TFBT) by one‐electron oxidation with a Ce^IV salt and characterized by spectrophotometry and cyclic voltammetry (CV). Rate constants of H‐abstraction (k_H) by TFNO from a number of H‐donor benzylic substrates have been determined spectrophotometrically in MeCN solution at 25 °C. A radical H‐atom transfer (HAT) route of oxidation is substantiated for TFNO by several pieces of evidence. The kinetic data also testify the relevance of stereoelectronic effects upon the HAT reactivity of TFNO. Copyright © 2010 John Wiley & Sons, Ltd.     

An existence result for a class of quasilinear elliptic eigenvalue problems in unbounded domains

We consider a nonlinear eigenvalue problem under Robin boundary conditions in a domain with (possibly noncompact) smooth boundary. The problem involves a weighted p–Laplacian operator and subcritical nonlinearities satisfying Ambrosetti–Rabinowitz type conditions. Using Morse theory and a cohomological local splitting as in Degiovanni et al. (Commun Contemp Math 12:475–486, 2010), we prove the existence of a nontrivial weak solution for all (real) values of the eigenvalue parameter. Our result is new even in the semilinear case p = 2 and complements some recent results obtained in Autuori et al. (Adv Anal Equ 18:1–48, 2013).     

A clustering approach for scenario tree reduction: an application to a stochastic programming portfolio optimization problem

This paper deals with the problem of scenario tree reduction for stochastic programming problems. In particular, a reduction method based on cluster analysis is proposed and tested on a portfolio optimization problem. Extensive computational experiments were carried out to evaluate the performance of the proposed approach, both in terms of computational efficiency and efficacy. The analysis of the results shows that the clustering approach exhibits good performance also when compared with other reduction approaches.