A Selective,Nontoxic, OFF–ON Fluorescent Molecular Sensor Based on 8‐Hydroxyquinoline for Probing Cd2+ in Living Cells

In spite of the fact that cadmium(II) has been recognized as a highly toxic element and that excessive exposure to this metal ion has been reported to have many adverse effects on human health, very few selective and specific fluorescent probes are available for imaging Cd²⁺ in living cells. Herein, we report the spectroscopic and photochemical characterization of 5‐(5‐chloro‐8‐hydroxyquinolinylmethyl)‐2,8‐dithia‐5‐aza‐2,6‐pyridinophane ( L ) as a fluorescent sensor for the selective imaging of Cd²⁺ in living cells. In particular, the response of L to Cd²⁺ was first assessed in aqueous solutions, sodium dodecyl sulfate micelles, and liposomes, and subsequently in living cells by fluorescence microscopy techniques. Cytofluorimetric analyses of leukemic HL‐60 cells loaded with L also allowed evaluation of the toxicity of the probe and the selective analysis of its intracellular fluorescence in the presence of Cd²⁺. Furthermore, the 1:1 complex species [Cd( L )H₂O]²⁺ responsible for the OFF–ON chelation enhancement of fluorescence (CHEF) effect on L was structurally characterized; time‐dependent DFT calculations allowed the prediction of theoretical excitations, which were comparable with the experimental ones.     

Multifunctional hybrid materials based on transparent poly(methyl methacrylate) reinforced by lanthanoid hydroxo clusters

Three pentanuclear lanthanoid hydroxo clusters of composition [Ln(OH)(5)(abzm)(10)], where Ln = Eu, Tb, Ho and abzm = di(4-allyloxy)benzoylmethanide, have been prepared. The structures have been characterised by means of IR, Raman, elemental analyses and X-ray diffraction, showing a pyramidal square-based cluster core. The clusters (Tb and Ho) exhibit Curie-Weiss Law behaviour, displaying antiferromagnetic ordering at low temperatures. The emission properties of the Eu cluster demonstrate the abzm(-) ligand is an efficient antenna (λ(ex) = 420 nm) only for the sensitisation of Eu luminescence in the visible range, via energy transfer to the (5)D(0) state of the trivalent metal. The clusters have been reacted in the presence of methyl methacrylate and azobisisobutyronitrile to prepare reinforced polymers via radical polymerisation. The obtained materials exhibit swelling upon immersion into organic solvents up to ≈ 110% of their original size, in agreement with the presence of cluster-crosslinked polymeric chains. Also, no loss of transparency was observed in the preparation of the materials. The characteristic red emission of the Eu cluster in also retained in the polymeric material.     

Young Integrals and SPDEs

In this note, we study the non-linear evolution problem $dY_t = -A Y_t dt + B(Y_t) dX_t,$ where $XIn this note, we study the non-linear evolution problem where is a -H?lder continuous function of the time parameter, with values in a distribution space, and the generator of an analytical semigroup. Then, we will give some sharp conditions on in order to solve the above equation in a function space, first in the linear case (for any value of in ), and then when satisfies some Lipschitz type conditions (for ). The solution of the evolution problem will be understood in the mild sense, and the integrals involved in that definition will be of Young type.     

A Numerical Approach to Copolymers at Selective Interfaces

We consider a model of a random copolymer at a selective interface which undergoes a localization/delocalization transition. In spite of the several rigorous results available for this model, the theoretical characterization of the phase transition has remained elusive and there is still no agreement about several important issues, for example the behavior of the polymer near the phase transition line. From a rigorous viewpoint non coinciding upper and lower bounds on the critical line are known. In this paper we combine numerical computations with rigorous arguments to get to a better understanding of the phase diagram. Our main results include:

Bayesian estimation and prediction for the transformed Wiener degradation process

This paper proposes some Bayesian inferential procedures for the transformed Wiener (TW) process, a new degradation process that has been recently suggested in the literature to describe degradation phenomena where degradation increments are not necessarily positive and depend stochastically on the current degradation level. These procedures have been expressly conceived to allow one incorporating into the inferential process the type of prior information, on meaningful physical characteristics of the observed degradation process, that is generally available in practical settings. Several different prior distributions are proposed, each of them reflecting a specific degree of knowledge on the observed phenomenon. Simple strategies for eliciting the prior hyper‐parameters from the available prior information are provided. Estimates of the TW process parameters and some functions thereof are retrieved by adopting a Monte Carlo Markov Chain technique. Procedures that allow predicting the degradation increment, the useful life of a new unit, and the remaining useful life of a used unit are also provided. Finally, an application is developed on the basis of a set of real degradation measurements of some infrared light‐emitting diodes, widely used in communication systems. The obtained results demonstrate the feasibility of the proposed Bayesian approach and the flexibility of the TW process.     

On the number of Waring decompositions for a generic polynomial vector

We prove that a general polynomial vector $(f_1,f_2,f_3)$ in three homogeneous variables of degrees $(3,3,4)$ has a unique Waring decomposition of rank 7. This is the first new case we are aware of, and likely the last one, after five examples known since the 19th century and the binary case. We prove that there are no identifiable cases among pairs $(f_1,f_2)$ in three homogeneous variables of degree $(a,a+1)$, unless $a=2$, and we give a lower bound on the number of decompositions. The new example was discovered with Numerical Algebraic Geometry, while its proof needs Nonabelian Apolarity.     

Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties

The tetrabutylammonium (TBA⁺) salts of square‐planar monoanionic gold complexes of the unsymmetrically substituted Ar,H‐edt^2? 1,2‐dithiolene ligands (Ar,H‐edt^2?=arylethylene‐1,2‐dithiolato; Ar=phenyl ( 1 ^?), 2‐naphthyl ( 2 ^?), and 1‐pyrenyl ( 3 ^?)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species ( 1 , 2 , and 3 , respectively) were obtained in CH₂Cl₂ solution at room temperature by diiodine oxidation. The single‐crystal X‐ray diffraction structural data collected for (TBA⁺)( 2 ^?), supported by DFT theoretical calculations, are consistent with the ene‐1,2‐dithiolate form of the ligand and the Au^III oxidation state. All complexes feature intense near‐IR absorptions (at about 1.5 μm) in their neutral states and Vis‐emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3 ^?/ 3 couple. The spectroscopic and electrochemical features of 1 ^x? and 2 ^x? (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time‐dependent (TD) DFT calculations.     

In situ and frontal polymerization for the consolidation of porous stones: a unilateral NMR and magnetic resonance imaging study

Consolidation treatment of porous materials was performed by in situ and frontal polymerization of acrylic monomers inside a porous stone. To study the penetration of the polymer inside the stone and its consolidating effects we used water as a contrast agent, detecting its penetration using unilateral NMR and magnetic resonance imaging. All data obtained on differently treated stones were compared with corresponding ones obtained analyzing both untreated stones and stones simply painted with a well-known polymeric protective agent. In situ polymerization of acrylic monomers inside porous stones has been demonstrated to be an extremely powerful consolidating method, whereas thermally initiated frontal polymerization seems less efficient. In both cases the optimal choice of monomers is still open and requires further study. Our data indicate that unilateral NMR represents an inexpensive and simple technique for the non-invasive observation of the water uptake and of the effect of consolidation procedures in porous materials.     

Complexity-entropy causality plane: A useful approach to quantify the stock market inefficiency

The complexity-entropy causality plane has been recently introduced as a powerful tool for discriminating Gaussian from non-Gaussian process and different degrees of correlations [O.A. Rosso, H.A. Larrondo, M.T. Martín, A. Plastino, M.A. Fuentes, Distinguishing noise from chaos, Phys. Rev. Lett. 99 (2007) 154102]. We propose to use this representation space to distinguish the stage of stock market development. Our empirical results demonstrate that this statistical physics approach is useful, allowing a more refined classification of stock market dynamics.