Metal Organic Framework-235 (MOF-235) Modified Carbon Paste Electrode for Catechol Determination in Water

MOF-235 is presented as an orange powder, with crystals of the octahedral formation. It was already used as adsorbent to remove different compounds from water; however, no attempts have been published about the exploration of the MOF-235 application as electrochemical sensor for organic compounds yet. MOF-235 was synthetized and after that, it was characterized by SEM, XRD and FTIR. Graphite electrodes (GEs) were modified with different MOF-235 ratio (5 %, 7 %, 10 %, 12 % and 14 %) and these modified GEs were characterized by cyclic voltammetry (CV) measurements in order to determine the effect of MOF-235 concentration on the current response. Results indicated that, a significant improvement on the current response was attained at MOF-235(10 %)/GE respect to unmodified GE. This behavior is related to the pore structure and multiple active sites on the MOF surface. The performance of the MOF-235(10 %)/GE as electrochemical sensor for detecting catechol was assessed by differential pulse voltammetry (DPV). Catechol detection response of MOF-based sensor provided a detection limit of about 12.79 μmol L⁻¹ with a correlation coefficient (R²) of about 0.9928 ranging from 12 to 514 μmol L⁻¹. Finally, MOF-235(10 %)/GE was used to determine catechol in real water matrixes.     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

Bursting synchronization in networks with long-range coupling mediated by a diffusing chemical substance

Many networks of physical and biological interest are characterized by a long-range coupling mediated by a chemical which diffuses through a medium in which oscillators are embedded. We considered a one-dimensional model for this effect for which the diffusion is fast enough so as to be implemented through a coupling whose intensity decays exponentially with the lattice distance. In particular, we analyzed the bursting synchronization of neurons described by two timescales (spiking and bursting activity), and coupled through such a long-range interaction network. One of the advantages of the model is that one can pass from a local (Laplacian) type of coupling to a global (all-to-all) one by varying a single parameter in the interaction term. We characterized bursting synchronization using an order parameter which undergoes a transition as the coupling parameters are changed through a critical value. We also investigated the role of an external time-periodic signal on the bursting synchronization properties of the network. We show potential applications in the control of pathological rhythms in biological neural networks.     

Evaluation of Pesticide Contamination of Ground Water in Two Agricultural Areas of Portugal

In two Portuguese agricultural areas, "Beira Litoral" and "Ribatejo e Oeste", several pesticides regularly applied in vineyards, maize, potato, tomato for industry, apple, pear and rice were detected in ground water. Atrazine was the most frequently detected, being found in 70% of the total of 79 sites selected in the year 2000, followed by its metabolites desethylatrazine and desisopropylatrazine with frequencies of detection, respectively, of 56% and 48% and by simazine (37%), alachlor (25%), metolachlor (24%) and metribuzin (15%). Other pesticides and metabolites i.e. 3,4-dichloroaniline, dimethoate, f and g -endosulfan, lindane, molinate and prometryn were also detected but at lower occurrences. Pesticides were detected mainly in ground water wells used for irrigation purposes, although in some locations they were also found in water wells used for human consumption. In this study, it was also observed a seasonal variation of pesticide residues in ground water of shallow and deep wells.     

Coherent control in the presence of intrinsic decoherence: proton transfer in large molecular systems

An efficient semiclassical approach is developed and used to calculate the coherent-control map and time dependent decoherence measure for the excited-state proton transfer dynamics associated with the keto-enolic tautomerization reaction of 2-(2'-hydroxyphenyl)-oxazole. The method extends the usual bichromatic coherent-control scenario to simulate control at finite times after photoexcitation of the system. Extensive coherent control is demonstrated in a large molecule despite the ultrafast decoherence phenomena, providing results of broad theoretical and experimental interest.     

Electronic ferroelectricity in the falicov-kimball model

I show that a spontaneous electric polarization exists in the solution of the Falicov-Kimball model by mapping the strong coupling limit of this Hamiltonian into an xxz spin 1/2 model with a magnetic field. In this way, I determine the phase diagram of the strongly interacting model and show the existence of a transition to a mixed-valence regime containing two phases: an orbitally ordered state and a Bose-Einstein condensation of excitons with a built-in electric polarization.     

Rabi flopping in a two-level system with a time-dependent energy renormalization: intersubband transitions in quantum wells

We obtain pulse-driven Rabi oscillations guided by a generalization of the rotating-wave approximation to include, in the optical-Bloch equations, two-level systems with a time-varying transition energy. We achieve this by using chirped pulses with the central frequency given by the time-varying transition energy. Using this approach, we predict Rabi oscillations in intersubband transitions in a two-subband n-type modulation-doped quantum well by taking into account the time-dependent intersubband energy-gap renormalization due to depolarization-shift effects. We obtain Rabi oscillations for jpi (j=0,1,2, ) pulses in the presence of dephasing.