Quantitative Analysis of the Interactions of Metal Complexes and Amphiphilic Systems: Calorimetric, Spectroscopic and Theoretical Aspects

Metals and metal-based compounds have many implications in biological systems. They are involved in cellular functions, employed in the formation of metal-based drugs and present as pollutants in aqueous systems, with toxic effects for living organisms. Amphiphilic molecules also play important roles in the above bio-related fields as models of membranes, nanocarriers for drug delivery and bioremediating agents. Despite the interest in complex systems involving both metal species and surfactant aggregates, there is still insufficient knowledge regarding the quantitative aspects at the basis of their binding interactions, which are crucial for extensive comprehension of their behavior in solution. Only a few papers have reported quantitative analyses of the thermodynamic, kinetic, speciation and binding features of metal-based compounds and amphiphilic aggregates, and no literature review has yet addressed the quantitative study of these complexes. Here, we summarize and critically discuss the recent contributions to the quantitative investigation of the interactions of metal-based systems with assemblies made of amphiphilic molecules by calorimetric, spectrophotometric and computational techniques, emphasizing the unique picture and parameters that such an analytical approach may provide, to support a deep understanding and beneficial use of these systems for several applications

Asymptotic Entanglement Dynamics and Geometry of Quantum States

A given dynamics for a composite quantum system can exhibit several distinct properties for the asymptotic entanglement behavior, like entanglement sudden death, asymptotic death of entanglement, sudden birth of entanglement, etc. A classification of the possible situations was given in [M. O. Terra Cunha, {\emph{New J. Phys}} {\bf{9}}, 237 (2007)] but for some classes there were no known examples. In this work we give a better classification for the possibile relaxing dynamics at the light of the geometry of their set of asymptotic states and give explicit examples for all the classes. Although the classification is completely general, in the search of examples it is sufficient to use two qubits with dynamics given by differential equations in Lindblad form (some of them non-autonomous). We also investigate, in each case, the probabilities to find each possible behavior for random initial states.Comment: 9 pages, 2 figures; revised version accepted for publication in J. Phys. A: Math. Theo

Resonant effects in a SQUID qubit subjected to non adiabatic changes

By quickly modifying the shape of the effective potential of a double SQUID flux qubit from a single-well to a double-well condition, we experimentally observe an anomalous behavior, namely an alternance of resonance peaks, in the probability to find the qubit in a given flux state. The occurrence of Landau-Zener transitions as well as resonant tunneling between degenerate levels in the two wells may be invoked to partially justify the experimental results. A quantum simulation of the time evolution of the system indeed suggests that the observed anomalous behavior can be imputable to quantum coherence effects. The interplay among all these mechanisms has a practical implication for quantum computing purposes, giving a direct measurement of the limits on the sweeping rates possible for a correct manipulation of the qubit state by means of fast flux pulses, avoiding transitions to non-computational states.Comment: 6 pages and 6 figures. The paper, as it is, has been accepted for publication on PRB on March 201

Dissipation and entanglement dynamics for two interacting qubits coupled to independent reservoirs

We derive the master equation of a system of two coupled qubits by taking into account their interaction with two independent bosonic baths. Important features of the dynamics are brought to light, such as the structure of the stationary state at general temperatures and the behaviour of the entanglement at zero temperature, showing the phenomena of sudden death and sudden birth as well as the presence of stationary entanglement for long times. The model here presented is quite versatile and can be of interest in the study of both Josephson junction architectures and cavity-QED.Comment: 14 pages, 3 figures, submitted to Journal of Physics A: Mathematical and Theoretica

New Biopsy Forceps for Gastrointestinal Endoscopy

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Antioxidant and UV-Blocking Functionalized Poly(Butylene Succinate) Films

The introduction of a limited number of functional groups on poly(butylene succinate) (PBS) chains by covalent bonding can impart new properties to the polymer without modifying its thermal and mechanical properties. In pursuit of a viable approach to obtain light- and heat-stabilized PBS samples, the nitroxide radical coupling (NRC) reaction between PBS macroradicals and the 3,5-di-tert-butyl-4-hydroxybenzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (BHB-TEMPO), a functionalizing agent bearing a sterically-hindered antioxidant phenol moiety, is here proposed. The reaction was initiated by peroxide and carried out in solution and in a melt. The functionalized materials were characterized by UV-visible spectroscopy (UV-Vis), proton nuclear magnetic resonance (1H-NMR), and size exclusion chromatography (SEC) analysis to gain structural information and by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) to investigate the thermal properties. In addition, films of the samples were subjected to thermal and photo-oxidative aging to assess their resistance to degradative processes. Finally, the PBS film with the highest degree of functionalization showed the ability to protect β-carotene, a molecule found in food and drugs and that is very sensitive to UV light, from degradation. This result suggests the use of this material (either alone or blended with other biopolyesters) for biodegradable and compostable active packaging

Assessment, pharmacological therapy and rehabilitation management of musculoskeletal pain in children with mucopolysaccharidoses: a scoping review

Pain of musculoskeletal origin is very common in young patients affected by Mucopolysaccharidoses. This scoping review evaluates the evidence for assessment, pharmacological treatment and rehabilitation management for musculoskeletal pain of the latter

Lanthanide Identity Governs Guest-Induced Dimerization in LnIII[15-MCCuIIN(L-pheHA)-5])3+ Metallacrowns

Series of lanthanide-containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (LnIII[15-MC (Formula presented.) N(L-pheHA)-5])3+ metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host-guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host-guest-host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides)