Beyond exciton theory: a time-dependent DFT and Franck-Condon study of perylene diimide and its chromophoric dimer

The diimide perylene motif exhibits a dramatic intensity reversal between the 0 --> 0 and 0 --> 1 vibronic bands upon pi-pi stacking; this distinct spectral property has previously been used to measure folding dynamics in covalently bound oligomers and synthetic biological hybrid foldamers. It is also used as a tool to assess organization of the pi-stacking, indicating the presence of H- or J-aggregation. The zeroth-order exciton model, often used to describe the optical properties of chromophoric aggregates, is solely a transition dipole coupling scheme, which ignores the explicit electronic structure of the system as well as vibrational coupling to the electronic transition. We have therefore examined the optical properties of gas-phase perylene tetracarboxylic diimide (PTCDI) and its chromophoric dimer as a function of conformation to relate the excited-state distributions predicted by exciton theory with that of time-dependent density functional theory (TDDFT). Using ground- and excited-state geometries, the Franck-Condon (FC) factors for the lowest energy molecular nature electronic transition have been calculated and the origin of the intensity reversal of 0 --> 0 and 0 --> 1 vibronic bands has been proposed.     

Ketene dithioacetal derivatives of 1-phenyl-3,5-dioxopyrazolidine. Synthesis and NMR characterization

1-Phenyl-3,5-dioxopyrazolidine 1 reacts with carbon disufide and alkyl halides in presence of excess of sodium acetate in dimethylformamide to afford the ketene dithioacetals 3a-h . The ¹³C chemical shift assignments of these compounds were made on the basis of two-dimensional nmr studies performed on the N-methylketene dithioacetal derivative 4.     

Cancer Initiation,Progression and Resistance: Are Phytocannabinoids from Cannabis sativa L. Promising Compounds?

Cannabis sativa L. is a source of over 150 active compounds known as phytocannabinoids that are receiving renewed interest due to their diverse pharmacologic activities. Indeed, phytocannabinoids mimic the endogenous bioactive endocannabinoids effects through activation of CB1 and CB2 receptors widely described in the central nervous system and peripheral tissues. All phytocannabinoids have been studied for their protective actions towards different biological mechanisms, including inflammation, immune response, oxidative stress that, altogether, result in an inhibitory activity against the carcinogenesis. The role of the endocannabinoid system is not yet completely clear in cancer, but several studies indicate that cannabinoid receptors and endogenous ligands are overexpressed in different tumor tissues. Recently, in vitro and in vivo evidence support the effectiveness of phytocannabinoids against various cancer types, in terms of proliferation, metastasis, and angiogenesis, actions partially due to their ability to regulate signaling pathways critical for cell growth and survival. The aim of this review was to report the current knowledge about the action of phytocannabinoids from Cannabis sativa L. against cancer initiation and progression with a specific regard to brain, breast, colorectal, and lung cancer as well as their possible use in the therapies. We will also report the known molecular mechanisms responsible for such positive effects. Finally, we will describe the actual therapeutic options for Cannabis sativa L. and the ongoing clinical trials.     

Unexpected inverse correlations and cooperativity in ion-pair phase transfer

Liquid/liquid extraction is one of the most widely used separation and purification methods, where a forefront of research is the study of transport mechanisms for solute partitioning and the relationships that these have to solution structure at the phase boundary. To date, organized surface features that include protrusions, water-fingers, and molecular hinges have been reported. Many of these equilibrium studies have focused upon small-molecule transport – yet the extent to which the complexity of the solute, and the competition between different solutes, influence transport mechanisms have not been explored. Here we report molecular dynamics simulations that demonstrate that a metal salt (LiNO₃) can be transported via a protrusion mechanism that is remarkably similar to that reported for H₂O by tri-butyl phosphate (TBP), a process that involves dimeric assemblies. Yet the LiNO₃ out-competes H₂O for a bridging position between the extracting TBP dimer, which in-turn changes the preferred transport pathway of H₂O. Examining the electrolyte concentration dependence on ion-pair transport unexpectedly reveals an inverse correlation with the extracting surfactant concentration. As [LiNO₃] increases, surface adsorbed TBP becomes a limiting reactant in correlation with an increased negative surface charge induced by excess interfacial NO₃⁻, however the rate of transport is enhanced. Within the highly dynamic interfacial environment, we hypothesize that this unique cooperative effect may be due to perturbed surface organization that either decreases the energy of formation of transporting protrusion motifs or makes it easier for these self-assembled species to disengage from the surface.

A forefront of research in separations science (specifically liquid–liquid extraction) is the study of transport mechanisms for solute partitioning, and the relationships that these have to solution structure at the phase boundary.     

Research about transmission of the mechanical vibration done by machine-tools on the group of bones shoulder-neck-head

Different researches have shown that long–term exposure to whole–body vibration can induce different injuries like back pain, injuries of the different part of the body, disturbing the physical and intellectual activities. The resulted diseases could be occasional or could be for ever. Bearing in mind that vibration is applied on the hand or feet, the health rick can be assessed if the forces transmitted in the shoulder during vibration are known. To estimate the forces a biomechanical model has been developed in which the shoulder, neck and head are represented by rigid bodies. The bodies are connected by visco–elastic joint elements. The applied forces are resulted from experimental measurements. To assess the health risk the forces must be divised in two components, an ascendant one and a descendent one. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectrophotometric determination of cobalt with mucic acid

A procedure for the spectrophotometric determination of cobalt with mucic acid is proposed. The absorption spectra, pH, amount of reagent, temperature, and time are studied. Beer's law is obeyed in the range 2.3 and 28.3 μg Co(III)/ml, the Ringbom optimal interval falls between about 9.5 and 25.0 μg Co(III)/ml. The molar absorptivity is 1.4 × 10³ liter/ mol · cm. The stoichiometry of the reaction takes place in the metal-to-ligand ratio of 1:1. The stability constants of the complex are calculated. At the same time, the interferences produced by the commonest ions are studied. The method has been successfully applied to the determination of cobalt in vitamin B₁₂.     

Using micelles for a new approach to fluorescent sensors for metal cations

A new approach based on self-assembly inside micelles has been individuated to prepare a system behaving as a water-operating selective fluorescent sensor for Cu2+ and Ni2+.     

Bicyclic units of

We prove that the group generated by the bicyclic units of has torsion for . This answers a question of Sehgal (1993).

     

X-ray absorption signatures of hydrogen-bond structure in water–alcohol solutions

Despite fundamental importance, the experimental characterization of the hydrogen bond network, particularly in multicomponent protic solutions, remains a challenge. Although recent work has experimentally validated that the oxygen K-edge X-ray absorption spectra is sensitive to local hydrogen bond patterns in pure water and aqueous alcohol solutions, the generality of this observation is unknown—as is the sensitivity to the electronic structure of the alcohol cosolvent. In this work, we investigate the electronic structure of water solvated alcohol model geometries using energy specific time-dependent density functional theory to calculate oxygen K-edge X-ray excitations. We find that the geometry of dangling hydrogen bonds in pure water is the main contributor to the pre-edge feature seen in the X-ray absorption spectra, agreeing with previous experimental and theoretical work. We then extend this result to solvated alcohol systems and observe a similar phenomenon, yet importantly, the increase of electron donation from alkyl chains to the alcohol OH group directly correlates to the strength of the core excitation on the dangling hydrogen bond model geometry. This trend arises from a stronger transition dipole moment due to electron localization on the OH group.     

“Clinic laboratory accreditation with ISO 15189:2007 in the European Union”: report of the VI European symposium on clinical laboratory and in vitro diagnostic industry

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