Irreversibility, entropy and incomplete information

The open system has been proved to be a system with perfect accessibility represented as a probability space in which is defined a PA-measure. But, the PA-measure is not yet known; consequently, it is difficult to develop the statistical thermodynamics for an irreversible system. Here its integral expression is obtained in order to its use in the statistical thermodynamic analysis of the complex and irreversible systems.     

Advantages of using multiple-echo image combination and asymmetric triangular phase masking in magnetic resonance venography at 3 T

The present work explores the possibility of localizing veins with magnetic resonance venography using susceptibility weighted imaging. It also seeks new approaches, directed by the spatial specificity of activated brain regions, that have sufficient precision for practical use in functional MRI studies. A 3D flow compensated multiple gradient echo sequence, featuring optimized T2* weighting within a reasonable time of acquisition (11 min) and a small voxel size (0.5x0.5x1 mm3), was used to acquire MR images at 3 T. Post-processing consisted of homodyne filtering, linear phase scaling and magnitude masking prior to minimum intensity projection (mIP). The multiple echo approach provided a satisfactory (48+/-7%) increase in signal-to-noise ratio with respect to conventional methods. Specific features of the blood oxygenation level-dependent phase effect were simulated and used for designing and exploring different phase masking methods in relation to vessel morphology and MRI voxel geometry. As with simulations, the best results were obtained with an asymmetric triangular phase masking, featuring an improved venographic contrast without any increase in the full-width at half-maximum. The multiple echo approach provided satisfactory vessel localization capacity by using asymmetric triangular phase masking and a 4-mm-thick mIP. The venographic contrast obtained enabled the detection of vessels with diameter down to approximately 500 microm, suggesting the applicability of the proposed method as an additional technique in fMRI studies.     

Nucleon aPF2 Superfluid Pairing Gap in Asymmetry Nuclear Matter

The 3 P F2 superfluidity of neutron and proton is investigated in isospin-asymmetric nuclear matter within the Brueckner-Hartree-Fock approach and the BCS theory by adopting the Argonne V14 and the Argonne V18 nucleonnucleon interactions. We find that pairing gaps in the 3PF2 channel predicted by adopting the AV14 interaction are much larger than those by the AV18 interaction. As the isospin-asymmetry increases, the neutron 3 pF2 superfluidity is found to increase rapidly, whereas the proton one turns out to decrease and may even vanish at high enough asymmetries. As a consequence, the neutron 3pF2 superfluidity is much stronger than the proton one at high asymmetries and it predominates over the proton one in dense neutron-rich matter.     

Self-assembled fluorescent chemosensors

Self-assembling and self-organizing methodologies are powerful tools for the "bottom-up" approach for the realization of complex structure with functional properties. Recently, this concept has been extended to the design of fluorescent chemosensors providing new exciting potentialities for the development of innovative sensing systems. This Concept Article deals mainly with this new approach and discusses its evolution, applications, and limitations.     

A kinematical approach to conformal cosmology

We present an alternative cosmology based on conformal gravity, as originally introduced by H. Weyl and recently revisited by P. Mannheim and D. Kazanas. Unlike past similar attempts our approach is a purely kinematical application of the conformal symmetry to the Universe, through a critical reanalysis of fundamental astrophysical observations, such as the cosmological redshift and others. As a result of this novel approach we obtain a closed-form expression for the cosmic scale factor R(t) and a revised interpretation of the space–time coordinates usually employed in cosmology. New fundamental cosmological parameters are introduced and evaluated. This emerging new cosmology does not seem to possess any of the controversial features of the current standard model, such as the presence of dark matter, dark energy or of a cosmological constant, the existence of the horizon problem or of an inflationary phase. Comparing our results with current conformal cosmologies in the literature, we note that our kinematic cosmology is equivalent to conformal gravity with a cosmological constant at late (or early) cosmological times. The cosmic scale factor and the evolution of the Universe are described in terms of several dimensionless quantitites, among which a new cosmological variable δ emerges as a natural cosmic time. The mathematical connections between all these quantities are described in details and a relationship is established with the original kinematic cosmology by L. Infeld and A. Schild. The mathematical foundations of our kinematical conformal cosmology will need to be checked against current astrophysical experimental data, before this new model can become a viable alternative to the standard theory.     

Direct Cu-mediated aromatic 18F-labeling of highly reactive tetrazines for pretargeted bioorthogonal PET imaging

Pretargeted imaging can be used to visualize and quantify slow-accumulating targeting vectors with short-lived radionuclides such as fluorine-18 – the most popular clinically applied Positron Emission Tomography (PET) radionuclide. Pretargeting results in higher target-to-background ratios compared to conventional imaging approaches using long-lived radionuclides. Currently, the tetrazine ligation is the most popular bioorthogonal reaction for pretargeted imaging, but a direct ¹⁸F-labeling strategy for highly reactive tetrazines, which would be highly beneficial if not essential for clinical translation, has thus far not been reported. In this work, a simple, scalable and reliable direct ¹⁸F-labeling procedure has been developed. We initially studied the applicability of different leaving groups and labeling methods to develop this procedure. The copper-mediated ¹⁸F-labeling exploiting stannane precursors showed the most promising results. This approach was then successfully applied to a set of tetrazines, including highly reactive H-tetrazines, suitable for pretargeted PET imaging. The labeling succeeded in radiochemical yields (RCYs) of up to approx. 25%. The new procedure was then applied to develop a pretargeting tetrazine-based imaging agent. The tracer was synthesized in a satisfactory RCY of ca. 10%, with a molar activity of 134 ± 22 GBq μmol⁻¹ and a radiochemical purity of >99%. Further evaluation showed that the tracer displayed favorable characteristics (target-to-background ratios and clearance) that may qualify it for future clinical translation.

A simple, scalable and reliable direct ¹⁸F-labeling procedure has been developed and applied to obtain a pretargeting tetrazine-based imaging agent with favorable in vivo characteristics.     

Efficient and accurate modeling of electron photoemission in nanostructures with TDDFT

We derive and extend the time-dependent surface-flux method introduced in [L. Tao, A. Scrinzi, New J. Phys. 14, 013021 (2012)] within a time-dependent density-functional theory (TDDFT) formalism and use it to calculate photoelectron spectra and angular distributions of atoms and molecules when excited by laser pulses. We present other, existing computational TDDFT methods that are suitable for the calculation of electron emission in compact spatial regions, and compare their results. We illustrate the performance of the new method by simulating strong-field ionization of C₆₀ fullerene and discuss final state effects in the orbital reconstruction of planar organic molecules.     

Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands

A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (PhthalaPhos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2-acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1-yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3-phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect.