Semi‐heterogeneous Dual Nickel/Photocatalysis using Carbon Nitrides: Esterification of Carboxylic Acids with Aryl Halides

Cross‐coupling reactions mediated by dual nickel/photocatalysis are synthetically attractive but rely mainly on expensive, non‐recyclable noble‐metal complexes as photocatalysts. Heterogeneous semiconductors, which are commonly used for artificial photosynthesis and wastewater treatment, are a sustainable alternative. Graphitic carbon nitrides, a class of metal‐free polymers that can be easily prepared from bulk chemicals, are heterogeneous semiconductors with high potential for photocatalytic organic transformations. Here, we demonstrate that graphitic carbon nitrides in combination with nickel catalysis can induce selective C?O cross‐couplings of carboxylic acids with aryl halides, yielding the respective aryl esters in excellent yield and selectivity. The heterogeneous organic photocatalyst exhibits a broad substrate scope, is able to harvest green light, and can be recycled multiple times. In situ FTIR was used to track the reaction progress to study this transformation at different irradiation wavelengths and reaction scales.     

Holographic dark energy interacting with dark matter in a closed Universe

A cosmological model of an holographic dark energy interacting with dark matter throughout a decaying term of the form Q=3(λ₁ρDE+λ₂ρm)H$Q=3({\lambda }_1{\rho }_{\mathrm{DE}}+{\lambda }_2{\rho }_m)H$ is investigated. General constraint on the parameters of the model are found when accelerated expansion is imposed and we found a phantom scenario, without any reference to a specific equation of state for the dark energy. The behavior of equation of state for dark energy is also discussed.     

Influence of fixed electric charges on potential profile across the squid axon membrane

The potential profile for a model of squid axon membrane has been determined for two physiological states: resting and action states. The non-linear Poisson-Boltzmann equation has been solved by considering the volumetric charge densities due to charges dissolved in an electrolytic solution and fixed on both glycocalyx and cytoplasmatic proteins. Results showing the features of the potential profile along the outer electrolytic region are similar for both resting and action states. However, the potential fall along glycocalyx at action state is lower than at resting. A small variation in the Na⁺ concentration drastically affects the surface membrane potentials and vice versa. We conclude that effects on the potential profile due to surface lipidic bilayer charge and contiguous electric double layers are more relevant than those provoked by fixed charges distributed along the cell cytoplasm.     

DCOOD optically pumped by a 13CO2 laser: new terahertz laser lines

In this work we report on new optically pumped THz laser lines from deuterated formic acid (DCOOD). An isotopic ¹³CO₂ laser was used for the first time as a pump source for this molecule, and a Fabry–Perot cavity was used as a THz laser resonator. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines. We could observe six new laser lines in the range from 303.8 μm (0.987 THz) to 725.1 μm (0.413 THz). The lines were characterized according to wavelength, relative polarization, relative intensity, and optimum working pressure. The transferred lamb-dip technique was used to measure the frequency absorption transition for both of these laser lines. Furthermore, we also present a catalogue of all THz laser lines generated from DCOOD.     

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.     

Compositional and electrical properties of Cr,Nb, Cr/Nb,CrNbN, and CrN/NbN multilayers grown using the d.c. magnetron sputtering technique

Cr, Nb, Cr/Nb, CrN_x, NbN_x, CrNbN, and (CrN/NbN)_n structures were produced on Si and glass substrates, using the d.c. magnetron sputtering technique. Compositional analysis, based on binding energies of Cr, Nb, and N, was carried out by means of X-ray photoelectron spectroscopy (XPS). Through Auger electron spectroscopy (AES), depth profiles were obtained, allowing to demonstrate the multilayers production. Surface morphological characteristics, as roughness and grain size, were evaluated by atomic force microscopy (AFM), revealing very smooth surfaces, that is a consequence of the deposition parameters used in the synthetization experiments. Finally, for different configurations, conductivity measurements were carried out, revealing the influence of nitrogen content and temperature on electron transport. It was found that substoichiometric nitrides (CrN_0.35 and NbN_0.12) exhibited the highest conductivity, because the nitrogen atoms act as donor of electrons.     

Radioactivity characterization of 125I brachytherapy seeds used in prostate cancer treatment

Journal of Radioanalytical and Nuclear Chemistry - A procedure for characterizing the activity amount of 125I seed was developed in order to establish a secondary standard activity measurement...