No abstract

Falcipain-2 and falcipain-3 are papain-family cysteine proteases of the malaria parasite Plasmodium falciparum that are responsible for host hemoglobin hydrolysis to provide amino acids for parasite protein synthesis. Different heteroarylnitrile derivatives were studied as potential falcipain inhibitors and therefore potential antiparasitic lead compounds, with the 5-substituted-2-cyanopyrimidine chemical class emerging as the most potent and promising lead series. Through a sequential lead optimization process considering the different positions present in the initial scaffold, nanomolar and subnanomolar inhibitors at falcipains 2 and 3 were identified, with activity against cultured parasites in the micromolar range. Introduction of protonable amines within lead molecules led to marked improvements of up to 1000 times in activity against cultured parasites without noteworthy alterations in other SAR tendencies. Optimized compounds presented enzymatic activities in the picomolar to low nanomolar range and antiparasitic activities in the low nanomolar range.

A nonlinear optical effect is shown to occur in gallium and indium selenides at photon energies of the order of 1.5 eV. It corresponds to transitions from a lower-energy valence band to the uppermost one when a nonequilibrium degenerate hole gas is created in the latter by a laser pulse. This inter-valence-band transition is allowed by crystal symmetry. Its oscillator strength is estimated through the f-sum rule and turns out to be about two orders of magnitude higher than that of the fundamental transition. The intensity of this effect is stronger when the pump pulse photon energy is close to that of the inter-valence-band transition; a condition that can be fulfilled only in indium selenide. The transient behavior of the sample transmittance is shown to be controlled by the balance between absorption and stimulated emission, which depends on the hole quasi-Fermi level and the gap renormalization due to Coulomb interaction in the electron-hole gas generated by the pump.

In this paper we review some recent results on the electronic structure of III − VI layered semiconductors and its dependence under pressure, stressing the specific features that differentiate their behaviour from that of tetrahedrally coordinated semiconductors. We will focus on several unexpected results that have led to changes in the image that was currently accepted a few years ago. Intralayer bond angles change under pressure and the layer "thickness" remains virtually constant or increases. As a consequence, models based in intra-and inter-layer deformation potentials fail in explaining the low pressure nonlinearity of the band gap. Numerical-atomic-orbital/density-functional-theory electronic structure calculations allow for an interpretation of the evolution of the absorption edge under pressure. In particular, they show how the structure of the non-degenerated valence band maximum in InSe becomes more complex under pressure leading to a non-conventional direct-to-indirect crossover. The valence band maximum in InSe above 4 GPa exhibits a quite singular feature: a "ring-shaped" constant energy surface and, consequently, a density of states depending on energy as in 2D electronic systems.

Refractive index and absorption coefficient of GaTe for light polarized in the optical axis directions in the layer plane are determined from transmission measurements. The refractive index is determined in the wavelength range from 0.7 to 25 μm and the absorption coefficient in the range of energies from 1.6 to 2 eV at room temperature and at 30 K. The optical constants are found to be anisotropic in the layer plane. The refractive index dispersion is interpreted through a Phillips‐Van Vechten model and the Penn gaps for each direction are found to be EPg(⊥b) = 3.37 eV and EPg(‖b) = 3.58 eV. In the long‐wavelength region a polar phonon contribution is also taken into account. The absorption edge is found to be very slightly anisotropic, which is shown to be coherent with the Se pz‐like character of the valence band.