Directed ortho-lithiation of unprotected diphenylphosphinic acids

Directed ortho lithiation of diphenylphosphinic acid and subsequent electrophilic trapping provides mono ortho-functionalized derivatives including enantiopure γ-aminophosphinic acids in moderate yields. Copper catalyzed coupling of the ortho anion leads to biphenyl-2,2′-diylbis(phenylphosphinic acid), a phosphorus analogue of biphenyl-2,2′-dicarboxylic acid. Preliminary studies of the metal-binding abilities of this O,O-chelating ligand towards a series of metal cations are included.     

Multiple Keys for a Single Lock: The Unusual Structural Plasticity of the Nucleotidyltransferase (4′)/Kanamycin Complex

The most common mode of bacterial resistance to aminoglycoside antibiotics is the enzyme‐catalysed chemical modification of the drug. Over the last two decades, significant efforts in medicinal chemistry have been focused on the design of non‐ inactivable antibiotics. Unfortunately, this strategy has met with limited success on account of the remarkably wide substrate specificity of aminoglycoside‐modifying enzymes. To understand the mechanisms behind substrate promiscuity, we have performed a comprehensive experimental and theoretical analysis of the molecular‐recognition processes that lead to antibiotic inactivation by Staphylococcus aureus nucleotidyltransferase 4′(ANT(4′)), a clinically relevant protein. According to our results, the ability of this enzyme to inactivate structurally diverse polycationic molecules relies on three specific features of the catalytic region. First, the dominant role of electrostatics in aminoglycoside recognition, in combination with the significant extension of the enzyme anionic regions, confers to the protein/antibiotic complex a highly dynamic character. The motion deduced for the bound antibiotic seem to be essential for the enzyme action and probably provide a mechanism to explore alternative drug inactivation modes. Second, the nucleotide recognition is exclusively mediated by the inorganic fragment. In fact, even inorganic triphosphate can be employed as a substrate. Third, ANT(4′) seems to be equipped with a duplicated basic catalyst that is able to promote drug inactivation through different reactive geometries. This particular combination of features explains the enzyme versatility and renders the design of non‐inactivable derivatives a challenging task.     

Onset of Chiral Adenine Surface Growth

The structure and stability of adenine crystals and thin layers has been studied by using scanning tunneling microscopy, X‐ray diffraction, and density functional theory calculations. We have found that adenine crystals can be grown in two phases that are energetically quasi‐degenerate, the structure of which can be described as a pile‐up of 2D adenine planes. In each plane, the structure can be described as an aggregation of adenine dimers. Under certain conditions, kinetic effects can favor the growth of the less stable phase. These results have been used to understand the growth of adenine thin films on gold under ultra‐high vacuum conditions. We have found that the grown phase corresponds to the α‐phase, which is composed of stacked prochiral planes. In this way, the adenine nanocrystals exhibit a surface that is enantiopure. These results could open new insight into the applications of adenine in biological, medical, and enantioselective or pharmaceutical fields.     

Radioanalytical assessment of environmental contamination around non-remediated uranium mining legacy site and radium mobility

During the past century extensive uranium mining took place in Portugal for radium and uranium production. One such uranium mine was the Boco Mine, in operation during the 1960s and 70s. Mining waste and open pits were left uncovered since mine closure. During the nineties a quarry for sand extraction was operated in the same site and water from a local stream was extensively used in sand sieving. Downstream the mine area, agriculture soil is used for cattle grazing. Water from the stream, water wells, soil, pasture and sheep meat were now analyzed for radionuclides of uranium natural series. The U-series radionuclide ²²⁶Ra was generally the highest in concentrations especially in soil, pasture, and in internal organs of sheep. ²²⁶Ra concentrations were 1,093 ± 96 Bq/kg (dry weight, dw) in soil, 43 ± 3 Bq/kg (dw) in pasture, and 193 ± 84 mBq/kg (wet weight, ww) in muscle tissue of sheep. Other sheep internal organs displayed much higher ²²⁶Ra concentrations, such as the brain and kidneys with 1,850 ± 613 mBq/kg (ww) and 6,043 ± 6,023 mBq/kg (ww), respectively. Results of analyses of tissue samples from sheep grown in a comparison area were 2 to 16 times lower, depending on the organ. Absorbed radiation doses for internal organs were computed and may exceed 5.2 mGy/y in the case of kidneys, near three times higher than in animals from the reference area, but below the threshold for biological effects. Radionuclide transfer in the terrestrial food chain and radiation exposure of the human population is discussed.     

Pressure-induced two-color photoluminescence in MnF(2) at room temperature

A novel two-color photoluminescence (PL) is found in MnF(2) at room temperature under high pressure. Contrary to low-temperature PL, PL at room temperature is unusual in transition-metal concentrated materials like MnF(2), since the deexcitation process at room temperature is fully governed by energy transfer to nonradiative centers. We show that room-temperature PL in MnF(2) originates from two distinct Mn(2+) emissions in the high-pressure cotunnite phase. The electronic structure and the excited-state dynamics are investigated by time-resolved emission and excitation spectroscopy at high pressure.