A designed phenylalanyl-tRNA synthetase variant allows efficient in vivo incorporation of aryl ketone functionality into proteins

Incorporation of non-natural amino acids into proteins in vivo expands the scope of protein synthesis and design. p-Acetylphenylalanine was incorporated into recombinant dihydrofolate reductase (DHFR) in Escherichia coli via a computationally designed mutant form of the phenylalanyl-tRNA synthetase of the host. DHFR outfitted with ketone functionality can be chemoselectively ligated with hydrazide reagents under mild conditions.     

A new abietane and two dimeric abietane diterpenes from the black heartwood of Cryptomeria japonica

Three new diterpenes, sugikurojins A-C (1-3) were isolated from the black heartwood of Cryptomeria japonica. The structure of sugikurojin A was deduced to be 19-hydroxy-6,7-dehydroferruginol on the basis of extensive NMR experiments. Sugikurojin B was a dimer of 6,7-dihydroxyferruginol and 6,7-dehydroferruginol with a 6-O-11' linkage. Sugikurojin C was a dimeric ferruginol with 6-O-7' and 7-O-6' linkages. Also obtained in this investigation were the known compounds formosaninol (4), 15 sesquiterpenes (5-19), 16 diterpenes (20-35), three phenylpropanoids (36-38), and a phenolic compound (39).     

Thermal behaviour of sericite clays as precursors of mullite materials

Thermal analysis of some sericite clays, from several deposits in Spain, which are not exploited at this time, has been studied. The samples have been previously characterized by mineralogical and chemical analysis. Sericite clays have interesting properties, with implications in ceramics and advanced materials, in particular concerning the formation of mullite by heating. According to this investigation by differential thermal and thermogravimetric analysis (DTA-TG), the sericite clay samples can be classified as: Group (I), sericite–kaolinite clays, with high or medium sericite content, characterized by an endothermic DTA peak of dehydroxylation of kaolinite with mass loss, which overlapped with dehydroxylation of sericite, and Group (II), sericite–kaolinite–pyrophyllite clays, with broader endothermic DTA peaks, in which kaolinite is dehydroxylated first and later sericite and pyrophyllite with the main mass loss, appearing the peaks overlapped. X-ray diffraction analysis of the heated sericite clay samples evidenced the decomposition of dehydroxylated sericite and its disappearance at 1050 °C, with formation of mullite, the progressive disappearance of quartz and the formation of amorphous glassy phase. The vitrification temperature is ~ 1250 °C in all these samples, with slight variations in the temperatures of maximum apparent density (2.41–2.52 g mL^?1) in the range 1200–1300 °C. The fine-grained sericite content and the presence of some mineralogical components contribute to the formation of mullite and the increase in the glassy phase by heating. Mullite is the only crystalline phase detected at 1400 °C with good crystallinity. SEM revealed the dense network of rod-shaped and elongated needle-like mullite crystals in the thermally treated samples. These characteristics are advantageous when sericite clays are applied as ceramic raw materials.     

Coincidence counting for PGNAA applications: Is it the optimum method?

Summary One of the main advantages of γ-γ coincidence counting is the reduction of the background spectrum, pulse pile-up, and summing effects (for simple schemes). For prompt gamma-ray neutron activation analysis (PGNAA), the sources of background include the gamma-rays from the natural background, from surrounding materials, from the neutron source, and from detector neutron activation. While this counting approach effectively increases the signal-to-noise (S/N) ratio, it also decreases the signal counting rate. This adds some practical limitations to using this approach. In this work, two examples are presented for the efficient use of the coincidence counting approach.     

Catalysis of the silica sol-gel process by divalent transition metal bis(acetylacetonate) complexes

Transition metal bis(acetylacetonate) complexes of Co(II), Ni(II), Cu(II), and Zn(II) have been found to be active catalysts for the sol-gel process. The catalytic activity of these complexes decreases in going from Co(II) to Zn(II) and is highest for the acetylacetonate ligand system. 29Si NMR studies show that the complexes act primarily as condensation catalysts and are, in that regard, similar to Br?nsted bases such as hydroxide. Mechanistically, however, they appear to differ significantly from hydroxide in how they induce condensation. This is revealed in the catalyst concentration dependence, which is 1/2 order for the metal complexes and 1st order in hydroxide. Differences are also apparent in the thermochemical parameters that indicate that the metal complexes act to increase the entropy of the transition state leading to condensation. The catalytic activity is proportional to the degree of ligand dissociation of the metal complex, and experiments suggest that the active catalytic species is specifically the first dissociation product, MII(acac)+.     

Biphasic photochemistry: time-resolved spectra of adsorbed hydrocarbons

Time-resolved fluorescence spectra were measured for pyrene and naphthalene adsorbed on a silica gel surface using the time-correlated photon-counting technique Excimer-Iike emission was observed within an excitation lamp duration of a few nanoseconds with both pyrene and naphthalene. It is suggested, from the excitation spectra, that ground state complexes of the adsorbates are responsible for the formation of the excimer-like emission.