Phenylalanine‐Derived Imidazolines Bearing Heteroaromatic Pendants: Synthesis,Characterization, and Application in the Asymmetric Henry Reaction

Starting from L ‐phenylalanine, (2S)‐3‐phenylpropane‐1,2‐diamine has been prepared and used as building block for the construction of the imidazoline ring. Four new optically pure NH‐imidazolines bearing different six‐membered heteroaromatic substituents on the C(2) position have been prepared and subsequently N‐modified. N‐Substitution afforded two regioisomers that were separated. Some of them proved to be instable and hydrolyzed to diamides. The molecular structures of NH‐imidazolines, both N‐substituted regioisomers, as well as diamides, were unambiguously confirmed by X‐ray‐analysis and NMR spectra. The successfully prepared imidazolines, as well as diamides, were applied as catalysts in a Cu(II)‐catalyzed Henry reaction achieving 26–98% chemical yields and enantiomeric excesses of 3–42%.     

Synthesis of Potentially Biologically Active 6‐(1,3‐Butadiynyl)purines

1,3‐Alkadiynyl(trimethyl)silanes were prepared by the Negishi or Sonogashira reactions of bromoethynyl(trimethyl)silane with several terminal alkynes in 34–75% yield. However, the direct Hiyama coupling of these compounds with 6‐iodopurine derivatives has not been successful. Therefore, a modified Sonogashira reaction using TBAF or CsF for in situ removal of the trimethylsilyl group has been utilized. This methodology afforded the desired 6‐(1,3‐butadiynyl)purines in 47–87% yield.     

Exploiting the 1,2,3‐Triazole Moiety to Generate Carbazole Molecular Architectures through Click Approach

Reaction of 3,6‐dichlorocarbazole with propargyl bromide in the presence of a basic medium gave an N‐propargylated carbazole. The latter compound was converted into molecular architectures containing 1,2,3‐triazole moiety through Cu(I)‐catalyzed 1,3‐cycloaddition reaction with different azides. Similarly, 2‐azidomethyl benzothiazole was cliched with N‐Boc‐protected N´‐propargyl glutamate to give the biomolecule 2‐triazolylmethyl product.     

Dunaliella tertiolecta (Chlorophyta) Avoids Cell Death Under Ultraviolet Radiation By Triggering Alternative Photoprotective Mechanisms

The effect of different ultraviolet radiation (UVR) treatments combining PAR (P), UVA (A) and UVB (B) on the molecular physiology of Dunaliella tertiolecta was studied during 6 days to assess the response to chronic UVR exposure. UVR reduced cell growth but did not cause cell death, as shown by the absence of SYTOX Green labeling and cellular morphology. However, caspase‐like enzymatic activities (CLs), (regarded as cell death proteases), were active even though the cells were not dying. Maximal quantum yield of fluorescence (F_v/F_m) and photosynthetic electron transport rate (ETR) dropped. Decreased nonphotochemical quenching (NPQ) paralleled a drop in xanthophyll cycle de‐epoxidation under UVB. Reactive oxygen species (ROS) and D1 protein accumulation were inversely correlated. PAB exhibited elevated ROS production at earlier times. Once ROS decayed, D1 protein recovered two‐fold compared with P and PA at later stages. Therefore, PsbA gene was still transcribed, suggesting ROS involvement in D1 recovery by its direct effect on mRNA‐translation. We add evidence of an UVB‐induced positive effect on the cells when P is present, providing photoprotection and resilience, by means of D1 repair. This allowed cells to survive. The photoprotective mechanisms described here (which are counterintuitive in principle) conform to an important ecophysiological response regarding light stress acclimation.     

Electrochemical determination of basic biochemical properties of enzyme enterokinase

Monatshefte für Chemie - Chemical Monthly - Basic biochemical properties such as Michaelis constant (K M), turnover number (k cat), and the ratio between these two kinetic parameters of enzyme...