Endonuclease III (EndoIII) is a bifunctional DNA glycosylase that removes oxidized pyrimidines from DNA. The genome of Deinococcus radiodurans encodes for an unusually high number of DNA glycosylases, including three EndoIII enzymes (drEndoIII1-3). Here, we compare the properties of these enzymes to those of their well-studied homologues from E. coli and human. Our biochemical and mutational data, ...

Phorbazoles are polychlorinated heterocyclic secondary metabolites isolated from a marine sponge and several of these natural products have shown inhibitory activity against cancer cells. In this work, a synthesis of the trichlorinated phorbazole B using late stage electrophilic chlorination was developed. The synthesis relied on the use of an oxazole precursor, which was protected with an iodine ...

A class of DNA folds/structures known collectively as G-quadruplexes (G4) commonly forms in guanine-rich areas of genomes. G4-DNA is thought to have a functional role in the regulation of gene transcription and telomerase-mediated telomere maintenance and, therefore, is a target for drugs. The details of the molecular interactions that cause stacking of the guanine-tetrads are not well-understood, ...

Explicit calculations of vertical and adiabatic ionization potentials of cyclopropane derivatives with modern DFT methods have underscored the possibility of unusually large reorganization energies (defined as the difference between vertical and adiabatic ionization potentials) of 0.5–1.0 eV for several compounds. Such is the case for ionization of the twist-bent σ-bond of trans-bicyclo[4.1.0]hept-3-ene ...

Multi-photon absorption properties, particularly two-photon absorption (2PA), of fluorescent proteins (FPs) have made them attractive tools in deep-tissue clinical imaging. Although the diversity of photophysical properties for FPs is wide, there are some caveats predominant among the existing FP variants that need to be overcome, such as low quantum yields and small 2PA cross-sections. From a ...

A detailed TDDFT study (with all-electron STO-TZ2P basis sets and the COSMO solvation model) has been carried out on the effect of diprotonation on the UV−vis−NIR spectra of free-base tetraphenylporphyrin and tetrakis(p-aminophenyl)porphyrin. The diprotonated forms have been modeled as their bis-formate complexes, i.e., as so-called porphyrin diacids. The dramatic redshift of the Q-band of ...

Structural features of proton-deficient heteroaromatic natural products, such as the breitfussins, can severely complicate their characterization by NMR spectroscopy. For the breitfussins in particular, the constitution of the five-membered oxazole central ring cannot be unequivocally established via conventional NMR methods when the 4′-position is halogenated. The level of difficulty is exacerbated ...

Polyhydroxyalkanoates (PHAs) are natural biodegradable polyesters that are produced by numerous prokaryotic microorganisms primarily as a carbon- and energy reserve. The PhaC enzyme catalyzes the last step in the PHA biosynthesis pathway and synthesizes PHA polymers from hydroxyalkanoic acids. A type I PhaC from a PHAproducing marine bacterium Brevundimonas sp. KH11J01 (BrPhaC) was identified, ...

We present a heuristic mechanism for the origin of the unusual triplet lasing from (E)-3-(((4-nitrophenyl)imino)methyl)-2H-thiochroman-4-olate·BF₂. We demonstrate that whereas the moderate lifetime (1.03 μs) of the first triplet state (T₁) prohibits triplet–triplet annihilation, the relatively faster S₁ → T₁ intersystem crossing and the 10⁴ times ...