The Coronavirus-19 transmitted through physical contact, droplets, and fomites caused severe respiratory disease resulting in high mortality worldwide. The COVID-19 pandemic caused innumerable hardships, panic, and restrictions of movement which negatively affected the assessment of healthcare services like breast cancer diagnosis in many countries. The results from the histopathological diagnosis of breast tumours have been routinely employed for the treatment and management of these diseases.
View Article and Find Full Text PDFWe report a mechanistic investigation of calcium bistriflimide-mediated sulfur(VI)-fluoride exchange (SuFEx) between sulfonyl fluorides and amines. We determine the likely pre-activation resting state─a calcium bistriflimide complex with ligated amines─thus allowing for corroborated calculation of the SuFEx activation barrier at ∼21 kcal/mol, compared to 21.5 ± 0.
View Article and Find Full Text PDFMethanol titrations of partially deuterated 1,4- and 1,3-diols dissolved in nonpolar solvents such as CDCl and benzene- have provided H NMR measurements of OH/OD isotope shifts, diagnostic for intact intramolecular hydrogen bonds, under conditions of increasing protic solvent concentration. 1,4- and 1,3-diols with conformationally favored intramolecular OH/OH hydrogen bonds can be titrated to constant isotope shift values, albeit with variable sign, in the presence of excess methanol equivalents, providing evidence for intact intramolecular hydrogen bonds under these conditions. Conversely, the isotope shift in a 1,3-diol with a conformationally labile intramolecular hydrogen bond titrated to zero when in the presence of excess equivalents methanol, consistent with intramolecular hydrogen bond rupture under these conditions.
View Article and Find Full Text PDFBacteria that colonize animals must overcome, or coexist, with the reactive oxygen species products of inflammation, a front-line defense of innate immunity. Among these is the neutrophilic oxidant bleach, hypochlorous acid (HOCl), a potent antimicrobial that plays a primary role in killing bacteria through nonspecific oxidation of proteins, lipids, and DNA. Here, we report that in response to increasing HOCl levels, Escherichia coli regulates biofilm production via activation of the diguanylate cyclase DgcZ.
View Article and Find Full Text PDFQuantum mechanical calculations reveal the preferred mechanism and origins of chemoselectivity for HOCl-mediated oxidation of zinc-bound thiolates implicated in bacterial redox sensing. Distortion/interaction models show that minimizing geometric distortion at the zinc complex during the rate-limiting nucleophilic substitution step controls the mechanistic preference for OH over Cl transfer with HOCl and the chemoselectivity for HOCl over H O .
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