Mechanistic investigation into phenol oxidation by IBX elucidated by DFT calculations

Density functional theory (DFT) at the SMD/M06-2X/def2-TZVP//SMD/M06-2X/LANL2DZ(d),6-31G(d) level was used to explore the regioselective double oxidation of phenols by a hypervalent iodine(v) reagent (IBX) to give o-quinones.

Nanocrystalline cellulose prepared by double oxidation as reinforcement in polyvinyl alcohol hydrogels

As a biopolymer with high mechanical strength, nanocellulose was increasingly studied to improve polymer properties. In this study, nanocrystalline cellulose (NCC) was efficiently isolated from eucalyptus pulp by double oxidation (ammonium persulfate oxidation and ultrasonic oxidation). The total yield of NCC (405.1 ± 180.5 nm long and 31.7 ± 9.5 nm wide) was 38.3%. A novel hybrid hydrogel was produced from polyvinyl alcohol (PVA) and NCC using the freeze-thaw technique. In this hybrid architecture, hydrogen bonds were formed between PVA and NCC. With the increasing proportion of NCC, the pore size of hydrogels shank gradually and the structure of the hybrid hydrogels became denser. The tensile strength of PVA/NCC hybrid hydrogels increased by 42.4% compared to the neat PVA hydrogel. The results showed that NCC can improve the swelling, thermal properties, and water evaporation rate of PVA hydrogels due to the hydrophilic hydroxyl groups of NCC and hydrogen bonds between PVA and NCC, indicating that PVA hydrogels would have a wider range of application due to the existence of NCC, a green hybrid filler. Most importantly, this novel double oxidation method for preparing nanocellulose will promote an efficient production of nanocellulose.

Synthesis and Reactivity of Precolibactin 886

<div>The clb gene cluster encodes the biosynthesis of metabolites known as precolibactins and colibactins. The clb pathway is found in gut commensal E. coli, and clb metabolites are thought to initiate colorectal cancer via DNA cross-linking. Precolibactin 886 (1) is one of the most complex isolated clb metabolites; it contains a 15-atom macrocycle and an unusual 5-hydroxy-3-oxazoline ring. Here we report confirmation of the structural assignment via a biomimetic synthesis of precolibactin 886 (1) proceeding through the amino alcohol 9. Double oxidation of 9 afforded the unstable α-ketoimine 2 which underwent macrocyclization to precolibactin 886 (1) upon HPLC purification (3% from 9). Studies of the putative precolibactin 886 (1) biosynthetic precursor 2, the model α-ketoimine 25, and the α-dicarbonyl 26 revealed that these compounds are susceptible to nucleophilic rupture of the C36–C37 bond. Moreover, cleavage of 2 produces other known clb metabolites or biosynthetic intermediates. This unexpected reactivity explains the difficulties in isolating full clb metabolites and accounts for the structure of a recently identified colibactin–adenine adduct. The colibactin peptidase ClbP deacylates synthetic precolibactin 886 (1) to form a non-genotoxic pyridone, suggesting precolibactin 886 (1) lies off-path of the major biosynthetic route.</div>

Synthesis and Reactivity of Precolibactin 886

<div>The clb gene cluster encodes the biosynthesis of metabolites known as precolibactins and colibactins. The clb pathway is found in gut commensal E. coli, and clb metabolites are thought to initiate colorectal cancer via DNA cross-linking. Precolibactin 886 (1) is one of the most complex isolated clb metabolites; it contains a 15-atom macrocycle and an unusual 5-hydroxy-3-oxazoline ring. Here we report confirmation of the structural assignment via a biomimetic synthesis of precolibactin 886 (1) proceeding through the amino alcohol 9. Double oxidation of 9 afforded the unstable α-ketoimine 2 which underwent macrocyclization to precolibactin 886 (1) upon HPLC purification (3% from 9). Studies of the putative precolibactin 886 (1) biosynthetic precursor 2, the model α-ketoimine 25, and the α-dicarbonyl 26 revealed that these compounds are susceptible to nucleophilic rupture of the C36–C37 bond. Moreover, cleavage of 2 produces other known clb metabolites or biosynthetic intermediates. This unexpected reactivity explains the difficulties in isolating full clb metabolites and accounts for the structure of a recently identified colibactin–adenine adduct. The colibactin peptidase ClbP deacylates synthetic precolibactin 886 (1) to form a non-genotoxic pyridone, suggesting precolibactin 886 (1) lies off-path of the major biosynthetic route.</div>