Photoswitchable and long-lived seven-membered cyclic singlet diradicals for the bioorthogonal photoclick reaction.

Annularly 1,3-localized singlet diradicals are energetic and homolytic intermediates, but commonly too short-lived for widespread utilization. Herein, we describe a direct observation of a long-lived and seven-membered singlet diradical, oxepine-3,6-dione-2,7-diyl (OXPID), spectroscopic experiments and also theoretical evidence from computational studies, which is generated photo-induced ring-expansion of 2,3-diaryl-1,4-naphthoquinone epoxide (DNQO). The photo-generated OXPID reverts to the thermally stable σ-bonded DNQO with in the μs level, thus constituting a novel class of T-type molecular photoswitches with high light-energy conversion efficiency ( = 7.

Simultaneously enhancing the crystallization rate and fire retardancy of poly(lactic acid) by using a novel bifunctional additive trimethylamine phenylphosphonate.

Simultaneously regulating the crystallizing and combustion behaviors of poly(lactic acid) (PLA) will be conducive to its further development in the fields of electronic appliances, automotive and rail transit materials. To achieve this goal, a novel bifunctional additive triethylamine phenylphosphonate (TEAP) was synthesized through acid-base neutralization reaction between trimethylamine and phenylphosphonic acid. When TEAP was added into PLA, the crystallization behaviors of PLA/TEAP assessed by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) suggested that TEAP acted as a nucleating agent and plasticizer for PLA, which effectively increased the crystallization rate of PLA.

Expanding the functionality of proteins with genetically encoded dibenzo[,][1,4,5]thiadiazepine: a photo-transducer for photo-click decoration.

Genetic incorporation of novel noncanonical amino acids (ncAAs) that are specialized for the photo-click reaction allows the precisely orthogonal and site-specific functionalization of proteins in living cells under photo-control. However, the development of a r̲ing-strain l̲oadable d̲ipolarophile (RILD) as a genetically encodable reporter for photo-click bioconjugation with spatiotemporal controllability is quite rare. Herein, we report the design and synthesis of a photo-switchable d̲ib̲enzo[,][1,4,5]t̲hiad̲iazepine-based a̲lanine (DBTDA) ncAA, together with the directed evolution of a pyrrolysyl-tRNA synthetase/tRNA pair (PylRS/tRNA), to encode the DBTDA into recombinant proteins as a RILD in living cells.

Build-up of double carbohelicenes using nitroarenes: dual role of the nitro functionality as an activating and leaving group.

The construction of double carbohelicenes is highly fascinating yet challenging work. Disclosed herein is a streamlined and simplified synthetic route to double carbohelicenes starting from nitroarenes through sequential nitro-activated -C-H arylation, denitrative alkenylation and intramolecular cyclodehydrogenation. In this synthetic strategy, the nitro group plays a dual role namely as a leaving group for the denitrative alkenylation and as an activating group for -C-H arylation, which is distinct from those of aryl halides in a conventional coupling reaction.

A methylation platform of unconventional inert aryl electrophiles: trimethylboroxine as a universal methylating reagent.

Methylation is one of the most fundamental conversions in medicinal and material chemistry. Extension of substrate types from aromatic halides to other unconventional aromatic electrophiles is a highly important yet challenging task in catalytic methylation. Disclosed herein is a series of transition metal-catalyzed methylations of unconventional inert aryl electrophiles using trimethylboroxine (TMB) as the methylating reagent.

A Col I and BCP ceramic bi-layer scaffold implant promotes regeneration in osteochondral defects.

Osteochondral defects occur in the superficial cartilage region, intermediate calcified cartilage, and subchondral bone. Due to the limited regenerative capacity and complex zonal structure, it is critically difficult to develop strategies for osteochondral defect repair that could meet clinical requirements. In this study, type I collagen (Col I) and BCP ceramics were used to fabricate a new bi-layer scaffold for regeneration in osteochondral defects.