Photo-mediated ring contraction of saturated heterocycles

Saturated heterocycles are found in numerous therapeutics as well as bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light-mediated ring contraction of α-acylated saturated heterocycles. This unconventional transformation is orthogonal to traditional ring contractions, challenging the paradigm for diversification of heterocycles including piperidine, morpholine, thiane, tetrahydropyran, and tetrahydroisoquinoline derivatives. The success of this Norrish Type II variant rests on reactivity differences between photoreactive ketone groups in specific chemical environments. This strategy was applied to late-stage remodeling of pharmaceutical derivatives, peptides, and sugars.

Photo-initiated ground state chemistry: How important is it in the atmosphere?

Carbonyls are among the most abundant volatile organic compounds in the atmosphere. They are central to atmospheric photochemistry as absorption of near-UV radiation by the C=O chromophore can lead to photolysis. If photolysis does not occur on electronic excited states, non-radiative relaxation to the ground state will form carbonyls with extremely high internal energy. These “hot” molecules can access a range of ground state reactions. Up to nine potential ground state reactions are investigated at the B2GP-PLYP-D3/def2-TZVP level of theory for a dataset of 20 representative carbonyls. Almost all are energetically accessible under tropospheric conditions. Comparison with experiment suggests the most significant ground state dissociation pathways will be concerted triple fragmentation in saturated aldehydes, Norrish type III dissociation to form another carbonyl, and H2-loss involving the formyl H atom in aldehydes. Tautomerisation, leading to more reactive unsaturated species, is also predicted to be energetically accessible and is likely to be important when there is no low-energy ground state dissociation pathway, for example in α,β-unsaturated carbonyls and some ketones. The concerted triple fragmentation and H2-loss pathways have immediate atmospheric implication to global H2 production and tautomerisaton has implication to the atmospheric production of organic acids.

Degradation and Stabilization of Poly(Butylene Adipate-Co- Terephthalate)/Polyhydroxyalkanoate Biodegradable Mulch Films Under Different Aging Tests

The degradation and stability of biodegradable films determine the service length of mulch films in actual use. Most biodegradable polymers degrade too fast to meet the required durability of mulch films. The objective of this work is to investigate the degradation behaviors of poly(butylene adipate-co-terephthalate) (PBAT) /polyhydroxyalkanoate (PHA) blend mulch films. Several different types of stabilizers were incorporated in the biodegradable blends to provide protection for the PHA/PBAT films during thermal processing and aging on agricultural fields. The degradation process of the films was systematically studied under an Accelerated Aging Test (AAT) and a Soil Aging Test (SAT). Adding a light stabilizer, UV stabilizer, or antioxidant to the mulch films led to significant improvement in the retention of mechanical properties of the films under both AAT and SAT. Morphological evolution of the films with or without a UV stabilizer as a function of aging times was studied by Scanning Electron Microscopy (SEM). The results of thermal properties and crystallinity revealed damage of crystal structure of the films during AAT. Spectrocopic results indicated that the films underwent both hydrolysis and photodegradative chain scissions (Norrish Type I/II reactions and photo-oxidation). The degradation mechanisms of the PHA/PBAT biodegradable mulch films were proposed.