Gated electron sharing within dynamic naphthalene diimide-based oligorotaxanes.

The controlled self-assembly of well-defined and spatially ordered π-systems has attracted considerable interest because of their potential applications in organic electronics. An important contemporary pursuit relates to the investigation of charge transport across noncovalently coupled components in a stepwise fashion. Dynamic oligorotaxanes, prepared by template-directed methods, provide a scaffold for directing the construction of monodisperse one-dimensional assemblies in which the functional units communicate electronically through-space by way of π-orbital interactions. Reported herein is a series of oligorotaxanes containing one, two, three and four naphthalene diimide (NDI) redox-active units, which have been shown by cyclic voltammetry, and by EPR and ENDOR spectroscopies, to share electrons across the NDI stacks. Thermally driven motions between the neighboring NDI units in the oligorotaxanes influence the passage of electrons through the NDI stacks in a manner reminiscent of the conformationally gated charge transfer observed in DNA.

Lower resource utilization for patients with healed diabetic foot ulcers during participation in a prevention program with foot temperature monitoring.

INTRODUCTION: We assessed the impact of a diabetic foot ulcer prevention program incorporating once-daily foot temperature monitoring on hospitalizations, emergency department and outpatient visits, and rates of diabetic foot ulcer recurrence and lower extremity amputations for patients with recently healed foot ulcers. RESEARCH DESIGN AND METHODS: In this retrospective analysis of real-world data, we enrolled 80 participants with a healed diabetic foot ulcer in a year-long foot ulcer recurrence prevention program. Four outpatient centers within a large integrated healthcare system in the USA contributed to enrollment. We evaluated diabetic foot-related outcomes and associated resource utilization for participants during three periods: the 2 years before the program, the year during the program, and after the program ended. We reported unadjusted resource utilization rates during the program and the periods before and after it. We then adjusted rates of outcomes in each phase using an interrupted time series approach, explicitly controlling for overall trends in resource utilization and recurrence during the three periods. RESULTS: Our unadjusted data showed high initial rates of resource utilization and recurrence before enrollment in the program, followed by lower rates during the program, and higher rates of resource utilization and similar rates of recurrence in the period following the end of the program. The adjusted data showed lower rates of hospitalizations (relative risk reduction (RRR)=0.52; number needed to treat (NNT)=3.4), lower extremity amputations (RRR=0.71; NNT=6.4), and outpatient visits (RRR=0.26; absolute risk reduction (ARR)=3.5) during the program. We also found lower rates of foot ulcer recurrence during the program in the adjusted data, particularly for wounds with infection or greater than superficial depth (RRR=0.91; NNT=4.4). CONCLUSIONS: We observed lower rates of healthcare resource utilization for high-risk participants during enrollment in a diabetic foot prevention program incorporating once-daily foot temperature monitoring. TRIAL REGISTRATION NUMBER: NCT04345016.

Formation of a hetero[3]rotaxane by a dynamic component-swapping strategy.

Acid-catalysed scrambling of the mechanically interlocked components between two different homo[3]rotaxanes, constituted of dumbbells containing two secondary dialkylammonium ion recognition sites encircled by two [24]crown-8 rings, each containing a couple of imine bonds, affords a statistical mixture of a hetero[3]rotaxane along with the two homo[3]rotaxanes, indicating that neither selectivity nor cooperativity is operating during the assembly process.