Stereoisomerism, stemming from the spatial orientation of components in molecular structures, plays a decisive role in nature. While the unconventional bonding found in mechanically interlocked molecules gives rise to unique expressions of stereochemistry, the exploration of their stereoisomers is still in its infancy. Sequence isomerism, characterized by variations in the ordering of mechanically interlocked components in catenanes and rotaxanes, mirrors the sequence variations found in biological macromolecules. Herein, we report the use of artificial molecular pumps for the precise and simple production of sequentially isomeric hetero[3]rotaxanes. Utilizing redox-driven pumping cassettes with different rings, we have synthesized two hetero[3]rotaxane isomers in high isolated yields from two [2]rotaxanes. This research represents a significant advance in sequential molecular assembly, paving the way for the development of sophisticated, functionalized, mechanically interlocked materials.

Download full-text PDF

Source
http://dx.doi.org/10.1021/jacs.4c09406DOI Listing

Publication Analysis

Top Keywords

mechanically interlocked
12
sequentially isomeric
8
isomeric hetero[3]rotaxanes
8
concise efficient
4
efficient synthesis
4
synthesis sequentially
4
hetero[3]rotaxanes stereoisomerism
4
stereoisomerism stemming
4
stemming spatial
4
spatial orientation
4

Similar Publications

Surface enzyme-polymerization endows Janus hydrogel tough adhesion and regenerative repair in penetrating orocutaneous fistulas.

Nat Commun

December 2024

Shanghai Key Laboratory of Anesthesiology and Brain Functional Modulation, Clinical Research Center for Anesthesiology and Perioperative Medicine, Translational Research Institute of Brain and Brain-Like Intelligence, Shanghai Fourth People's Hospital, School of Medicine, Tongji University, Shanghai, China.

Penetrating orocutaneous or oropharyngeal fistulas (POFs), severe complications following unsuccessful oral or oropharyngeal reconstruction, remain complex clinical challenges due to lack of supportive tissue, contamination with saliva and chewed food, and dynamic oral environment. Here, we present a Janus hydrogel adhesive (JHA) with asymmetric functions on opposite sides fabricated via a facile surface enzyme-initiated polymerization (SEIP) approach, which self-entraps surface water and blood within an in-situ formed hydrogel layer (RL) to effectively bridge biological tissues with a supporting hydrogel (SL), achieving superior wet-adhesion and seamless wound plugging. The tough SL hydrogel interlocked with RL dissipates energy to withstand external mechanical stimuli from continuous oral motions like chewing and swallowing, thus reducing stress-induced damage.

View Article and Find Full Text PDF

Capillary-Enhanced Biomimetic Adhesion on Icy Surfaces for High-Performance Antislip Shoe-Soles.

ACS Appl Mater Interfaces

December 2024

Centre for MicroElectroMechanical Systems (CMEMS), University of Minho, Azurem Campus, 4800-058 Guimaraes, Portugal.

The World Health Organization (WHO) reports 684,000 deaths/year due to slips and falls (SFs), with ∼38 million people requiring medical attention per annum. In particular, SFs on ice surfaces account for 45% of all SF incidents, costing over $100 billion globally in healthcare, intensive care, and insurance expenses. Current antislip solutions focus on hydrophobicity to repel interfacial fluids, aiming to maintain solid-to-solid contact.

View Article and Find Full Text PDF

Enoki-Inspired Microfibers and Extracellular Matrix Enhance Biaxially Interlocking Interfaces.

Small Struct

November 2024

Department of Surgery-Transplant and Mary & Dick Holland Regenerative Medicine Program, University of Nebraska Medical Center, Omaha, NE, 68198, USA.

Taking inspiration from diverse interlocking and adhesion structures found in nature, a biaxially interlocking interface is developed in this work. This interface is formed by interconnecting two electrostatically flocked substrates and its mechanical strength is enhanced through the incorporation of enoki mushroom-shaped microfibers and deposited extracellular matrix (ECM). Tips of flocked straight fibers can be transformed into mushroom shapes through thermal treatment.

View Article and Find Full Text PDF

Macrocycles represent one important class of functional molecules, and dynamic macrocycles with the potential of cleavability, adaptability, and topological conversion are challenging. Herein we report photoswitchable allosteric and topological control of dynamic covalent macrocycles and further the use in guest binding and mechanically interlocked molecules. The manipulation of competing ring-chain equilibria and bond formation/scission within reaction systems enabled light-induced structural regulation over dithioacetal and thioacetal dynamic bonds, accordingly realizing bidirectional switching between crown ether-like covalent macrocycles and their linear counterparts.

View Article and Find Full Text PDF

Strategy To Enhance Interfacial Properties: Preparation of Porous Polytetrafluoroethylene Fibers and the Adsorption of Initiators/Curing Agents.

Langmuir

December 2024

State Key Laboratory of Tribology in Advanced Equipment, Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China.

Polytetrafluoroethylene (PTFE) fibers exhibit high inertness and demonstrate limited interfacial bonding capabilities with other materials. To overcome this limitation, PTFE@ZnO fibers were developed by depositing the porous ZnO layer onto PTFE fibers via a hydrothermal reaction, and porous fibers were adsorbed curing agents or initiators. The interfacial shear strength (ILSS) of the composites demonstrated a significant improvement, particularly in the case of composites containing PTFE/initiator fibers, where the ILSS increased by 104.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!