Dataset Information

Squaraine rotaxanes with boat conformation macrocycles.

ABSTRACT: Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocycles with 1,4-phenylene sidewalls and 2,6-pyridine dicarboxamide bridging units are more likely to adopt boat conformations in the solid state than analogous squaraine rotaxane systems with isophthalamide-containing macrocycles. A truncated squaraine dye, with a secondary amine attached directly to the central C(4)O(2) core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is maintained in solution. Encapsulation as a rotaxane increases the dye's brightness by a factor of 6. The encapsulation process appears to constrain the dye and reduce deformation of the chromophore from planarity. This study shows how mechanical encapsulation as a rotaxane can be used as a rational design parameter to fine-tune the chemical and photochemical properties of squaraine dyes.

SUBMITTER: Fu N

PROVIDER: S-EPMC2847772 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Squaraine rotaxanes with boat conformation macrocycles.

Fu Na N Baumes Jeffrey M JM Arunkumar Easwaran E Noll Bruce C BC Smith Bradley D BD

The Journal of organic chemistry 20090901 17

Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocyc ...[more]

PMID: 19639940

Similar Datasets

Project description:Seagrass meadows commonly reside in shallow sheltered embayments typical of the locations that provide an attractive option for mooring boats. Given the potential for boat moorings to result in disturbance to the seabed due to repeated physical impact, these moorings may present a significant threat to seagrass meadows. The seagrass Zostera marina (known as eelgrass) is extensive across the northern hemisphere, forming critical fisheries habitat and creating efficient long-term stores of carbon in sediments. Although boat moorings have been documented to impact seagrasses, studies to date have been conducted on the slow growing Posidonia species' rather than the fast growing and rapidly reproducing Z. marina that may have a higher capacity to resist and recover from repeated disturbance. In the present study we examine swinging chain boat moorings in seagrass meadows across a range of sites in the United Kingdom to determine whether such moorings have a negative impact on the seagrass Zostera marina at the local and meadow scale. We provide conclusive evidence from multiple sites that Z. marina is damaged by swinging chain moorings leading to a loss of at least 6 ha of United Kingdom seagrass. Each swinging chain mooring was found to result in the loss of 122 m2 of seagrass. Loss is restricted to the area surrounding the mooring and the impact does not appear to translate to a meadow scale. This loss of United Kingdom seagrass from boat moorings is small but significant at a local scale. This is because it fragments existing meadows and ultimately reduces their resilience to other stressors. Boat moorings are prevalent in seagrass globally and it is likely this impairs their ecosystem functioning. Given the extensive ecosystem service value of seagrasses in terms of factors such as carbon storage and fish habitat such loss is of cause for concern. This indicates the need for the widespread use of seagrass friendly mooring systems in and around seagrass.

Dataset Information

Squaraine rotaxanes with boat conformation macrocycles.

Publications

Squaraine rotaxanes with boat conformation macrocycles.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets