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Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States.

ABSTRACT: By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature-controlled supramolecular copolymerization of chiral and achiral biphenyl tetracarboxamides in alkanes. The one-dimensional helical structures presented in this study are unique because they exhibit three distinct helical states, two of which are triggered by coassembling with monomeric water that is codissolved in the solvent. The self-assembly pathways are rationalized using a combination of mathematical fitting and simulations with a thermodynamic mass-balance model. We observe an unprecedented case of an "abnormal" S&S effect by changing the side chains of the achiral soldier. Although the molecular structure of these aggregates remains elusive, the coassembly of water is found to have a profound impact on the helical excess.

SUBMITTER: Van Zee NJ

PROVIDER: S-EPMC7705959 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States.

Van Zee Nathan J NJ Mabesoone Mathijs F J MFJ Adelizzi Beatrice B Palmans Anja R A ARA Meijer E W EW

Journal of the American Chemical Society 20201110 47

By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature ...[more]

PMID: 33169999

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Project description:ObjectiveCephalomedullary nails (CMN) are implants with a high success rate in the surgical treatment of trochanteric fractures. The aim of this study is to compare the radiological outcomes and mechanical complications of femoral trochanteric fractures treated with three different CMNs.MethodsIntertrochanteric fractures in patients aged 50 years and older treated with CMN between January 2016 and December 2021 were reviewed retrospectively. A total of 158 cases meeting the criteria were included to final analysis. Cases were divided into three groups based on the type of nail used (helical blade: group 1, n = 54; screw: group 2, n = 53; winged screw: group 3, n = 51). Demographic characteristics, mechanical complications, reduction quality, tip-apex distances (TAD) and Cleveland zones were compared between the groups. Femoral neck shortening, varus collapse, lag sliding, changes in abductor length were compared between study groups. Factors affecting mechanical complications were also analyzed.ResultsStudy groups were homogenic in terms of demographic characteristics, fracture type and reduction quality. Regarding mechanical complications, no statistically significant difference was found between groups. All three implants had similar outcomes on femoral neck shortening, varus collapse and lag sliding. Pooled analysis of 158 cases showed that mechanical complications increase as the quality of reduction decreases (p = 0.000) same applies when TAD alters from the desired range (p = 0.025) and with non-optimally implanted blade according to Cleveland zones (p = 0, 000).ConclusionThe radiological outcomes and mechanical complications of helical blade, screw type blade and winged screw type blade proximal femoral nails are similar in selected group. Regardless of the device type, it is necessary to obtain high reduction quality, obtain TAD within described range and optimally place the blade according to Cleveland Zones to reduce the failure rate and avoid complications.

Dataset Information

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States.

Publications

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States.

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