Tröger's base-embedded pillararenes (), which combine Tröger's base () with dialkoxybenzene units, were prepared via a fragment-coupling macrocyclization strategy. The unit in macrocycle provides a fixed chiral source, while 1,4-alkoxybenzene segments flip quickly to change their arrangement, which could provide reversible conformational chirality for those macrocycles. This rare example of macrocycles holding both fixed and conformational chirality lays a good foundation for expanding pillararenes using the fixed chiral source.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.4c02572 | DOI Listing |
ACS Appl Bio Mater
January 2025
School of Chemistry, Pharmacy and Food Biosciences, University of Reading, Whiteknights, Reading RG6 6AD, U.K.
A series of tripodal (three-arm) lysine-based peptides were designed and synthesized and their self-assembly properties in aqueous solution and antimicrobial activity were investigated. We compare the behaviors of homochiral tripodal peptides (KKY)K and a homologue containing the bulky aromatic fluorenylmethoxycarbonyl (Fmoc) group Fmoc-(KKY)K, and heterochiral analogues containing k (d-Lys), (kkY)K and Fmoc-(kkY)K. The molecular conformation and self-assembly in aqueous solutions were probed using various spectroscopic techniques, along with small-angle X-ray scattering (SAXS) and cryogenic-transmission electron microscopy (cryo-TEM).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute of Organic Chemistry, University Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany.
In ion-pair catalysis, the last intermediate structures prior to the stereoselective transition states are of special importance for predictive models due to the high isomerization barrier between - and -substrate double bonds connecting ground and transition state energies. However, in prior experimental investigations of chiral phosphoric acids (CPA) solely the early intermediates could be investigated while the key intermediate remained elusive. In this study, the first experimental structural and conformational insights into ternary complexes with CPAs are presented using a special combination of low temperature and relaxation optimized N HSQC-NOESY NMR spectroscopy to enhance sensitivity.
View Article and Find Full Text PDFFood Res Int
January 2025
State Key Laboratory of Food Nutrition and Safety, Key Laboratory of Food Nutrition and Safety, Ministry of Education, College of Food Science and Engineering, Tianjin University of Science & Technology, No. 9, No. 13 Ave., TEDA, Tianjin 300457, China. Electronic address:
There is an urgent need for stable, plant-based Pickering foams to address the growing consumer demand for sustainable, low-calorie, aerated sweet foods. This study employed a cold plasma-assisted deamidation and glycosylation (CPDG) approach to promote hydrophilic reassembly of zein, resulting in the formation of sugar derivative-zein conjugates. This was accomplished by coupling deamidated zein with polyhydroxy sugars including sucralose (Suc), maltitol (Mal), mannitol (Man), and stevioside (Ste).
View Article and Find Full Text PDFSci Rep
January 2025
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, Poznan, 61 614, Poland.
The embellishing of the macrocycle core with sulfur substituents of varied sterical requirements changes the structural dynamics of chiral, triangular polyimines. Despite their formal high symmetry, these compounds adopt diverse conformations, in which the macrocycle core represents a non-changeable unit. DFT calculations reveal that the mutual arrangement of sulfur-containing substituents is controlled mainly by sterical interactions.
View Article and Find Full Text PDFChemistry
January 2025
Indian Institute of Technology Kanpur, Department of Chemistry, Kanpur, 208016, Kanpur, INDIA.
Herein, we report the precise control of molecular to supramolecular chirality induction at the single-molecule level just upon subtle modification in an achiral 'nano-size' trizinc(II) porphyrin trimer. A slight variation in the projection of the substituent at the periphery of the central porphyrin unit in a porphyrin trimer (host) resulted in pronounced changes in the interchromophoric arrangement, leading to distinct 'open' and 'closed' conformations. While 'open' form generates 'monomeric' complex with low CD amplitude, 'closed' form produces exclusive 'polymer' with large, amplified CD signal with opposite sign due to stronger intermolecular excitonic coupling.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!