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@ARTICLE{Vollhardt:453858,
author = {Vollhardt, D. and Dobner, B. and Brezesinski, G.},
title = {{I}nfluence of linkage type (ether or ester) on the
monolayer characteristics of single-chain glycerols at the
air–water interface},
journal = {Physical chemistry, chemical physics},
volume = {22},
number = {40},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {PUBDB-2021-00222},
pages = {23207 - 23214},
year = {2020},
abstract = {O-1-Alkylglycerols are ubiquitous constituents in various
biological materials but their biological significance is
still largely unknown. So far, reports about the striking
role of structural features on the interfacial properties of
1-O-alkylglycerol monolayers are quite rare. Therefore, in
the present paper 1-O-alkylglycerol monolayers are
comprehensively characterized on mesoscopic and molecular
scales in the accessible ranges of temperature and surface
pressure. Two Bragg peaks found for the condensed monolayer
phase of the racemates at all pressures investigated
indicate an orthorhombic structure with NN-tilted alkyl
chains at lower pressures and NNN-tilted chains at higher
pressures. In contrast to the continuous change of the tilt
angle, as observed for many amphiphile monolayers, the tilt
angle in 1-O-alkyl-rac-glycerol monolayers shows a jump-like
transition from the L$_2$ (NN tilt direction) to the Ov
phase (NNN tilt direction) with the consequence of different
slopes of 1/cos(t) vs. π in the two phases. This is the
most striking difference to the behavior of the
corresponding ester compound 1-stearoyl-rac-glycerol, having
an oblique phase between the two orthorhombic phases L$_2$
and Ov at low temperatures. The generic phase diagrams of
the 1-O-alkyl-rac-glycerol and 1-acyl-rac-glycerol
monolayers are essentially different. The influence of
chirality on the monolayer structure is weak and becomes
even weaker at high temperatures (rotator phases) and high
lateral compression. The GIXD results of the enatiomeric
pure compounds show the expected oblique lattice structure
characterized by three Bragg peaks at almost all lateral
pressures measured. The results of the GIXD studies are
complemented by other monolayer characteristics such as
π–A isotherms and mesoscopic domain topographies. The
π–A isotherms of 1-O-alkyl-rac-glycerols are similar to
those of the corresponding 1-acyl-rac-glycerols indicating
that the change from the ester linkage to the ether linkage
does not affect significantly the thermodynamic features.
However, pronounced differences in the topological structure
are observed. 1-O-hexadecyl-rac-glycerol monolayers form
three-armed domains whereby each arm is subdivided into two
segments with different molecular orientation. Also
fascinating chiral discrimination effects are observable,
demonstrated in the case of S-enantiomers by always
clockwise curved spirals at the domain periphery. The
1 : 1 racemic mixtures exhibit both clockwise and
counterclockwise curved spirals.},
cin = {DOOR ; HAS-User},
ddc = {540},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {899 - ohne Topic (POF3-899)},
pid = {G:(DE-HGF)POF3-899},
experiment = {EXP:(DE-H253)D-BW1-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:33029597},
UT = {WOS:000581596800035},
doi = {10.1039/D0CP04153J},
url = {https://bib-pubdb1.desy.de/record/453858},
}