Self-assembly mechanism of nanoparticles of Ni-based Prussian Blue analogues at the air/liquid interface: a synchrotron X-ray reflectivity study.
Prussian Blue analogue (PBA) nanoparticles can be self-assembled at air/liquid interfaces to build novel materials with interesting magnetic features. Herein, we study the influence of the size of PBA Cs0.4 Ni[Cr(CN)6 ]0.9 and K0.25 Ni[Fe(CN)6 ]0.75 nanoparticles on the self-assembly behavior by synchrotron X-ray reflectivity. Both nanoparticles show similar Z-potential values. The phospholipid dipalmitoylphosphatidylcholine and the amino surfactant dimethyldioctadecylammonium have been used as Langmuir monolayers to anchor the PBA nanoparticles and study the interplay of forces directing the self-assembly of the nanoparticles at the surfactant/liquid interface. Whereas Cs0.4 Ni[Cr(CN)6 ]0.…
X-ray diffraction of a protein crystal anchored at the air/water interface
We report the first successful in situ x-ray diffraction experiment with a 2D protein array at the lipid/water interface and demonstrate that the order can be controlled via lateral pressure or density. A protein (streptavidin) was bound to a monolayer of biotinylated lipid at the air/water interface, and diffraction of the protein layer could be measured to many orders. Compression of the monolayer changed the diffraction pattern drastically, indicating that the protein structure can be strongly influenced by external parameters like lateral pressure or density. From the width of the peaks, we find that aggregates consisting of as few as 100 monomers contribute to the diffraction. This ind…
Structure features and phase behaviour of amphiphilic N-tetradecyl-β-hydroxy-propionic acid amide monolayers
Abstract Two phase transitions of N-tetradecyl-β-hydroxy-propionic acid amide monolayers at the air/water interface were studied by means of pressure/surface area ( π A ) isotherms, Brewster angle microscopy (BAM) and synchrotron X-ray grazing-incidence diffraction (GID). At T≤15 °C the π A isotherms show two plateau regions indicating two first-order phase transitions. In the first main transition from the lowdensity fluid-like phase to a condensed phase, dendritic growth of condensed phase domains with six main growth directions was observed by BAM. A second transition from a condensed phase with large tilt angle to a condensed phase with smaller tilt angle and a denser arrangement of mol…
Condensed phases in monolayers of a triple-chain lecithin on water
Abstract A triple-chain phospholipid monolayer at the air-water interface is investigated by means of grazing incidence X-ray diffraction (GID). Analysis of the diffraction spot profiles parallel and perpendicular to the surface yields different ordered phases. On increasing the lateral pressure at different temperatures the hydrocarbon chains form tilted phases with a tilt toward the nearest neighbors and eventually a hexagonal lattice with vertical chain orientation.
Domain shapes and monolayer structures of triple-chain phospholipids on water
Two triple-chain phospholipid isomers were investigated at the air-water interface by means of fluorescence microscopy and grazing incidence X-ray diffraction (GID). The two lipids differ only in the position of the branched chain at the glycerol backbone. Fluorescence microscopy shows different domain sharp-edged domains. In the case of dendritic domains the chains are more tilted, the deviation from hexagonal symmetry is more pronounced and hence the lattice anisotropy is larger.
Influence of a hydrophilic spacer on the structure of a phospholipid monolayer
We present the results of thermodynamical and X-ray grazing incidence diffraction experiments performed on Langmuir monolayers of ether lipids with hydrophilic spacers between the glycerol backbone and the phosphatidylcholine head group: DHPC, DH-E01-PC, and DH-E02-PC. As a spacer the oxy-ethylene group is used, which is a typical hydrophilic unit of non-ionic tensides. It turns out that the introduction of the hydrophilic spacers leads to a fluidization of the monolayer and reduces the tilt angle of the chains.
Chirality effects on 2D phase transitions
Monolayers of the racemate and pure enantiomers of 1-hexadecyl-glycerol were investigated by grazing incidence X-ray diffraction (GID) at 5 and 20 °C on compression from 0 mN m−1 to pressures greater than 30 mN m−1. The racemate lattice is centred-rectangular for both temperatures at all investigated pressures. However, at both temperatures, there is a sharp phase transition from a low-pressure phase, in which the molecules are tilted towards nearest neighbours (NN) and the distortion azimuth also points towards NN, to a high-pressure phase, in which the molecules are tilted towards next-nearest neighbours (NNN) and an NNN-distorted lattice is observed. At 5 °C, the transition pressure is 1…
Domain formation in monolayers
For phospholipids at the air/water interface we demonstrate that molecular chirality in some, but not in all, cases influences the domain shapes. In other cases chirality in the head group region can cause a chiral structure considering the tail arrangement. This indicates head group ordering. Minute changes of the molecular structure may change domain morphology from circular to dendritic. This can be related to slight changes of the lattice structure. In case of a dendritic domain the chains are more tilted, the deviation from hexagonal symmetry is more pronounced, and hence the lattice anisotropy is larger. This can be understood also in view of recent simulations considering diffusion-l…
Separation of Enantiomers in a Monolayer of Racemic 3-Hexadecyl-oxy-propane-1,2-diol
Monolayers of a racemic mixture and of the pure S enantiomer of 3-hexadecyloxy-propane-1,2-diol have been characterized by thermodynamic measurements at the air/water interface as well as by fluorescence microscopy. The critical temperatire T c , the limiting molecular area at high pressure and the pressure π c corresponding to the observed main phase transition, derived from the isotherms, slightly depend on chiral purity
Head-group variations and monolayer structures of diol derivatives
Monolayers of 5 chemically modified diols varying the headgroup (nonadecane-1,2-diol (C1), hexadecyl-propane-1,3-diol (C2), hexadecyl-oxy-propane-1,2-diol (C3), hexadecyl-oxy-butane-1,2-diol (C4), hexadecanoyl-oxy-propane-1,2-diol (C5)) have been investigated by grazing incidence x-ray diffraction at 20°C and at different lateral pressures. C1 and C5 exhibit a centred-rectangular lattice with NN (nearest neighbour) tilt and NN distortion directions. In the case of C1 on increasing the lateral pressure the distortion changes to NNN (next-nearest neighbour direction) without a change in tilt direction (NN). This behaviour could not be observed for the other compounds. C3 and C4 display a phas…
Grazing-Incidence X-ray Diffraction Study of Octadecanoic Acid Monolayers
We report the observation of X-ray scattering profiles from monolayers of octadecanoic acid in the vicinity of room temperature and evidence for the existence near room temperature of all four hexatic rotator phases L2d, Ov, L‘1, and LS, which differ in the details of their molecular tilt. While the incontrovertible triple-reflection signature of the chiral L‘1 phase was not observed, we propose that the previously reported rapid annealing behavior in this phase can lead to the disappearance of one, and in some cases two, of the three peaks.
Brewster angle microscopy and X-ray GID studies of morphology and crystal structure in monolayers of N-tetradecyl-γ,δ-dihydroxypentanoic acid amide
First-order phase transitions from the low-density fluidlike phase to the condensed phase of monolayers of N-tetradecyl-γ,δ-dihydroxypentanoic acid amides at the air−water interface have been studied by π−A isotherms, Brewster angle microscopy (BAM), and synchrotron X-ray grazing incidence diffraction (GID). The thermodynamic differences between enantiomeric and racemic monolayers are too small to be measured. However, chiral discrimination is observable in the macroscopic domain morphology by BAM. The domains of the condensed phase grow dendritically. The characteristic shapes of domains of the pure S and R enantiomers are mirror images of each other. The domains of the racemic mixture are…
Chemical modification of Topaz surfaces
In chemisorption, one is typically faced with the problem that the two-dimensional structure of the organic layer does not match the structure of the inorganic substrate. This work describes the first steps toward an induced epitaxial correlation of organic compounds on an inorganic surface. The idea of this work was to use a single crystal with a two-dimensional surface structure, Topaz (001), that matches an alkyl chain lattice better than existing substrates. X-ray reflectivity and FTIR experiments prove the surface modification of the Topaz, which is probably an etherification of the reactive OH-groups on the Topaz (001) surface.
Incorporation of mRNA in Lamellar Lipid Matrices for Parenteral Administration
Molecular pharmaceutics 15(2), 642 - 651 (2018). doi:10.1021/acs.molpharmaceut.7b01022
Self-organization of amphiphilic N-acylated linear polyethyleneimines: investigation of a reversible monolayer collapse
Abstract Poly-N-4-decyloxybenzoylethyleneimine, highly crystalline in bulk, forms a stable monolayer at the air-water interface which undergoes a reversible collapse into a probable bilayer structure at higher surface pressures. We achieved transfer both from the monolayer and “bilayer” region of the polymer film at the water surface onto hydrophilic and hydrophobized quartz supports. Based on X-ray investigations on the deposited Langmuir-Blodgett films, a possible mechanism for the reversible collapse is proposed.