preparation-of-carbon-nanosheets-at-room-temperature

Preparation of Carbon Nanosheets at Room Temperature

Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds self-assemble into ...

Max Planck Institute of Colloids and Interfaces

The synthesis and characterization of a new series of catanionic multivalent analogs of GalCer is described. These systems are based on phosphonic acid terminated dendrimers and N-hexadecylamino lactitol moieties. Despite important structural differences that affect the dendrimers' outer-shell, these supramolecular assemblies showed a fairly comparable anti-HIV-1 activity. All compounds have submicromolar IC(50) in a cell-based HIV-infection model but also a high general cytotoxicity.

Multivalent catanionic GalCer analogs derived from first generation dendrimeric phosphonic acids.

Biocompatible magnetite nanoparticles trapped at the air/water interface.

The interfacial properties of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs, recently developed and described as promising nanotools for biomedical applications, have been investigated at the air/water interface. These Fe(3)O(4) NPs, capped with catechol-terminated random copolymer brushes of 2-(2-methoxyethoxy) ethyl methacrylate (MEO(2)MA) and oligo(ethylene glycol) methacrylate (OEGMA), with molar fractions of 90% and 10%, respectively, proved to be surface active. Surface tension measurements of aqueous dispersions of the NPs showed that the adsorption of the NPs at the air/water interface is time- and concentration-dependent. These NPs do not behave as classical amphiphiles. Once adsorbed at the air/water interface, they do not exchange with NPs in bulk, but they are trapped at the interface. This means that all NPs from the bulk adsorb to the interface until reaching maximum coverage of the interface, which corresponds to values between 6 × 10(-4) and 8 × 10(-4) mg/cm(2) and a critical equilibrium surface tension of ∼47 mN/m. Moreover, Langmuir layers of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs have been investigated by measuring surface pressure-area compression-expansion isotherms and in situ X-ray fluorescence spectra. The compression-expansion isotherms showed a plateau region above a critical surface pressure of ∼25 mN/m and a pronounced hysteresis. By using a special one-barrier Langmuir trough equipped with two surface pressure microbalances, we have shown that the NPs are squeezed out from the interface into the aqueous subphase, and they readsorb on the other side of the barrier. The results have been supported by TEM as well as AFM experiments of transferred Langmuir-Schaefer films on solid supports. This study shows the ability of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs to transfer from hydrophilic media (an aqueous solution) to the hydrophobic/hydrophilic interface (air/water interface) and back to the hydrophilic media. This behavior is very promising, opening studies of their ability to cross biological membranes.

Langmuir and Gibbs magnetite NP layers at the air/water interface.

Subgel phase structure in monolayers of glycosylphosphatidylinositol glycolipids.

While nature provides an endless variety of phospholipids presenting hydrolyzable ester linkages for the 1,2-positioned hydrocarbon tails, we designed and synthesized 1,3-diamidophospholipids which contain stable fatty acid amides. These new phospholipids form faceted unilamellar vesicles with mechanosensitive properties. Aiming to understand the mechanism responsible for this behavior at a molecular level, we investigated the 1,3-diamidophospholipid family in monolayers, a simplified model membrane system. Langmuir isotherms combined with in situ grazing incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XR), and infrared reflection-absorption spectroscopy (IRRAS) allowed the characterization of the monolayers from a structural and thermodynamical point of view. The existence of strong headgroup interactions due to the formation of a hydrogen-bonding network was clearly revealed by IRRAS and by the high rigidity of the monolayers. GIXD showed that only the longer chain compounds of the series (Pad-PC-Pad (1,3-dipalmitamidopropan-2-phosphocholine) and Sad-PC-Sad (1,3-distearamidopropan-2-phosphocholine) were able to form ordered monolayers. The chains are strongly tilted in a rigid lattice formed due to these hydrogen-bonding interactions between the headgroups. The thermodynamical analysis leads to a critical temperature of the monolayer which is clearly different from the main phase transition temperature in bulk, indicating that there must be a different structural arrangement of the 1,3-diamidophospholipids in monolayers and in bilayers.

Monolayer properties of 1,3-diamidophospholipids.

The use of highly brilliant synchrotron light sources in the middle of the 1980s for X-ray diffraction has revolutionized the research of condensed monolayers. Since then, monolayers gained popularity as convenient quasi two-dimensional model systems widely used in biophysics and material science. This review focuses on structures observed in one-component phospholipid monolayers used as simplified two-dimensional models of biological membranes. In a monolayer system the phase transitions can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction. Competing interactions between the different parts of the molecule are responsible for the different monolayer structures. These forces can be modified by chemical variations of the hydrophobic chain region, of the hydrophilic head group region or of the interfacial region between chains and head groups. Modifications of monolayer structures triggered by changes of the chemical structure of double-chain phospholipids are highlighted in this paper.

Grazing incidence X-ray diffraction studies of condensed double-chain phospholipid monolayers formed at the soft air/water interface.

The use of new sophisticated and highly surface sensitive techniques as synchrotron based X-ray scattering techniques and in-house infrared reflection absorption spectroscopy (IRRAS) has revolutionized the monolayer research. Not only the determination of monolayer structures but also interactions between amphiphilic monolayers at the soft air/liquid interface and molecules dissolved in the subphase are important for many areas in material and life sciences. Monolayers are convenient quasi-two-dimensional model systems. This review focuses on interactions between amphiphilic molecules in binary and ternary mixtures as well as on interfacial interactions with interesting biomolecules dissolved in the subphase. The phase state of monolayers can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction or IRRAS. The interactions can be indirectly determined by the observed structure changes. Additionally, the yield of enzymatic reaction can be quantitatively determined, secondary structures of peptides and proteins can be measured and compared with those observed in bulk. In this way, the influence of a confinement on the structural properties of biomolecules can be determined. The adsorption of DNA can be quantified as well as the competing adsorption of ions at charged interfaces. The influence of modified nanoparticles on model membranes can be clearly determined. In this review, the relevance and utility of Langmuir monolayers as suitable models to study physical and chemical interactions at membrane surfaces are clearly demonstrated.

Langmuir monolayers as models to study processes at membrane surfaces.

Glycosylphosphatidylinositols (GPIs) are often attributed with the ability to associate with the organized membrane microdomains. GPI fragment 1 forms a highly ordered subgel-phase structure characterized by ordering of both headgroups and alkyl chains in thin layers. While investigating the driving forces behind the formation of these ordered monolayers, we have studied polymorphism of 1 under different conditions employing surface-sensitive X-ray diffraction methods. Three distinct polymorphs of 1 (I, II, and III) were identified and characterized by grazing incidence X-ray diffraction. Polymorphs II (a condensed monolayer structure) and III (highly ordered subgel phase) coexist on an 8 M urea solution subphase allowing for a detailed thermodynamic and kinetic analysis of the processes leading to the formation of these polymorphs. They are enantiotropic and can be directly interconverted by changes in temperature or lateral surface pressure. As a consequence, polymorph III nuclei of critical size (or larger) could be formed by density fluctuations in a multicomponent system, and they could continue to exist for a period of time even under conditions that would normally not allow for the nucleation of polymorph III. The processes described here could also lead to the formation of patches of highly ordered structures in a disordered environment of a cell membrane suggesting that GPIs may play a role in the formation of such domains.

Versatility of a glycosylphosphatidylinositol fragment in forming highly ordered polymorphs.

Carbon nanostructures that feature two-dimensional extended nanosheets are important components for technological applications such as high-performance composites, lithium-ion storage, photovoltaics and nanoelectronics. Chemical functionalization would render such structures better processable and more suited for tailored applications, but typically this is precluded by the high temperatures needed to prepare the nanosheets. Here, we report direct access to functional carbon nanosheets of uniform thickness at room temperature. We used amphiphiles that contain hexayne segments as metastable carbon precursors and self-assembled these into ordered monolayers at the air/water interface. Subsequent carbonization by ultraviolet irradiation in ambient conditions resulted in the quantitative carbonization of the hexayne sublayer. Carbon nanosheets prepared in this way retained their surface functionalization and featured an sp(2)-rich amorphous carbon structure comparable to that usually obtained on annealing above 800 °C. Moreover, they exhibited a molecularly defined thickness of 1.9 nm, were mechanically self-supporting over several micrometres and had macroscopic lateral dimensions on the order of centimetres.

Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature.

A series of long-tail alkyl ethanolamine analogs containing amide-, urea-, and thiourea moieties was synthesized and the behavior of the corresponding monolayers was assessed on the Langmuir-Pockels trough combined with grazing incidence X-ray diffraction experiments and complemented by computer simulations. All compounds form stable monolayers at the soft air/water interface. The phase behavior is dominated by strong intermolecular headgroup hydrogen bond networks. While the amide analog forms well-defined monolayer structures, the stronger hydrogen bonds in the urea analogs lead to the formation of small three-dimensional crystallites already during spreading due to concentration fluctuations. The hydrogen bonds in the thiourea case form a two-dimensional network, which ruptures temporarily during compression and is recovered in a self-healing process, while in the urea clusters the hydrogen bonds form a more planar framework with gliding planes keeping the structure intact during compression. Because the thiourea analogs are able to self-heal after rupture, such compounds could have interesting properties as tight, ordered, and self-healing monolayers.

Rigid urea and self-healing thiourea ethanolamine monolayers.

A series of 1,3-diamido phosphocholines was synthesized, and their potential to form stable bilayers was investigated. Large and giant unilamellar vesicles produced from these new lipids form a wide variety of faceted liposomes. Factors such as cooling rates and the careful choice of the liposome preparation method influence the formation of facets. Interdigitation was hypothesized as a main factor for the stabilization of facets and effectively monitored by small-angle X-ray scattering measurements.

Bilayer properties of 1,3-diamidophospholipids.

The self-association properties of anti-HIV catanionic dendrimers as multivalent galactosylceramide (GalCer)-derived inhibitors are presented. The study was designed to elucidate the origin of the relatively high cytotoxicity values of these anti-HIV catanionic dendrimers, which have previously been found to exhibit in vitro anti-HIV activity in the submicromolar range. The physicochemical properties of these catanionic dendrimers were studied to tentatively correlate the structural parameters with self-association and biological properties. We can conclude from this study that the absence of correlation between the hydrophobicity and the cytotoxicity of the catanionic systems could be explained by the partial segregation of the different partners of the catanionic entities.

Influence of Structural Parameters on the Self-Association Properties of Anti-HIV Catanionic Dendrimers.

The molecular interactions of three biologically important galactocerebrosides have been studied in monolayers formed at the soft air/water interface as 2D model membranes. Highly surface-sensitive techniques as GIXD (grazing incidence X-ray diffraction), IRRAS (infrared reflection-absorption spectroscopy), and BAM (Brewster angle microscopy) have been used. The study reveals that small differences in the chemical structure have a relevant impact on the physical-chemical properties and intermolecular interactions. The presence of a 2-d-hydroxyl group in the fatty acid favored for GalCer C24:0 (2-OH) monolayers a higher hydration state of the headgroup at low lateral pressures (<25 mN/m) and a higher condensation effect above 30 mN/m. An opposite behavior was recorded for GalCer C24:0 and GalCer C24:1, for which the intermolecular interactions are defined by the weakly hydrated but strong H-bonded interconnected head groups. Additionally, the 15-cis-double bond in the fatty acid chain (nervonic acid) of GalCer C24:1 stabilized the LE phase but did not disturb the packing parameters of the LC phase as compared with the saturated compound GalCer C24:0.

Article	Year
Multivalent catanionic GalCer analogs derived from first generation dendrimeric phosphonic acids. Bioorganic & medicinal chemistry\| PubMed ID: 19942442	2010
Biocompatible magnetite nanoparticles trapped at the air/water interface. Chemphyschem : a European journal of chemical physics and physical chemistry\| PubMed ID: 21058385	2010
Langmuir and Gibbs magnetite NP layers at the air/water interface. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 21174426	2011
Subgel phase structure in monolayers of glycosylphosphatidylinositol glycolipids. Angewandte Chemie (International ed. in English)\| PubMed ID: 23135766	2012
Monolayer properties of 1,3-diamidophospholipids. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 23822198	2013
Grazing incidence X-ray diffraction studies of condensed double-chain phospholipid monolayers formed at the soft air/water interface. Advances in colloid and interface science\| PubMed ID: 24507806	2014
Langmuir monolayers as models to study processes at membrane surfaces. Advances in colloid and interface science\| PubMed ID: 24612663	2014
Versatility of a glycosylphosphatidylinositol fragment in forming highly ordered polymorphs. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24725055	2014
Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature. Nature chemistry\| PubMed ID: 24848231	2014
Rigid urea and self-healing thiourea ethanolamine monolayers. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 25594235	2015
Bilayer properties of 1,3-diamidophospholipids. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 25642598	2015
Influence of Structural Parameters on the Self-Association Properties of Anti-HIV Catanionic Dendrimers. Chemphyschem : a European journal of chemical physics and physical chemistry\| PubMed ID: 26377841	2015
Impact of Structural Differences in Galactocerebrosides on the Behavior of 2D Monolayers. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 26907993	2016

Cristina Stefaniu

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