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ACS Appl Bio Mater
2019 Aug 19;28:3639-3647. doi: 10.1021/acsabm.9b00489.
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Self-Assembly of a Catalytically Active Lipopeptide and Its Incorporation into Cubosomes.
Castelletto V
,
Edwards-Gayle CJC
,
Hamley IW
,
Pelin JNBD
,
Alves WA
,
Aguilar AM
,
Seitsonen J
,
Ruokolainen J
.
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The self-assembly and biocatalytic activity of the proline-functionalized lipopeptide PRW-NH-C16 are examined and compared to that of the related PRW-O-C16 lipopeptide, which differs in having an ester linker between the lipid chain and tripeptide headgroup instead of an amide linker. Lipopeptide PRW-NH-C16 self-assembles into spherical micelles above a critical aggregation concentration, similar to the behavior of PRW-O-C16 reported previously [B. M. Soares et al. Phys. Chem. Chem. Phys., 2017, 19, 1181-1189]. However, PRW-NH-C16 shows an improved catalytic activity in a model aldol reaction. In addition, we explore the incorporation of the biocatalytic lipopeptide into lipid cubosomes. SAXS shows that increasing lipopeptide concentration leads to an expansion of the monoolein cubosome lattice spacing and a loss of long-range cubic order as the lipopeptide is encapsulated in the cubosomes. At higher loadings of lipopeptide, reduced cubosome formation is observed at the expense of vesicle formation. Our results show that the peptide-lipid chain linker does not influence self-assembly but does impart an improved biocatalytic activity. Furthermore, we show that lipopeptides can be incorporated into lipid cubosomes, leading to restructuring into vesicles at high loadings. These findings point the way toward the future development of bioactive lipopeptide assemblies and slow release cubosome-based delivery systems.
Scheme 1. Molecular
Structures of PRW-NH-C16 and PRW–O-C16
Figure 1. Spectroscopic characterization
of PRW-NH-C16 self-assembly
in water: cac = 0.04 wt % PRW-NH-C16 is determined from
the concentration dependence of the emission wavelength of tryptophan
(a) and the ANS assay (b); (c) CD spectra below and above the cac,
(d) FTIR data above the cac.
Figure 2. Self-assembly of PRW-NH-C16. (a) Cryo-TEM image showing
micelles. (b) SAXS data (open symbols) with a model fit (red line)
to the core–shell micelle form factor.
Figure 3. (a) SAXS
profiles for cubosomes made of 10 wt % monoolein + 1 wt
% F127 and loaded with (i) 0, (ii) 0.1, (iii) 0.2, and (iv) 0.3 wt
% PRW-NH–CH16. (b) Dependence of the spacing of
the first reflection in panel a with the concentration of peptide.
Figure 4. Cryo-TEM images of cubosomes made of 10 wt %
monoolein + 1 wt %
F127 and loaded with (a–d) 0, (e, f) 0.1, and (g, h) 0.3 wt
% PRW-NH-C16. Scale bars are (a, c, g) 100 or (e) 50 nm.
Panels b, d, f, and h are FFT images of panels a, c, e, and g, respectively.
Figure 5. Representative cryo-TEM images of cubosomes
made of 10 wt % monoolein
+ 1 wt % F127 and loaded with (a) 0.1, (b) 0.2, and (c) 0.3 wt % PRWNH-C16. Scale bars are 100 nm. (d) Counting of cubosomes vs vesicles
as a function of the PRW-NH-C16 concentration, measured
from the corresponding cryo-TEM images.
Figure 6. Cytotoxicity data, conditions
as indicated. Error bars indicate
standard deviations of technical errors. (a) 161Br fibroblasts. (b)
MCF-7 human breast cancer cells.
Barauskas,
Cubic phase nanoparticles (Cubosome): principles for controlling size, structure, and stability.
2005, Pubmed
Barauskas,
Cubic phase nanoparticles (Cubosome): principles for controlling size, structure, and stability.
2005,
Pubmed
Barth,
Infrared spectroscopy of proteins.
2007,
Pubmed
Barth,
The infrared absorption of amino acid side chains.
2000,
Pubmed
Boge,
Freeze-dried and re-hydrated liquid crystalline nanoparticles stabilized with disaccharides for drug-delivery of the plectasin derivative AP114 antimicrobial peptide.
2018,
Pubmed
Boge,
Lipid-Based Liquid Crystals As Carriers for Antimicrobial Peptides: Phase Behavior and Antimicrobial Effect.
2016,
Pubmed
Breßler,
SASfit: a tool for small-angle scattering data analysis using a library of analytical expressions.
2015,
Pubmed
Casal,
Polymorphic phase behaviour of phospholipid membranes studied by infrared spectroscopy.
1984,
Pubmed
Castelletto,
Self-Assembly of the Toll-Like Receptor Agonist Macrophage-Activating Lipopeptide MALP-2 and of Its Constituent Peptide.
2016,
Pubmed
Castelletto,
Self-Assembly, Tunable Hydrogel Properties, and Selective Anti-Cancer Activity of a Carnosine-Derived Lipidated Peptide.
2019,
Pubmed
Castelletto,
Influence of end-capping on the self-assembly of model amyloid peptide fragments.
2011,
Pubmed
Cheetham,
Supramolecular nanostructures formed by anticancer drug assembly.
2013,
Pubmed
Cui,
Self-assembly of peptide amphiphiles: from molecules to nanostructures to biomaterials.
2010,
Pubmed
Czeslik,
Temperature- and pressure-dependent phase behavior of monoacylglycerides monoolein and monoelaidin.
1995,
Pubmed
Dehsorkhi,
Self-assembling amphiphilic peptides.
2014,
Pubmed
Eker,
Abeta(1-28) fragment of the amyloid peptide predominantly adopts a polyproline II conformation in an acidic solution.
2004,
Pubmed
Gaussier,
Replacement of trifluoroacetic acid with HCl in the hydrophobic purification steps of pediocin PA-1: a structural effect.
2002,
Pubmed
Hamley,
Lipopeptides: from self-assembly to bioactivity.
2015,
Pubmed
Hamley,
Self-assembly of three bacterially-derived bioactive lipopeptides.
2013,
Pubmed
Hawe,
Extrinsic fluorescent dyes as tools for protein characterization.
2008,
Pubmed
Keiderling,
Unfolded peptides and proteins studied with infrared absorption and vibrational circular dichroism spectra.
2002,
Pubmed
Kluzek,
Influence of a pH-sensitive polymer on the structure of monoolein cubosomes.
2017,
Pubmed
Kulkarni,
Monoolein: a magic lipid?
2011,
Pubmed
Larsson,
Stability of polycarbonate and polystyrene surfaces after hydrophilization with high intensity oxygen RF plasma.
2002,
Pubmed
Löwik,
Peptide based amphiphiles.
2004,
Pubmed
Matson,
Peptide Self-Assembly for Crafting Functional Biological Materials.
2011,
Pubmed
Meikle,
Incorporation of antimicrobial peptides in nanostructured lipid membrane mimetic bilayer cubosomes.
2017,
Pubmed
Mulet,
Advances in drug delivery and medical imaging using colloidal lyotropic liquid crystalline dispersions.
2013,
Pubmed
Murgia,
Drug-loaded fluorescent cubosomes: versatile nanoparticles for potential theranostic applications.
2013,
Pubmed
Pelton,
Spectroscopic methods for analysis of protein secondary structure.
2000,
Pubmed
Qiu,
The phase diagram of the monoolein/water system: metastability and equilibrium aspects.
2000,
Pubmed
Rodríguez-Llansola,
Supramolecular catalysis with extended aggregates and gels: inversion of stereoselectivity caused by self-assembly.
2010,
Pubmed
Rodríguez-Llansola,
Switchable performance of an L-proline-derived basic catalyst controlled by supramolecular gelation.
2009,
Pubmed
Sagalowicz,
Crystallography of dispersed liquid crystalline phases studied by cryo-transmission electron microscopy.
2006,
Pubmed
Silva,
Structural behaviour and gene delivery in complexes formed between DNA and arginine-containing peptide amphiphiles.
2016,
Pubmed
Soares,
Chiral organocatalysts based on lipopeptide micelles for aldol reactions in water.
2017,
Pubmed
,
Echinobase
Tyler,
Electrostatic swelling of bicontinuous cubic lipid phases.
2015,
Pubmed
Vivian,
Mechanisms of tryptophan fluorescence shifts in proteins.
2001,
Pubmed
Woody,
Circular dichroism spectrum of peptides in the poly(Pro)II conformation.
2009,
Pubmed
Woody,
Circular dichroism.
1995,
Pubmed
Yaghmur,
Emulsified microemulsions and oil-containing liquid crystalline phases.
2005,
Pubmed
Yaghmur,
Tuning curvature and stability of monoolein bilayers by designer lipid-like peptide surfactants.
2007,
Pubmed
Yaghmur,
Characterization and potential applications of nanostructured aqueous dispersions.
2009,
Pubmed
Zha,
Self-assembly of cytotoxic peptide amphiphiles into supramolecular membranes for cancer therapy.
2013,
Pubmed
Zhao,
Potential of Bacillus subtilis lipopeptides in anti-cancer I: induction of apoptosis and paraptosis and inhibition of autophagy in K562 cells.
2018,
Pubmed
Zozulia,
Catalytic peptide assemblies.
2018,
Pubmed