Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

Jennings, James; Carter, Matthew C. D.; Son, Chang Yun; Cui, Qiang; Lynn, David M.; Mahanthappa, Mahesh K.

doi:10.1021/acs.langmuir.0c01369

“…Based on previous experience with amine-based lipidoids with epoxide tails [26] we initially screened the temperature-dependent self-assembly of these new lipidoids following protonation by 1.0 M H2SO4. Samples were first annealed at 75°C in excess 1.0 M H2SO4 to encourage the system to reach its equilibrium protonated state.…”

Section: Lipidoid Prsa Screeningmentioning

confidence: 99%

“…This is consistent with previous results from epoxide-based lipidoids, where non-lamellar phases were only accessible when the 3NB headgroup was fully protonated. [26] Evidently, the extent of counterion hydration is also a significant factor determining the preferred LC phase. FTIR analysis showed higher water content in the 3NB10B' phosphate relative to the same lipidoid sulfate and chloride (Figure 3D).…”

Section: The Role Of Counterions In Prsamentioning

confidence: 99%

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids

Jennings

¹

,

Pabst

²

2022

Preprint

View full text Add to dashboard Cite

Bicontinuous cubic phases offer advantageous routes to a broad range of applied materials ranging from drug delivery devices to membranes. However, a priori design of molecules that assemble into these phases remains a technological challenge. In this article, high-throughput synthesis of lipidoids which undergo protonation-driven self-assembly (PrSA) into liquid crystalline phases is conducted. With this screening approach we discover 12 different multi-tail lipidoid structures capable of assembling into the bicontinuous double gyroid phase. The large quantity of morphological data uncovers unexpected design criteria that enable phase selection as a function of lipidoid headgroup size and architecture, tail length and architecture and counterion identity. Surprisingly, combining branched headgroups with bulky tails forces lipidoids to adopt unconventional pseudo-disc conformations that pack into double gyroid networks, entirely distinct from other synthetic or biological amphiphiles within bicontinuous cubic phases. From a multitude of possible applications, we demonstrate two examples of functional materials from lipidoid LCs. Firstly, the fabrication of highly aligned lipidoid gyroid films by interfacial PrSA, which are rapidly responsive to the external medium. Secondly, we show that colloidally-dispersed lipidoid cubosomes, e.g. for drug-delivery, are easily assembled using top-down solvent evaporation methods.

show abstract

“…Two previous studies described how lipidoids comprising a tetraamine headgroup and 6 linear epoxide tails had a strong tendency to undergo PrSA into lamellar and inverse micellar cubic LLC phases. 25,26 Given the broader range of commerciallyavailable structures we focused in this study on acrylates to produce lipidoids with four or more tails, using polyamine headgroups containing at least two primary amines and/or up to four secondary amines. Where more than one phase was observed, spots are colored with the initial phase on the left and the emergent phase (i.e.…”

Section: High-throughput Lipidoid Synthesismentioning

confidence: 99%

“…1D SAXS data from 3NB10B at 25 °C was imported into JANA2006 75 software and the structure factor intensity for each of the 6 assigned peaks fitted using a Le Bail refinement as described previously. 26 SUPERFLIP 76 was then applied to the structure factor intensity data as a charge-flipping algorithm which reconstructed 3D electron density maps of the double gyroid unit cell. These 3D maps were plotted and visualized in VESTA 77 .…”

Section: Representative Synthesis Of Lipidoids (3n10b)mentioning

confidence: 99%

See 1 more Smart Citation

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids

Jennings

¹

,

Pabst

²

2022

Preprint

0

View full text Add to dashboard Cite

Bicontinuous cubic phases offer advantageous routes to a broad range of applied materials ranging from drug delivery devices to membranes. However, a priori design of molecules that assemble into these phases remains a technological challenge. In this article, high-throughput synthesis of lipidoids which undergo protonation-driven self-assembly (PrSA) into liquid crystalline phases is conducted. With this screening approach we discover 12 different multi-tail lipidoid structures capable of assembling into the bicontinuous double gyroid phase. The large quantity of morphological data uncovers unexpected design criteria that enable phase selection as a function of lipidoid headgroup size and architecture, tail length and architecture and counterion identity. Surprisingly, combining branched headgroups with bulky tails forces lipidoids to adopt unconventional pseudo-disc conformations that pack into double gyroid networks, entirely distinct from other synthetic or biological amphiphiles within bicontinuous cubic phases. From a multitude of possible applications, we demonstrate two examples of functional materials from lipidoid LCs. Firstly, the fabrication of highly aligned lipidoid gyroid films by interfacial PrSA, which are rapidly responsive to the external medium. Secondly, we show that colloidally-dispersed lipidoid cubosomes, e.g. for drug-delivery, are easily assembled using top-down solvent evaporation methods.

show abstract

Predictive Molecular Models for Charged Materials Systems: From Energy Materials to Biomacromolecules

Jeong

¹

,

Jeong

²

,

Lee

³

et al. 2022

Self Cite

View full text Add to dashboard Cite

Electrostatic interactions play a dominant role in charged materials systems. Understanding the complex correlation between macroscopic properties with microscopic structures is of critical importance to develop rational design strategies for advanced materials. But the complexity of this challenging task is augmented by interfaces present in the charged materials systems, such as electrode–electrolyte interfaces or biological membranes. Over the last decades, predictive molecular simulations that are founded in fundamental physics and optimized for charged interfacial systems have proven their value in providing molecular understanding of physicochemical properties and functional mechanisms for diverse materials. Novel design strategies utilizing predictive models have been suggested as promising route for the rational design of materials with tailored properties. Here, an overview of recent advances in the understanding of charged interfacial systems aided by predictive molecular simulations is presented. Focusing on three types of charged interfaces found in energy materials and biomacromolecules, how the molecular models characterize ion structure, charge transport, morphology relation to the environment, and the thermodynamics/kinetics of molecular binding at the interfaces is discussed. The critical analysis brings two prominent field of energy materials and biological science under common perspective, to stimulate crossover in both research field that have been largely separated.

show abstract

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

Cited by 8 publications

References 78 publications

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids

Predictive Molecular Models for Charged Materials Systems: From Energy Materials to Biomacromolecules

Contact Info

Product

Resources

About