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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Amphiphilic Heterografted Molecular Bottlebrushes with Tertiary Amine-Containing Side Chains as Efficient and Robust pH-Responsive Emulsifiers

Here, by combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli-responsive polymers, we show that MBBs with randomly grafted poly(n-butyl acrylate) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH-responsive emulsifiers. Water-in-toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water-insoluble, and the MBBs desorbed from the interface, causing de-emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Temperature controlled transformations of giant unilamellar vesicles of amphiphilic triblock copolymers synthesized via microfluidic mixing

We report on a simple approach for synthesis of temperature-responsive giant unilamellar vesicles (GUVs) from poly(N-vinylcaprolactam) 15 -block-poly(dimethylsiloxane) 65 -block-poly(N-vinylcaprolactam) 15 (PVCL 15 -PDMS65-PVCL 15 ) triblock copolymer and non-temperature responsive small and giant vesicles from novel poly(N-vinylpyrrolidone)-block-poly(dimethylsiloxane)-block-poly(N-vinylpyrrolidone) (PVPON 15 -PDMS 65 -PVPON 15 and PVPON 6- PDMS 30- PVPON 6 ) triblock copolymers using microfluidic mixing at 25 °C. We show that temperature-responsive PVCL 15 -PDMS 65- PVCL 15 GUVs with the average diameter of 1.4 ± 0.2 µm while being stable at room temperature for at least 14 days, transformed irreversibly into small vesicles of 168 ± 40 nm after incubation of their aqueous solution at 42 °C for 24 h. We hypothesized that this transformation is induced by local compressive stresses of the vesicle membrane due to the collapse of PVCL blocks above the copolymer lower critical solution temperature (LCST) leading to the decrease of the vesicle membrane thickness. Consequently, we found that the temperature-induced size transformation of the PVCL-based GUVs at 42°C can be suppressed by substituting PVCL with its hydrophilic homologue PVPON, or by suppressing the PVCL's LCST behavior through hydrogen-bonding with tannic acid molecules. In the former case, novel PVPON n -PDMS m -PVPON n triblock copolymers (n = 15, m = 65 and n = 6, m = 30) assemble into vesicles stable from 25 °C to 55 °C as confirmed by optical and electron microscopy, dynamic light scattering (DLS) and small-angle neutron scattering (SANS). In the latter, hydrogen bonding interactions of PVCL with the polyphenol tannic acid (TA) at room temperature resulted in stable PVCL-based GUVs at 42°C as confirmed by optical, electron, and atomic force microscopies. We also found that physical crosslinking of the PVCL corona through hydrogen bonding with TA in PVCL 15- PDMS 65- PVCL 15 GUVs will delay their low pH-induced degradation at 37°C by 48 h compared to non-modified GUVs. Our findings open opportunities for the development of temperature-regulated stable micro-vehicles that would change their structural characteristics in the physiologically relevant temperature range from 25 to 42°C and can be utilized for cell mimicking studies. The developed GUVs also have potential in theranostic drug delivery as substitutes for polymer microcapsules and lipid microbubbles as well as for stimuli-triggered sensing, protection, and rapid response in an aqueous environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Nanostructural and rheological transitions of pH-responsive supramolecular systems involving a zwitterionic amphiphile and a triamine

Supramolecular aqueous complexes of a synthesized zwitterionic surfactant, 2-(dimethyl(octadecyl)ammonio)acetate (stearyl betaine) and diethylenetriamine, have been found to display pH-tunable rheological properties without the need for a co-surfactant. For this supramolecular system, the dynamically changing interplay among the constituents is responsible for the rich phase behavior including hollow nanotubules, bilayers, and vesicles. A further hypothesis is that hollow nanotubular structure is highly desirable for achieving chain entanglement geometries with reduced mesh size. The rheological properties of the suspension were measured using a rotational rheometer. An analysis using zero-shear viscosities at various temperatures as well as differential scanning calorimetry(DSC) helped shed light on thermodynamic and phase transitions taking place. The morphology of the suspension was analyzed by using a combination of small angle x-ray scattering(SAXS) and atomic force microscopy(AFM). Large steady-shear viscosities (up to ~160 Pa.s) and viscoelastic behavior was observed in acidic conditions which diminished upon increasing the pH. A novel analysis consisting of measured thermodynamic quantities such as activation energy(E a ) and enthalpy of transition(ΔH T ) further allude to the rich pH-sensitive nanoarchitecture of the system. Rather than commonly observed wormlike micelles, hollow nanotubules, as long as 1.6 µm were observed at pH 4 which disintegrated to bilayer sheets and vesicles upon increasing pH. Finally, gaining a comprehensive understanding from all the results, a transition mechanism between different suspension architectures was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.

99 GENERAL AND MISCELLANEOUS↗