Small-angle neutron scattering (SANS) was used to investigate the size and shape of zwitterionic dodecyl phosphocholine (C12PC) micelles formed at various concentrations above its critical micelle concentration (CMC = 0.91 mM). The predominant spherical shape of micelles is revealed by SANS while the average micellar size was found to be broadly consistent with the hydrodynamic diameters determined by dynamic light scattering (DLS). Cryogenic tunneling electron microscopy (cryo-TEM) shows a uniform distribution of structures, proposing micelle monodispersity ( Supporting Information ). H/D substitution was utilized to selectively label the chain, head, or entire surfactant so that structural distributions within the micellar assembly could be investigated using fully protonated, head-deuterated, and tail-deuterated PC surfactants in D2O and fully deuterated surfactants in H2O. Using the analysis software we have developed, the four C12PC contrasts at a given concentration were simultaneously analyzed using various core-shell models consisting of a hydrophobic core and a shell representing hydrated polar headgroups. Results show that at 10 mM, C12PC micelles can be well represented by a spherical core-shell model with a core radius and shell thicknesses of 16.9 ± 0.5 and 10.2 ± 2.0 Å (total radius 27.1 ± 2.0 Å), respectively, with a surfactant aggregation number of 57 ± 5. As the concentration was increased, the SANS data revealed an increase in core-shell mixing, characterized by the emergence of an intermediate mixing region at the spherical core-shell interface. C12PC micelles at 100 mM were found to have a core radius and shell thicknesses of 19.6 ± 0.5 and 7.8 ± 2.0 Å, with an intermediate mixing region of 3.0 ± 0.5 Å. Further reduction in the shell thickness with concentration was also observed, coupled with an increased mixing of the core and shell regions and a reduction in miceller hydration, suggesting that concentration has a significant influence on surfactant packing and aggregation within micelles.

Nonionic alkyl ethoxylates (C(n)E(m)) have been extensively studied for their adsorption, aggregation, and solubilization individually and in small groups. In this work, we report a more systematic study of the effects of alkyl chain (tail) and ethoxylate (head) length on the size, shape, and extent of intermixing within the C(n)E(m) micelles in aqueous solution. Data from small angle neutron scattering (SANS) and nuclear magnetic resonance (NMR) were combined to undertake the structural characterization of micelles formed from the two separate series of surfactants C(n)E6 (n = 10, 12, 14) and C12E(m) (m = 5, 6, 8, 10, 12). The micellar core volume (V(core)) could be well determined with reasonable accuracy and linked to the hydrophilic-lipophilic balance (HLB) of the surfactant, with a sharp size and shape transition occurring around HLB = 12.5. NOESY NMR results revealed protrusions of the terminal methylene groups into the ethoxylate shell, thus providing direct experimental evidence for the phenomenon of "roughness" or intermixing of the core-shell interface. These detailed studies are compared with previous investigations on this model surfactant system.

This study reports the development and use of a novel thermoresponsive polymeric nanofilm for controlling cell adhesion and growth at 37 °C, and then cell detachment for cell recovery by subsequent temperature drop to the ambient temperature, without enzymatic cleavage or mechanical scraping. A copolymer, poly(N-isopropylacrylamide-co-hydroxypropyl methacrylate-co-3-(trimethoxysilyl)propyl methacrylate) (abbreviated PNIPAAm copolymer), was synthesized by free radical polymerization. The thermoresponses of the copolymer in aqueous solution were demonstrated by dynamic light scattering (DLS) through detecting the sensitive changes of copolymer aggregation against temperature. The DLS measurements revealed the lower critical solution temperature (LCST) at approximately 30 °C. The PNIPAAm film stability and robustness was provided through silyl cross-linking within the film and with the hydroxyl groups on the substrate surface. Film thickness, stability, and reversibility with respect to temperature switches were examined by spectroscopic ellipsometry (SE), atomic force microscopy (AFM), and contact angle measurements. The results confirmed the high extent of thermosensitivity and structural restoration based on the alterations of film thickness and surface wettability. The effective control of adhesion, growth, and detachment of HeLa and HEK293 cells demonstrated the physical controllability and cellular compatibility of the copolymer nanofilms. These PNIPAAm copolymer nanofilms could open up a convenient interfacial mediation for cell film production and cell expansion by nonenzymatic and nonmechanical cell recovery.

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