Nano-Imprinted Thin Films of Reactive, Azlactone-Containing Polymers: Combining Methods for the Topographic Patterning of Cell Substrates with Opportunities for Facile Post-Fabrication Chemical Functionalization

Approaches to the fabrication of surfaces that combine methods for the topographic patterning of soft materials with opportunities for facile, post-fabrication chemical functionalization could contribute significantly to advances in biotechnology and a broad range of other areas. Here, we report methods that can be used to introduce well defined nano- and microscale topographic features to thin films of reactive polymers containing azlactone functionality using nanoimprint lithography (NIL). We demonstrate that NIL can be used to imprint topographic patterns into thin films of poly(2-vinyl-4,4- dimethylazlactone) and a copolymer of methyl methacrylate and 2-vinyl- 4,4-dimethylazlactone using silicon masters having patterns of grooves and ridges ranging in width from 400 nm to 2μm, demonstrating the potential f this method to transfer patterns to films of these reactive polymers over a range of feature sizes and densities. We demonstrate further that the azlactone functionality of these polymers survives temperatures and pressures associated with NIL, and that topographically patterned films can be readily functionalized post-fabrication by treatment of surface-accessible azlactone functionality with small molecules and polymers containing primary amines. The results of experiments in which NIH-3T3 cells were seeded onto films imprinted with lined patterns having a pitch of 4 demonstrated that cells attach and proliferate on these azlactone-containing films and that they align in the direction of the imprinted pattern. Finally, we demonstrate that the treatment of these materials with amine-functionalized poly(ethylene glycol) (PEG) can be used to create regions of topographically patterned films that prevent cell adhesion. The results of this study suggest approaches to the functionalization of topographically patterned surfaces with a broad range of chemical functionality (e.g., peptides, proteins, carbohydrates, etc.) of biotechnological interest. The ability to manipulate and define both the physical topography and chemical functionality of these reactive materials could provide opportunities to investigate the combined effects of substrate topography and chemical functionality on cell behavior and may also be useful in a broad range of other applications

Nano-Imprinted Thin Films of Reactive, Azlactone-Containing Polymers: Combining Methods for the Topographic Patterning of Cell Substrates with Opportunities for Facile Post-Fabrication Chemical Functionalization

Laser scanning confocal microscopy (LSCM) and atomic force microscopy (AFM) were used to characterize changes in nanoscale structure that occur when ultrathin polyelectrolyte multilayers (PEMs) are incubated in aqueous media. The PEMs investigated here were fabricated by the deposition of alternating layers of plasmid DNA and a hydrolytically degradable polyamine onto a precursor film composed of alternating layers of linear poly(ethylene imine) (LPEI) and sodium poly(styrene sulfonate) (SPS). Past studies of these materials in the context of gene delivery revealed transformations from a morphology that is smooth and uniform to one characterized by the formation of nanometer-scale particulate structures. We demonstrate that in-plane registration of LSCM and AFM images acquired from the same locations of films fabricated using fluorescently labeled polyelectrolytes allows the spatial distribution of individual polyelectrolyte species to be determined relative to the locations of topographic features that form during this transformation. Our results suggest that this physical transformation leads to a morphology consisting of a relatively less disturbed portion of film composed of polyamine and DNA juxtaposed over an array of particulate structures composed predominantly of LPEI and SPS. Characterization by scanning electron microscopy and energy-dispersive X-ray microanalysis provides additional support for this interpretation. The combination of these different microscopy techniques provides insight into the structures and dynamics of these multicomponent thin films that cannot be achieved using any one method alone, and could prove useful for the further development of these assemblies as platforms for the surface-mediated delivery of DNA

Dramatic reduction of the effect of nanoconfinement on the glass transition of polymer films via addition of small-molecule diluent

At time of publication, all authors were at Northwestern University. Christopher Ellison is currently Asst. Professor at the University of Texas at Austin.The effect of nanoconfinement on the glass transition temperature T8 in thin polymer films is studied as a function of added small-molecule diluent or plasticizer. The decrease [increase] in T8 found in nanoconfined, neat polystyrene [poly(2-vinyl pyridine)] is suppressed by added diluent, with 13–20 nm thick polystyrene films exhibiting bulk T8 upon addition of 9 wt% pyrene or 4 wt% dioctylphthalate. This is explained by a connection between the size scale of the cooperative dynamics associated with T8, which decreases with added diluent, and the size scale of the nanoconfinement effect.Chemical Engineerin

A thicker Antarctic ice stream during the mid-Pliocene warm period

This work is supported by Stockholm University (APS), Norwegian Polar Institute/NARE under Grant “MAGIC-DML” (OF), the US National Science Foundation under Grant No. OPP-1542930 (NAL and JMH), Swedish Research Council under Grant No. 2016-04422 (JMH and APS), and the German Research Foundation Priority Programme 1158 “Antarctic Research” under Grant No. 365737614 (IR and Matthias Prange). R.S.J. is supported by the Australian Research Council under grants DE210101923 and SR200100005 (Securing Antarctica’s Environmental Future). The computations and data handling were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Centre (NSC), partially funded by the Swedish Research Council through grant agreement No. 2018-05973.Ice streams regulate most ice mass loss in Antarctica. Determining ice stream response to warmer conditions during the Pliocene could provide insights into their future behaviour, but this is hindered by a poor representation of subglacial topography in ice-sheet models. We address this limitation using a high-resolution model for Dronning Maud Land (East Antarctica). We show that contrary to dynamic thinning of the region’s ice streams following ice-shelf collapse, the largest ice stream, Jutulstraumen, thickens by 700 m despite lying on a retrograde bed slope. We attribute this counterintuitive thickening to a shallower Pliocene subglacial topography and inherent high lateral stresses at its flux gate. These conditions constrict ice drainage and, combined with increased snowfall, allow ice accumulation upstream. Similar stress balances and increased precipitation projections occur across 27% of present-day East Antarctica, and understanding how lateral stresses regulate ice-stream discharge is necessary for accurately assessing Antarctica’s future sea-level rise contribution.Publisher PDFPeer reviewe

A topographic hinge-zone divides coastal and inland ice dynamic regimes in East Antarctica

The impact of late Cenozoic climate on the East Antarctic Ice Sheet is uncertain. Poorly constrained patterns of relative ice thinning and thickening impair the reconstruction of past ice-sheet dynamics and global sea-level budgets. Here we quantify long-term ice cover of mountains protruding the ice-sheet surface in western Dronning Maud Land, using cosmogenic Chlorine-36, Aluminium-26, Beryllium-10, and Neon-21 from bedrock in an inverse modeling approach. We find that near-coastal sites experienced ice burial up to 75–97% of time since 1 Ma, while interior sites only experienced brief periods of ice burial, generally <20% of time since 1 Ma. Based on these results, we suggest that the escarpment in Dronning Maud Land acts as a hinge-zone, where ice-dynamic changes driven by grounding-line migration are attenuated inland from the coastal portions of the East Antarctic Ice Sheet, and where precipitation-controlled ice-thickness variations on the polar plateau taper off towards the coast

Antarctic ice stream thickening under Pliocene warmth

Ice streams regulate most ice mass loss in Antarctica. Determining their response to Pliocene warmth could provide insights into their future behaviour, but is hindered by poor representation of subglacial topography in ice-sheet models. We address this limitation using a high-resolution regional model for Dronning Maud Land (East Antarctica). We show that the region’s largest ice stream, Jutulstraumen, thickens by 700 m under warm late-Pliocene conditions despite ice-shelf collapse and a retrograde bed slope, while nearby ice streams thin. While it is known that unstable retreat on a retrograde slope can be slowed under certain conditions, this finding illustrates that an ice stream can thicken and gain mass. We attribute thickening to high lateral stresses at its flux gate, which constrict ice drainage. Similar stress balances occur today in 27% of East Antarctica, and understanding how lateral stresses regulate ice-stream discharge is necessary for accurately assessing Antarctica’s sea-level rise contribution

Antarctic ice stream thickening under Pliocene warmth

Ice streams regulate most ice mass loss in Antarctica. Determining their response to Pliocene warmth could provide insights into their future behaviour, but is hindered by poor representation of subglacial topography in ice-sheet models. We address this limitation using a high-resolution regional model for Dronning Maud Land (East Antarctica). We show that the region’s largest ice stream, Jutulstraumen, thickens by 700 m under warm late-Pliocene conditions despite ice-shelf collapse and a retrograde bed slope, while nearby ice streams thin. While it is known that unstable retreat on a retrograde slope can be slowed under certain conditions, this finding illustrates that an ice stream can thicken and gain mass. We attribute thickening to high lateral stresses at its flux gate, which constrict ice drainage. Similar stress balances occur today in 27% of East Antarctica, and understanding how lateral stresses regulate ice-stream discharge is necessary for accurately assessing Antarctica’s sea-level rise contribution