TY - JOUR A1 - Chandran, Sivasurender A1 - Dold, Stefanie A1 - Buvignier, Amaury A1 - Krannig, Kai-Steffen A1 - Schlaad, Helmut A1 - Reiter, Günter A1 - Reiter, Renate T1 - Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States JF - Langmuir N2 - Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b01212 SN - 0743-7463 VL - 31 IS - 23 SP - 6426 EP - 6435 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Das, Abhijna A1 - El-Tawargy, Ahmed S. A1 - Khechine, Emna A1 - Noack, Sebastian A1 - Schlaad, Helmut A1 - Reiter, Günter A1 - Reiter, Renate T1 - Controlling Nucleation in Quasi-Two-Dimensional Langmuir Poly(L-lactide) Films through Variation of the Rate of Compression JF - Langmuir N2 - We studied morphological changes in a quasi-two-dimensional Langmuir film of low molar mass poly(L-lactide) upon increasing the surface density, starting from randomly distributed molecules to a homogeneous monolayer of closely packed molecules, followed by nucleation and growth of mesoscopic, three-dimensional clusters from an overcompressed monolayer. The corresponding nucleation density of mesoscopic clusters within the monolayer can be tailored through variation of the rate of compression. For a given surface density and temperature, the nucleation probability was found to increase linearly with the rate of compression, allowing to adjust the density of mesoscopic clusters over nearly 2 orders magnitude. Y1 - 2019 U6 - https://doi.org/10.1021/acs.langmuir.9b00619 SN - 0743-7463 VL - 35 IS - 18 SP - 6129 EP - 6136 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Das, Abhijna A1 - Noack, Sebastian A1 - Schlaad, Helmut A1 - Reiter, Günter A1 - Reiter, Renate T1 - Exploring pathways to equilibrate Langmuir polymer films JF - Langmuir N2 - Focusing on the phase-coexistence region in Langmuir films of poly(L-lactide), we investigated changes in nonequilibrated morphologies and the corresponding features of the isotherms induced by different experimental pathways of lateral compression and expansion. In this coexistence region, the surface pressure II was larger than the expected equilibrium value and was found to increase upon compression, i.e., exhibited a nonhorizontal plateau. As shown earlier by using microscopic techniques [Langmuir 2019, 35, 6129-6136], in this plateau region, well-ordered mesoscopic clusters coexisted with a surrounding matrix phase. We succeeded in reducing Pi either by slowing down the rate of compression or through increasing the waiting time after stopping the movement of the barriers, which allowed for relaxations in the coexistence region. Intriguingly, the most significant pressure reduction was observed when recompressing a film that had already been compressed and expanded, if the recompression was started from an area value smaller than the one anticipated for the onset of the coexistence region. This observation suggests a "self-seeding" behavior, i.e., pre-existing nuclei allowed to circumvent the nucleation step. The decrease in Pi was accompanied by a transformation of the initially formed metastable mesoscopic clusters into a thermodynamically favored filamentary morphology. Our results demonstrate that it is practically impossible to obtain fully equilibrated coexisting phases in a Langmuir polymer film, neither under conditions of extremely slow continuous compression nor for long waiting times at a constant area in the coexistence region which allow for reorganization. Y1 - 2020 U6 - https://doi.org/10.1021/acs.langmuir.0c01268 SN - 0743-7463 VL - 36 IS - 28 SP - 8184 EP - 8192 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Knecht, Volker A1 - Reiter, Guenter A1 - Schlaad, Helmut A1 - Reiter, Renate T1 - Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations JF - Langmuir N2 - Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(gamma-benzyl-L-glutamate) (PBLG) peptides at the water/vapor interface. Preformed PBLG mono- or bilayers homogeneously covering the water surface laterally collapse in tens of nanoseconds, exposing significant proportions of empty water surface. This behavior was also observed in recent AFM experiments at similar areas per monomer, where a complete coverage had been assumed in earlier work. In the simulations, depending on the area per monomer, either elongated clusters or fibrils form, whose heights (together with the portion of empty water surface) increase over time. Peptides tend to align with respect to the fiber axis or with the major principal axis of the cluster, respectively. The aspect ratio of the cluster observed is 1.7 and, hence, comparable to though somewhat smaller than the aspect ratio of the peptides in alpha-helical conformation, which is 2.2. The heights of the fibrils is 3 nm after 20 ns and increases to 4.5 nm if the relaxation time is increased by 2 orders of magnitude, in agreement with the experiment. Aggregates with heights of about 3 or 4.5 nm are found to correspond to local bi- or trilayer structures, respectively. Y1 - 2017 U6 - https://doi.org/10.1021/acs.langmuir.7b01455 SN - 0743-7463 VL - 33 SP - 6492 EP - 6502 PB - American Chemical Society CY - Washington ER -