Interface-induced crystallization via prefreezing: A first order prewetting transition

Ann-Kristin Flieger, M. Schulz, and T. Thurn-Albrecht

Experimental Polymer Physics, Institute of Physics, Martin Luther University Halle-Wittenberg, 06120 Halle, Germany

Interface-induced crystallization of a liquid on a solid substrate can either occur via heterogeneous nucleation or via prefreezing. Whereas heterogeneous nucleation takes place at finite supercooling below the melting temperature Tm, in prefreezing a crystalline layer is formed at the surface of a solid substrate already above Tm. Wetting theory predicts a jump in thickness at the formation and a divergence upon approaching coexistence. However, the thickness of the prefreezing layer has not been experimentally measured so far.

We studied ultrathin films of polycaprolactone (PCL) during the crystallization on graphite. With in-situ AFM-measurements we observe prefreezing instead of heterogeneous nucleation. The corresponding crystalline layer is formed at a temperature above the bulk melting temperature. Similar observations were already made for polyethylene on graphite [1]. In that case however, a direct measurement of the thickness of the prefreezing layer was not possible. Here, we show directly the finite thickness of the prefreezing layer for PCL. It forms with a thickness of a few nanometers which further increases during cooling. This observation demonstrates the transition is of first order, as expected for a prewetting transition.

The results prove that prefreezing can be described by common wetting theory. The studied system PCL-graphite is of importance for applications since graphitic materials are widely used as fillers for PCL.

[1] A.-K. Löhmann, T. Henze, and T. Thurn-Albrecht, PNAS 49, 17368-17372 (2014). (link)

Crystallization in melts of semi-flexible hard polymer chains: An interplay of entropies and dimensions

T. Shakirov, W. Paul

Institut für Physik, Martin Luther Universität Halle-Wittenberg, 06099 Halle 

Stochastic Approximation Monte Carlo simulations [1] are employed to obtain the complete thermodynamic equilibrium information for a melt of short, semi-flexible polymer chains with purely repulsive intermolecular interactions. Thermodynamics is obtained based on the density of states of our simple coarse-grained model, which varies by up to 5000 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density [2]. The lyotropic three-dimensional orientational ordering transition drives the crystallization and is accompanied by a two-dimensional hexagonal ordering transition in the plane perpendicular to the chains. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition is similar to the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. The tilt of the chain axis with respect to the lamella surface makes this a rotator II phase.

[1] B. Werlich, T. Shakirov, M. P. Taylor, W. Paul, Comput. Phys. Commun. 186, 65, (2015) (link)
[2] T. Shakirov, W. Paul, preprint

The Functional Role of Nanocrystals in Native and Artificial Spider Silk

A. M. Anton and F. Kremer

Peter Debye Institute for Soft Matter Physics, University of Leipzig, Linnéstr. 5, 04103 Leipzig

Spider dragline silk exhibits remarkable characteristics such as exceptional toughness arising from high tensile strength combined with great elasticity. Its mechanical properties are based on a refined architecture on the molecular scale: Proteins with highly repetitive core motifs aggregate into nanometer-sized crystals, rich non alanine in β-sheet secondary structure, surrounded by an amorphous, glycine rich matrix. During spinning the less ordered parts are elongated, which orients both substructures and gives rise to an inherent non-equilibrium state. Thus, external stress is directly transferred to the crystallites, as demonstrated by FTIR experiments in combination with uniaxial stress [1] or hydrostatic pressure [2].Spider dragline silk exhibits remarkable characteristics such as exceptional toughness arising from high tensile strength combined with great elasticity. Its mechanical properties are based on a refined architecture on the molecular scale: Proteins with highly repetitive core motifs aggregate into nanometer-sized crystals, rich non alanine in β sheet secondary structure, surrounded by an amorphous, glycine rich matrix. During spinning the less ordered parts are elongated, which orients both substructures and gives rise to an inherent non-equilibrium state. Thus, external stress is directly transferred to the crystallites, as demonstrated by FTIR experiments in combination with uniaxial stress [1] or hydrostatic pressure [2].Even though the protein structure has been thoroughly studied, until recently it was not possible to artificially re-create this exceptional (morphological and functional) architecture. We show that wet spinning of a novel biomimetic protein results in fibers with a similar nanostructure as the natural template. However, only post spinning strain induces a microscopic non-equilibrium that gives rise to a similar mechanism of energy dissipation as in natural spider silk and comparable macroscopic toughness [3,4].

[1] P. Papadopoulos, J. Sölter, and F. Kremer, Eur. Phys. J. E 24, 193 (2007). (link)
[2] A. M. Anton, C. Kuntscher, F. Kremer et al., Macromolecules 46, 4919 (2013). (link)
[3] A. Heidebrecht, T. Scheibel et al., Adv. Mater. 27, 2189 (2015). (link)
[4] A. M. Anton, M. Beiner, T. Scheibel, F. Kremer et al, manuscript submitted

Serine substitution in Amyloid-β – a possible link between β-Methylamino-L-alanine and Alzheimer’s disease?

A. Korn1, M. Krüger2, S. Roßner3, D. Huster1

1Institute of Medical Physics and Biophysics, University of Leipzig, D-04107 Leipzig, Germany.
2Institute of Anatomy, University of Leipzig, D-04103 Leipzig, Germany
3Paul-Flechsig-Institut für Hirnforschung, Liebigstraße 19 D-04103 Leipzig, Germany

β-Methylamino-L-alanine (BMAA) was found as a possible reason for increased ALS-PDC (amyotrophic lateral sclerosis–parkinsonism/dementia complex) [1]. It is a non- proteinogenic amino acid produced by cyanobacteria that can be enriched via the food chain in plants, seafood, higher animals, and humans [2]. This is a critical factor because cyanobacteria are known for their excessive blooms not only in marine ecosystems but also in lakes that are used as fresh water source for millions of people supplying BMAA to human nutrition [3].
Although BMAA is known as a neurotoxin for several decades, its mode of action is still topic of controversial discussions. One of the more commonly accepted pathologic pathways is its function as a neurotransmitter mimetic where it can overstimulate glutamate receptors, deplete glutathione, increase free radical concentration and subsequently leads to neuronal damage [4]. Besides this, BMAA can also be misincorporated in proteins. Recent findings showed that serine tRNA synthetase accepts BMAA as substrate which may finally lead to a serine-BMAA substitution [5].
Assuming that BMAA can substitute Ser8 or Ser26 of Amyloid-β, the question arises if this may alter Amyloid-β fibrillation and structure leading to a higher risk for neurodegenerative pathogenesis.

[1] J. Pablo, S.A. Banack, PA Cox, T.E. Johnson, S. Papapetropoulos, W.G. Bradley, A. Buck, D.C. Mash, Acta Neurologica Scandinavica, 120, 216 (2009) (link)
[2] C.L. Garcia-Rodenas, M. Affolter, G. Vinyes-Pares, C.A. De Castro, L.G, Karagounis, Y.M. Zhang, P.Y Wang, S.K Thakkar, Nutrients, 8, 606, (2016) (link)
[3] M. Monteiro, M. Costa, C. Moreira, V.M. Vasconcelos, M.S. Baptista, Journal of Applied Phycology, 29, 879 (2017) (link)
[4] F. D’Mello, N. Braidy, H. Marcal, G. Guillemin, F. Rossi, M. Chinian, D. Laurent, C. Teo, B.A. Neilan, Neurotoxicity Research, 31, 245 (2017) (link)

Deformation and nano-void formation of β-phase isotactic polypropylene during uniaxial stretching

T. Kawai and S. Kuroda

Graduate School of Science and Engineering, Gunma University, Ota, Gunma 373-0057, Japan

Pseudo-hexagonal β-form is known to transform into thermodynamically stable monoclinic α -form during elongation. It is also reported that the nano-sized void is formed during deformation. Since the crystal deformation/void formation mechanism of β-iPP is not fully understood, we aim in this study to clarify the deformation behavior of β-iPP in both terms of crystal transformation (angstrom scale) and the void formation (nanometer scale). The film of β-iPP was prepared by melt crystallization of PP with 0.2% DCNDCA as a nucleating agent (kβ = 0.94). The samples were drawn uniaxially at 100ºC with fixed strain rate of 0.66 min-1. Synchrotron radiation WAXD/SAXS measurements were performed at BL40B2 in SPring-8, Japan. Deformation of β -iPP proceeded as follows; (i) at the yielding point of ε = 0.1 β-form started to decrease followed by increase in amorphous fraction. (ii) at ε = 0.4, α-form crystal with the chain orientation parallel to the stretching direction was formed. Importantly, as soon as α -form crystallized, formation of nano-sized void was initiated. Above findings strongly suggest that the β -form transforms to amorphous and/or mesomorphic state before recrystallization into α-form crystal. A detailed analysis on void structure by means of SAXS streak scattering is also to be discussed based on lamellar deformation during elongation.

Spatial Orientation and Order of Molecular Subunits in Films of Organic Semiconductors

A. M. Anton and F. Kremer

Peter Debye Institute for Soft Matter Physics, Leipzig University, Linnéstr. 5, 04013 Leipzig

Conjugated donor/acceptor copolymers have obtained significant attention due to their soft matter properties combined with semiconducting characteristics, which allows for their operation in organic field effect transistors or solar cells, for instance [1]. Because the devices’ macroscopic properties arise from the materials’ molecular organization, a detailed understanding of the microscopic structure is essential for targeted developments. In order to shed light on the spatial orientation and order in thin films of P(NDI2OD-T2) the technique of Infrared Transition Moment Orientational Analysis (IR-TMOA) is employed. Therefore, the absorbance of structure-specific bands depending on the inclination of the sample and on the polarization of the IR light is evaluated [2,3]. This enables to determine the tensor of absorption separately for the respective molecular moieties as well as to deduce the orientation of atomistic planes defined through the polymer subunits, relative to the substrate and hence relative to each other. We found that the solvent used for spin coating (chlorobenzene or a chloronaphthalene:xylene mixture) determines the alignment of the T2 part (either face on or edge on), whereas the NDI unit is not affected. On the other hand, the inclination of the NDI plane is well retained for diverse sample thicknesses in between nano- and micrometers.

[1] A. C. Arias, J. D. MacKenzie, I. McCulloch, J. Rivnay, A. Salleo, Chem. Rev. 110, 3 (2010). (link)
[2] A. M. Anton, R. Steyrleuthner, W. Kossack, D. Neher, F. Kremer, JACS 137, 6034 (2008). (link)
[3] A. M. Anton, R. Steyrleuthner, W. Kossack, D. Neher, F. Kremer, Macromolecules 49, 1798 (2016). (link)

Crystallization of Supramolecular Polymers Linked by Multiple Hydrogen Bonds

Pengju Pan, Jianna Bao, Xiaohua Chang, Ruoxing Chang, Guorong Shan, Yongzhong Bao

State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, 38 Zheda Road, Hangzhou 310027, P. R. China.

Supramolecular polymers (SMPs) have different crystallization behavior from conventional polymers. Crystallization of SMPs occurs in a “confined” and “dynamic” manner. Because of the reversible and stimuli-responsive natures of non-covalent bonds in SMPs, crystalline structure and crystallization kinetics of SMPs depend strongly on crystallization conditions (e.g., crystallization temperature, Tc). This offers a feasible way to tune the physical properties and functions of SMPs in processing. We first selected the 2-ureido-4[1H]-pyrimidione (UPy)-bonded poly(L-lactic acid) (PLLA) as a model SMP and investigated the crystallization kinetics, polymorphic crystalline structure, and phase transition of supramolecular PLLAs (SM-PLLAs). Crystallization rate and crystallinity of SM-PLLAs were strongly depressed as compared to the non-functionalized PLLA precursors. Crystalline structure of SM-PLLAs was sensitive to Tc. A low Tc (80~100 °C) facilitated the formation of metastable β crystals of PLLA in SM-PLLAs. The β crystals formed in SM-PLLAs transformed into the more stable α crystals in the following heating process. We further studied the stereocomplex crystallization between UPy-functionalized PLLA and poly(D-lactic acid) (PDLA). It was found that the stereocomplexation ability of PLLA and PDLA was highly improved after UPy end functionalization; this was ascribed to the enhanced interchain interaction.

[1] Chang, R. X., Pan, P. J., et al. Macromolecules 2015, 48, 7872. (link)
[2] Bao, J. N., Pan, P. J., et al. Polym. Chem. 2016, 7, 4891. (link)
[3] Bao, J. N.; Pan, P. J., et al. Cryst. Growth Des. 2016, 16, 1502. (link)

Structure and Morphology Orientation of Comb-like Polymers with Rigid Backbones

V. Danke1,2, G. Gupta1,2, and M. Beiner1,2

1Fraunhofer-Institut für Mikrostruktur von Werkstoffen und Systemen IMWS, Walter-Hülse-Straße 1, 06120, Halle, Germany
2Institut für Chemie, Martin Luther Universität Halle-Wittenberg, 06120, Halle, Germany

Comb-like polymers with rigid backbones and flexible side chains are an important class of functional materials with applications in various fields like organic semiconductors and light weight components in high performance composite materials. A common feature of such polymers is the formation of layered structures with typical spacing in the 1-3 nm range wherein the side chains (long methylene sequences) aggregate to form alkyl nanodomains [1]. Crystallographic analysis in poly (1,4-phenylene-2,5-n-didecyloxy terephthalate) (PPDOT) and poly (2,5-didecyloxy-1,4-phenylene vinylene) (DOPPV) each having 10 alkyl carbons per side chain shows that PPDOT exhibits an orthorhombic unit cell, whereas the DOPPV is characterized by a monoclinic unit cell. The interplay between backbone and side chain packing within the alkyl nanodomain leading to different crystallographic states is discussed. Investigations on molecular orientation in extruded fibers of poly (1,4-phenylene-2,5-n-dialkyloxy terephthalate)s (PPAOT) and poly (2,5-dialkyloxy-1,4-phenylene vinylene)s (AOPPV) show that the backbones in case of PPAOT align along the shear direction whereas in AOPPV they align preferentially perpendicular to the shear direction [2]. Potential reasons for the differences in the preferred orientations for PPAOT and AOPPV are considered.

[1] About different packing states of alkyl groups in comb-like polymers with rigid backbones. T. Babur, G. Gupta and M. Beiner, Soft Matter, 2016, 12, 8093-8097 (link)
[2] Interrelations Between Side Chain and Main Chain Packing in Different Crystal Modifications of Alkoxylated Polyesters. G. Gupta, V. Danke, T. Babur, and M. Beiner. J. Phys. Chem. B, 2017, 121, 4583-45. (link)

Influence of Propylene-based Elastomer on Stress-whitening for Impact copolymer

Ying Lu2, Yingying Sun1, Lan Li1 and Yongfeng Men2

1ExxonMobil Asia Pacific Research & Development Co., Ltd, 1099 Zixing Road, Minhang District, 200241 Shanghai, P.R. China
2State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, 130022 Changchun, P.R. China

Two pure impact copolymer polypropylenes (ICP), one pure homo-polypropylene (HPP) and their compounds with different type and fraction of VistamaxxTM propylene-based elastomer (“Vistamaxx”) were used to investigate the stress whitening activated in the impact processes via ultra-small angle X-ray scattering technique. A characteristic macroscopic whitening of deformed materials was showed due to the formation of voids or cavities with a typical size up to the wavelength of visible light, that is, some hundreds of nanometers. The stress whitening presented in ICP is confirmed to be caused by the interfaces existed between ethylene-propylene (EP) rubber and polypropylene (PP) matrix, such kind stress whitening is apparently unlike the one initiated in the crystal phase of HPP. In this study, Vistamaxx with high crystallinity can adjust the compatibility of EP rubber and PP matrix which results in a reduction of interfaces, thus, a phenomenon of reduced stress whitening can be observed in blends of ICP with Vistamaxx. However, the enhancement of stress whitening can be found in blends of ICP with Vistamaxx which occupied low crystallinity. Such behaviors can be assigned to the poor compatibility between Vistamaxx and PP matrix.

Early oligomers and the process of oligomerization of the amyloid peptides Aβ40 and Aβ42

Jana Rüdel, Maria Ott

Institute of Physics, Martin-Luther-University Halle-Wittenberg

Similar to synthetic polymers like polyamides, amyloidogenic proteins as well as short peptide sequences display the inherent ability to form long and very stable fibers called fibrils. Along the pathway from a single peptide to the mature fibrils, various transient and long-lived intermediate states are formed spanning the whole range between small and mostly unstructured oligomers to well-ordered, β-sheet rich protofibrils. As early oligomeric states were found to be neurotoxic, they are a presumptive key to understand the development of neurodegenerative diseases [1].
In order to reveal the leading mechanisms of amyloid aggregation, we studied the appearance and development of early oligomeric states of the Aβ40- and the Aβ42-peptides using a combined approach of single-molecule fluorescence spectroscopy and imaging techniques, such as TEM and AFM. Additionally, thermodynamic stabilities of the detected amyloid aggregates were studied by the use of ultrafast-scanning calorimetry.
We could reveal and characterize soluble oligomers of the Aβ40- and the Aβ42-peptide and found distinct differences in terms of size distribution as well as the process of oligomerization. While the fibrillation of Aβ42-peptides includes small and large oligomers, the assembly of Aβ40-peptide display only small oligomers and an overall slower kinetic of fibril formation. We will discuss our results by the use of thermodynamic models of self-assembly.

[1] F. Bemporad and F. Chiti, Protein misfolded oligomers: Experimental approaches, mechanism of formation, and structure-toxicity relationships, Chem. Biol. 19 (2012), 315 (link)