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.

Multiplicity of Morphologies in Poly (L-lactide) Bioresorbable Vascular Scaffolds

Julia A. Kornfield

California Institute of Technology, Chemistry & Chemical Engineering,  Pasadena CA 91125

Poly(L-lactide), PLLA, is the structural material of the first clinically approved bioresorbable vascular scaffold (BVS), a promising alternative to permanent metal stents for treatment of coronary heart disease. BVSs are transient implants that support the occluded artery for 6 months, and are completely resorbed in 2 years. Clinical trials of BVSs report restoration of arterial vasomotion and elimination of serious complications such as Late Stent Thrombosis. It is remarkable that a scaffold made from PLLA, known as a brittle polymer, does not fracture when crimped onto a balloon catheter or during deployment in the artery. X-ray microdiffraction revealed how PLLA acquired ductile character and that the crimping process creates localized regions of extreme anisotropy; PLLA chains in the scaffold change orientation from the hoop direction to the radial direction over micron-scale distances. The multiplicity of morphologies in the crimped scaffold enable a low-stress response during deployment, which avoids fracture of the PLLA hoops and leaves them with the strength needed to support the artery. Thus, the transformations of the semicrystalline PLLA microstructure during crimping explain the unexpected strength and ductility of the current BVS and point the way to thinner resorbable scaffolds in the future.

[1] Ailianou, A.; Ramachandran, K.; Kossuth, M.; Oberhauser, J.P.; Kornfield, J.A.*; “Multiplicity of Morphologies in Poly (L-lactide) Bioresorbable Vascular Scaffolds,” PNAS, 113, 11670-11675 (2016). (link)

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).
[2] A. M. Anton, R. Steyrleuthner, W. Kossack, D. Neher, F. Kremer, JACS 137, 6024(2008).
[3] A. M. Anton, R. Steyrleuthner, W. Kossack, D. Neher, F. Kremer, Macromolecules 49, 1798 (2016).

Crystallization of Supramolecular Polymers

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.
[2] Bao, J. N., Pan, P. J., et al. Polym. Chem. 2016, 7, 4891.
[3] Bao, J. N.; Pan, P. J., et al. Cryst. Growth Des. 2016, 16, 1502.

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
[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.

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

Large area three-dimensional polarization control in P(VDF-TrFE) polymer films on graphite

R. Roth1, M. Koch2, J. Schaab2, M. Lilienblum2, T. Thurn-Albrecht1, and K. Dörr1

1Institute of Physics, Martin Luther University Halle-Wittenberg, 06099 Halle, Germany
2Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 1-5/10,
8093 Zürich, Switzerland

Ferroelectric polymers are attractive candidates for functional layers in electronic devices like non-volatile memories, piezo- and magnetoelectric sensors, and capacitor-based high speed energy storage devices. Unfortunately, such thin films often reveal low di- and piezoelectric responses due to reduced crystalline and electrical dipole order, leading to compensation effects and low effective electric performance. One of the best characterized and often applied ferroelectric polymers is poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)). We will present results on micron-sized domains with three dimensional ferroelectric polarization alignment in P(VDF-TrFE) films on graphite. The ferroelectric domains have been achieved by a combined procedure of electrical poling and mechanical annealing with an atomic force microscopy tip. They show strongly increased lateral and vertical piezoresponse compared to the as-prepared film and can be deliberately written and switched.

Effects of Hofmeister Ion Series on Stability of a Salt Bridge

S. Pylaeva, H. Elgabarty, and D. Sebastiani

Theoretical Chemistry, Institute of Chemistry, Martin Luther University Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120, Halle, Germany

Salt bridges are important components of protein structure stability. They can be defined as an interaction of two aminoacid side chains of opposite charge [1]. Such Coulomb attraction interaction is sensitive to presence of other charged species in the vicinity. Concentration of charged species – free ions can be significant in a crowded environment of a living cell. Additionally Hofmeister ion series have been shown to have a significant impact on structure and dynamics of water and solvated proteins [2, 3].

We have investigated effects of Hofmeister ion series on an arginine – aspartic acid salt bridge by means of computer simulations [4]. Changes in thermodynamic properties of a salt bridge and dynamic properties of their solvation shells will be discussed in a poster.

[1] J.E. Donald, D.W. Kulp, W.F. DeGrado, Proteins, 79(3), 898 (2011).
[2] C. Allolio, N. Salas-Illanes, Y.S. Desmukh, M.R. Hansen, D. Sebastiani, JPCB 117(34), 9939 (2013)
[3] M.D. Smith, L. Cruz, JPCB 117, 6614 (2013)
[4] M. Fyta, R. Netz, JCP 136, 124103 (2012).

Amyloid peptide aggregation near interfaces

T. John1,2,3, L.L. Martin3, H.J. Risselada1,4, and B. Abel1,2

1Leibniz Institute of Surface Modification, Leipzig (Germany)
2Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Leipzig University, Leipzig (Germany)
3School of Chemistry, Monash University, Clayton (Australia)
4Department of Theoretical Physics, Georg-August-University Göttingen, Göttingen (Germany)

Amyloid peptides aggregate into characteristic fibrils with cross-β-sheet structure, also known as amyloid plaque. They are associated with several diseases such as Alzheimer’s disease or type II diabetes. However, there is evidence that indicates the soluble transient oligomers, instead of mature fibrils, as the toxic species. Amyloid-forming peptides are natively soluble and only aggregate under certain circumstances. Comprehensive knowledge on the aggregation mechanism and a detailed characterisation of the transient species is essential to understand the physiological role of these peptides [1].

Interfaces, such as nanoparticles, can act to accelerate or inhibit peptide aggregation. Experimental studies and molecular dynamics simulations (MD) presented an accelerated fibril formation in the presence of citrate-stabilised gold nanoparticles [2,3]. The role of gold surfaces in oligomer formation and peptide aggregation is discussed in this study. Moreover, possible mechanisms for the observed acceleration of the peptide aggregation by a reduction of the conformational space that is sampled are presented.

[1] F. Chiti, and C.M. Dobson, Annu. Rev. Biochem., 75, 333 (2006).
[2] A. Gladytz, B. Abel, and H.J. Risselada, Angew. Chem., Int. Ed., 55, 11242 
[3] A. Gladytz, M. Wagner, T. Häupl, C. Elsner, and B. Abel, Part. Part. Syst. 
Charact., 32, 573 (2015).