A Molecular Dynamics Study of Mechanical and Conformational Properties of Conjugated Polymer Thin Films.

Understanding and predicting the mechanical and conformational properties of conjugated polymer (CP) thin films are a central focus in flexible electronic device research. Employing molecular dynamics simulations with an architecture-transferable chemistry-specific coarse-grained (CG) model of poly(3-alkylthiophene)s (P3ATs), developed by using an energy renormalization approach, we investigate the mechanical and conformational behavior of P3AT thin films during deformation. The density profiles and measures of local mobility identify a softer interfacial layer for all films, the thickness of which does not depend on M w or side-chain length. Remarkably, Young's modulus measured via nanoindentation is more sensitive to M w than for tensile tests, which we attribute to distinct deformation mechanisms. High-M w thin films show increased toughness, whereas longer side-chain lengths of P3AT resulted in lower Young's modulus. Fractures in low-M w thin films occur through chain pullout due to insufficient chain entanglement and crazing in the plastic region. Importantly, stretching promoted both chain alignment and longer conjugation lengths of P3AT, potentially enhancing its electronic properties. For instance, at room temperature, stretching P3HT thin films to 150% increases the conjugated length of P3HT thin films from 2.7 nm to 4.7 nm, aligning with previous experimental findings and all-atom simulation results. Furthermore, high-M w thin films display elevated friction forces due to the chain accumulation on the indenter, with negligible variations in the friction coefficient across all thin film systems. These findings offer valuable insights that enhance our understanding and guide the rational design of CP thin films in flexible electronics.

Effect of solvent quality and sidechain architecture on conjugated polymer chain conformation in solution.

Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C4H9 to -C12H25, poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A2 ranging from 0.3 to 4.7 × 10-3 cm3 mol g-2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A2, indicating a better polymer-solvent interaction, wherein A2 for toluene increases from -5.9 to 1.4 × 10-3 cm3 mol g-2, and in CB, A2 ranges from 1.0 to 4.7 × 10-3 cm3 mol g-2 when sidechain length increases from -C6H13 to -C12H25. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A2 (∼0.5 × 10-3 cm3 mol g-2) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics.

Understanding the thermomechanical behavior of graphene-reinforced conjugated polymer nanocomposites via coarse-grained modeling.

Graphene-reinforced conjugated polymer (CP) nanocomposites are attractive for flexible and electronic devices, but their mechanical properties have been less explored at a fundamental level. Here, we present a predictive multiscale modeling framework for graphene-reinforced poly(3-alkylthiophene) (P3AT) nanocomposites via atomistically informed coarse-grained molecular dynamics simulations to investigate temperature-dependent thermomechanical properties at a molecular level. Our results reveal reduced graphene dispersion with increasing graphene loading. Nanocomposites with shorter P3AT side chains, lower temperatures, and higher graphene content exhibit stronger mechanical responses, which correlates with polymer dynamics. The elastic modulus increases linearly with the graphene content, which slightly deviates from the "Halpin-Tsai" micromechanical model prediction. Local stiffness analysis shows that graphene possesses the highest stiffness, followed by the P3AT backbone and side chains. Deformation-induced stronger chain alignment of the P3AT backbone compared to graphene may further promote conductive behavior. Our findings provide insights into the dynamical heterogeneity of nanocomposites, paving the way for understanding and predicting their thermomechanical properties.

Crystallization and melting of polymer chains on graphene and graphene oxide.

This study employs all-atomistic (AA) molecular dynamics (MD) simulations to investigate the crystallization and melting behavior of polar and nonpolar polymer chains on monolayers of graphene and graphene oxide (GO). Polyvinyl alcohol (PVA) and polyethylene (PE) are used as representative polar and nonpolar polymers, respectively. A modified order parameter is introduced to quantify the degree of two-dimensional (2D) crystallization of polymer chains. Our results show that PVA and PE chains exhibit significantly different crystallization behavior. PVA chains tend to form a more rounded, denser, and folded-stemmed lamellar structure, while PE chains tend to form an elongated straight pattern. The presence of oxidation groups on the GO substrate reduces the crystallinity of both PVA and PE chains, which is derived from the analysis of modified order parameter. Meanwhile, the crystallization patterns of polymer chains are influenced by the percentage, chemical components, and distribution of the oxidation groups. In addition, our study reveals that 2D crystalized polymer chains exhibit different melting behavior depending on their polarity. PVA chains exhibit a more molecular weight-dependent melting temperature than PE chains, which have a lower melting temperature and are relatively insensitive to molecular weight. These findings highlight the critical role of substrate and chain polarity in the crystallization and melting of polymer chains. Overall, our study provides valuable insights into the design of graphene-based polymer heterostructures and composites with tailored properties.

Molecular Structure and Conformational Design of Donor-Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property.

Tuning the optoelectronic properties of donor-acceptor conjugated polymers (D-A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D-A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D-A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D-A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.

Crumpling Defective Graphene Sheets.

Upon crumpling, graphene sheets yield intriguing hierarchical structures with high resistance to compression and aggregation, garnering a great deal of attention in recent years for their remarkable potential in a variety of applications. Here, we aim to understand the effect of Stone-Wales (SW) defects, i.e., a typical topological defect of graphene, on the crumpling behavior of graphene sheets at a fundamental level. By employing atomistically informed coarse-grained molecular dynamics (CG-MD) simulations, we find that SW defects strongly influence the sheet conformation as manifested by the change in size scaling laws and weaken the self-adhesion of the sheet during the crumpling process. Remarkably, the analyses of the internal structures (i.e., local curvatures, stresses, and cross-section patterns) of crumpled graphene emphasize the enhanced mechanical heterogeneity and "glass-like" amorphous state elicited by SW defects. Our findings pave the way for understanding and exploring the tailored design of crumpled structure via defect engineering.

Crumpled Kirigami.

When a thin sheet is confined to a volume much smaller than its length (or width), it forms a complex state of sharp bends, point-like developable cones (d-cones) and extended ridges known as crumpled matter. One interesting feature of this state, is its high resistance to compression given its light weight. While the origins of this strength still remain a matter of debate, much has been learned through simple experiments and models. Very little work has explored how crumpling is affected by the sheet's topology, which is curious given the close relation between geometry and mechanics. In this work, we couple confocal microscopy with simple force experiments and coarse-grained molecular dynamics (CG-MD) simulations to explore how adding cuts to a sheet alters its behavior in the crumpled state. We find that cutting does not significantly alter the overall compressive behaviour: force scales as a power law irrespective of cuts and magnitudes are only slightly reduced by cutting. Remarkably, when examining regions of high curvature in the crumpled sheets we see evidence of significant changes in the distribution of curvature in cut sheets.

Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains.

The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (Tg ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher Tg . In this work, the Tg s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermally cleavable side chains at 140 °C, is found to remove more than 95% of alkyl side chains in 24 h, and raise the backbone Tg from 23 to 75 °C. Coarse grain molecular dynamics simulations are used to understand the Tg dependence on side chain cleavage. X-ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. The combined effect of enhancing Tg and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices.

ß-Sheet Richness of the Circulating Tumor-Derived Extracellular Vesicles for Noninvasive Pancreatic Cancer Screening.

Tumor-derived extracellular vesicles (EVs) are under intensive study for their potential as noninvasive diagnosis biomarkers. Most EV-based cancer diagnostic assays trace supernumerary of a single cancer-associated marker or marker signatures. These types of biomarker assays are either subtype-specific or vulnerable to be masked by high background signals. In this study, we introduce using the ß-sheet richness (BR) of the tumor-derived EVs as an effective way to discriminate EVs originating from malignant and nonmalignant cells, where EV contents are evaluated as a collective attribute rather than single factors. Circular dichroism, Fourier transform infrared spectroscopy, fluorescence staining assays, and a de novo workflow combining proteomics, bioinformatics, and protein folding simulations were employed to validate the collective attribute at both cellular and EV levels. Based on the BR of the tumorous EVs, we integrated immunoprecipitation and fluorescence labeling targeting the circulating tumor-derived EVs in serum and developed the process into a clinical assay, named EvIPThT. The assay can distinguish patients with and without malignant disease in a pilot cohort, with weak correlations to prognosis biomarkers, suggesting the potential for a cancer screening panel with existing prognostic biomarkers to improve overall performance.

Understanding the Role of Self-Adhesion in Crumpling Behaviors of Sheet Macromolecules.

Understanding the crumpling behavior of two-dimensional (2D) macromolecular sheet materials is of fundamental importance in engineering and technological applications. Among the various properties of these sheets, interfacial adhesion critically contributes to the formation of crumpled structures. Here, we present a coarse-grained molecular dynamics (CG-MD) simulation study to explore the fundamental role of self-adhesion in the crumpling behaviors of macromolecular sheets having varying masses or sizes. By evaluating the potential energy evolution, our results show that the self-adhesion plays a dominant role in the crumpling behavior of the sheets compared to in-plane and out-of-plane stiffnesses. The macromolecular sheets with higher adhesion tend to form a self-folding planar structure at the quasi-equilibrium state of the crumpling and exhibit a lower packing efficiency as evaluated by the fractal dimension of the system. Notably, during the crumpling process, both the radius of gyration Rg and the hydrodynamic radius Rh of the macromolecular sheet can be quantitatively described by the power-law scaling relationships associated with adhesion. The evaluation of the shape descriptors indicates that the overall crumpling behavior of macromolecular sheets can be characterized by three regimes, i.e., the less bent, intermediate, and highly crumpled regimes, dominated by edge-bending, self-adhesion, and further compression, respectively. The internal structural analysis further reveals that the sheet transforms from the initially ordered state to the disordered glassy state upon crumpling, which can be facilitated by greater self-adhesion. Our study provides fundamental insights into the adhesion-dependent structural behavior of macromolecular sheets under crumpling, which is essential for establishing the structure-processing-property relationships for crumpled macromolecular sheets.

Double-stranded Let-7 mimics, potential candidates for cancer gene therapy

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MicroRNAs (miRNAs), a class of small, single-stranded endogenous RNAs, act as post-transcriptional regulators of gene expression. The ability of one single miRNA regulating multiple functionally related mRNAs makes it a new potential candidate for cancer gene therapy. Let-7s miRNAs have been demonstrated as tumor-suppressor genes in various types of cancers, providing one choice of gene therapy by replenishing this miRNA. In the present studies, we demonstrate that the chemically synthesized, double-stranded Let-7 mimics can inhibit the growth and migration and induce the cell cycle arrest of lung cancer cell lines in vitro. Let-7 mimics silence gene expression by binding to the 3' UTR of targeting mRNAs. Mutation of seed sequence significantly depresses the gene silencing activity of Let-7 mimics. Our results also demonstrate that it is possible to increase the activity of Let-7s through mutating the sequence within the 3'end of the antisense strand. Directly, co-transfection Let-7 mimics with active siRNAs impairs the anti-cancer activities of Let-7 mimics. However, a 3-h interval between the introduction of Let-7 mimics and a kind of siRNA avoids the competition and enhances the anti-cancer activities of Let-7 mimics. Taken together, these results have revealed that Let-7s mimics are potential candidates for cancer gene therapy (AU)