Dynamics of polymer molecules with sacrificial bond and hidden length systems: towards a physically-based mesoscopic constitutive law.
Ontology highlight
ABSTRACT:
SUBMITTER: Elbanna AE
PROVIDER: S-EPMC3614968 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Incorporating hidden length into polymer chains can improve their mechanical properties, because release of the hidden length under mechanical loads enables localized strain relief without chain fracture. To date, the design of hidden length has focused primarily on the choice of the sacrificial bonds holding the hidden length together. Here we demonstrate the advantages of adding mechanochemical reactivity to hidden length itself, using a new mechanophore that integrates (Z)-2,3-diphenylcyclobutene-1,4-dicarboxylate, with hitherto unknown mechanochemistry, into macrocyclic cinnamate dimers. Stretching a polymer of this mechanophore more than doubles the chain contour length without fracture. DFT calculations indicate that the sequential dissociation of the dimer, followed by cyclobutene isomerization at higher forces yields a chain fracture energy 11 times that of a simple polyester of the same initial contour length and preserves high energy-dissipating capacity up to ∼3 nN. In sonicated solutions cyclobutene isomerizes to two distinct products by competing reaction paths, validating the computed mechanochemical mechanism and suggesting an experimental approach to quantifying the distribution of single-chain forces under diverse loading scenarios.
| S-EPMC7596784 | biostudies-literature
Project description:The fabrication of solution-processed nontoxic mesoporous Bi2S3 structures is demonstrated and the suitability of these structures for use in hybrid solar cells investigated. Mesoporous Bi2S3 electrodes are prepared via thermal decomposition of a thin film composed of a bismuth xanthate single source precursor. The resultant Bi2S3 films are made up of regular needles with approximate dimensions of 50×500 nm, as confirmed by scanning electron microscopy (SEM). The crystallinity of the Bi2S3 is found to be dependent on the annealing temperature, as determined by X-ray diffraction. The porous Bi2S3 films are infiltrated with the hole conductor P3HT to generate novel hybrid films, and laser-based transient absorption spectroscopy is used to interrogate the charge-separation reaction at the resulting Bi2S3/P3HT heterojunction. Specifically, optical excitation of the hybrid films results in efficient and long-lived charge separation (microsecond to millisecond timescale), thereby rendering such films suitable for the development of novel low-cost solar-energy conversion devices.
| S-EPMC4501321 | biostudies-literature
Project description:Constitutive laws and crystal plasticity in diamond deformation have been the subjects of substantial interest since synthetic diamond was made in 1950's. To date, however, little is known quantitatively regarding its brittle-ductile properties and yield strength at high temperatures. Here we report, for the first time, the strain-stress constitutive relations and experimental demonstration of deformation mechanisms under confined high pressure. The deformation at room temperature is essentially brittle, cataclastic, and mostly accommodated by fracturing on {111} plane with no plastic yielding at uniaxial strains up to 15%. At elevated temperatures of 1000°C and 1200°C diamond crystals exhibit significant ductile flow with corresponding yield strength of 7.9 and 6.3 GPa, indicating that diamond starts to weaken when temperature is over 1000°C. At high temperature the plastic deformation and ductile flow is meditated by the <110>{111} dislocation glide and a very active {111} micro-twinning.
| S-EPMC3500768 | biostudies-other
Project description:The molecular level transfer of stress from a stiff percolating filler to a stretchable matrix is a crucial and generic mechanism of toughening in soft materials. Yet the molecular details of how this transfer occurs have so far been experimentally unreachable. Model multiple network elastomers containing spiropyran (SP) force sensors incorporated into the stiff filler network or into the stretchable matrix network are used here to detect and investigate the mechanism of stress transfer between distinct populations of polymer strands. We find that as the filler network progressively breaks by random bond scission, there is a critical stress where cooperative bond scission occurs and the macroscopic stretch increases discontinuously by necking. Surprisingly, SP molecules reveal that even in the necked region both filler and matrix chains share the load, with roughly 90% of the SPs force-activated in the filler chains before necking still being loaded in the necked region where significant activation of the SP incorporated into the matrix chains occurs. This result, where both networks remain loaded upon necking, is qualitatively consistent with the model proposed by Brown, where holes or microcracks are formed in the stiff regions and are bridged by stretched matrix chains. Detection of merocyanine (i.e. activated SP) fluorescence by confocal microscopy shows that such microcrack formation is also active at the crack tip even for materials that do not exhibit macroscopic necking. Additionally, we demonstrate that when the ethyl acrylate monomer is replaced by hexyl methacrylate in the first network, preventing molecular connections between the two networks, the stress transmission is less efficient. This study outlines the different roles played by these multiple networks in the onset of fracture and provides molecular insights for the construction of molecular models of fracture of elastomers.
| S-EPMC8386638 | biostudies-literature
Project description:We investigate the rate-length scaling law of protein folding, a key undetermined scaling law in the analytical theory of protein folding. Available data yield statistically significant evidence for the existence of a rate-length law capable of predicting folding times to within about two orders of magnitude (over 9 decades of variation). Unambiguous determination of the functional form of such a law could provide key mechanistic insight into folding. Four proposed laws from literature (power law, exponential, and two stretched exponentials) are tested against one another, and it is found that the power law best explains the data by a modest margin. We conclude that more data is necessary to unequivocally infer the rate-length law. Such data could be obtained through a small number of protein folding experiments on large protein domains.
| S-EPMC3855161 | biostudies-literature
Project description:A constitutive model to describe the triaxial load-response spectrum of plain concrete in both tension and shear was developed. The inelastic phenomena are described using the plastic flow with direction determined by the gradient of the plastic potential. A new plastic potential is introduced and experimentally fitted to ensure better estimate of the load direction. This approach allows to control the inelastic dilatancy in terms of the inelastic deformation of the material. By overlaying the plastic potential on modified Etse and Willam's yield surface (both defined on the Haigh-Westergaard coordinates), the results showed that the two curves do not undergo similar stress states for a given strength level. It is, therefore, necessary that each surface goes through the current stress state to ensure adequate evaluation of normal vectors. A closed-form solution to accurately predict the triaxial stress state in concrete has been proposed. The predictive capabilities of the proposed model are evaluated by comparing predicted and measured stresses. The proposed model is shown to be accurate in predicting stress state of concrete.
| S-EPMC5452676 | biostudies-other
Project description:In the classical framework, the Navier-Stokes-Fourier equations are obtained through the linear uncoupled thermodynamic force-flux relations which guarantee the non-negativity of the entropy production. However, the conventional thermodynamic descrip- tion is only valid when the Knudsen number is sufficiently small. Here, it is shown that the range of validity of the Navier-Stokes-Fourier equations can be extended by incorporating the nonlinear coupling among the thermodynamic forces and fluxes. The resulting system of conservation laws closed with the coupled constitutive relations is able to describe many interesting rarefaction effects, such as Knudsen paradox, transpiration flows, thermal stress, heat flux without temperature gradients, etc., which cannot be predicted by the classical Navier-Stokes-Fourier equations. For this system of equations, a set of phenomenological boundary conditions, which respect the second law of thermodynamics, is also derived. Some of the benchmark problems in fluid mechanics are studied to show the applicability of the derived equations and boundary conditions.
| S-EPMC6237507 | biostudies-literature
Project description:Recent advances in 3D printing technology have enabled unprecedented design freedom across an ever-expanding portfolio of materials. However, direct 3D printing of soft polymeric materials such as polydimethylsiloxane (PDMS) is challenging, especially for structural complexities such as high-aspect ratio (>20) structures, 3D microfluidic channels (∼150 μm diameter), and biomimetic microstructures. This work presents a novel processing method entailing 3D printing of a thin-walled sacrificial metallic mold, soft polymer casting, and acidic etching of the mold. The proposed workflow enables the facile fabrication of various complex, bioinspired PDMS structures (e.g., 3D double helical microfluidic channels embedded inside high-aspect ratio pillars) that are difficult or impossible to fabricate using currently available techniques. The microfluidic channels are further infused with conductive graphene nanoplatelet ink to realize two flexible piezoresistive microelectromechanical (MEMS) sensors (a bioinspired flow/tactile sensor and a dome-like force sensor) with embedded sensing elements. The MEMS force sensor is integrated into a Philips 9000 series electric shaver to demonstrate its application in "smart" consumer products in the future. Aided by current trends in industrialization and miniaturization in metal 3D printing, the proposed workflow shows promise as a low-temperature, scalable, and cleanroom-free technique of fabricating complex, soft polymeric, biomimetic structures, and embedded MEMS sensors.
| S-EPMC7812595 | biostudies-literature
Project description:The MRE11-RAD50-Nijmegen breakage syndrome 1 (NBS1 [MRN]) complex accumulates at sites of DNA double-strand breaks (DSBs) in microscopically discernible nuclear foci. Focus formation by the MRN complex is dependent on MDC1, a large nuclear protein that directly interacts with phosphorylated H2AX. In this study, we identified a region in MDC1 that is essential for the focal accumulation of the MRN complex at sites of DNA damage. This region contains multiple conserved acidic sequence motifs that are constitutively phosphorylated in vivo. We show that these motifs are efficiently phosphorylated by caseine kinase 2 (CK2) in vitro and directly interact with the N-terminal forkhead-associated domain of NBS1 in a phosphorylation-dependent manner. Mutation of these conserved motifs in MDC1 or depletion of CK2 by small interfering RNA disrupts the interaction between MDC1 and NBS1 and abrogates accumulation of the MRN complex at sites of DNA DSBs in vivo. Thus, our data reveal the mechanism by which MDC1 physically couples the MRN complex to damaged chromatin.
| S-EPMC2315671 | biostudies-literature
Project description:Wafer-scale fabrication of complex nanofluidic systems with integrated electronics is essential to realizing ubiquitous, compact, reliable, high-sensitivity and low-cost biomolecular sensors. Here we report a scalable fabrication strategy capable of producing nanofluidic chips with complex designs and down to single-digit nanometre dimensions over 200?mm wafer scale. Compatible with semiconductor industry standard complementary metal-oxide semiconductor logic circuit fabrication processes, this strategy extracts a patterned sacrificial silicon layer through hundreds of millions of nanoscale vent holes on each chip by gas-phase Xenon difluoride etching. Using single-molecule fluorescence imaging, we demonstrate these sacrificial nanofluidic chips can function to controllably and completely stretch lambda DNA in a two-dimensional nanofluidic network comprising channels and pillars. The flexible nanofluidic structure design, wafer-scale fabrication, single-digit nanometre channels, reliable fluidic sealing and low thermal budget make our strategy a potentially universal approach to integrating functional planar nanofluidic systems with logic circuits for lab-on-a-chip applications.
| S-EPMC5264239 | biostudies-literature