scholarly journals Mechanochemistry unveils stress transfer during sacrificial bond fracture of tough multiple network elastomers

2021 ◽  
Author(s):  
Yinjun Chen ◽  
Gabriel Sanoja ◽  
Costantino Creton
Keyword(s):  
Molecular Level ◽  
Stress Transfer ◽  
Soft Materials ◽  
Multiple Network

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.

scholarly journals From force-responsive molecules to quantifying and mapping stresses in soft materials

2020 ◽  
Vol 6 (20) ◽  
pp. eaaz5093 ◽  
Author(s):  
Yinjun Chen ◽  
C. Joshua Yeh ◽  
Yuan Qi ◽  
Rong Long ◽  
Costantino Creton
Keyword(s):  
Direct Method ◽  
Soft Materials ◽  
Internal Force ◽  
Optical Observations ◽  
Innovative Tool ◽  
Loaded Crack ◽  
Cross Linker ◽  
Multiple Network ◽  
Spatially Varying ◽  
Random Nature

Directly quantifying a spatially varying stress in soft materials is currently a great challenge. We propose a method to do that by detecting a change in visible light absorption. We incorporate a spiropyran (SP) force–activated mechanophore cross-linker in multiple-network elastomers. The random nature of the network structure of the polymer causes a progressive activation of the SP force probe with load, detectable by the change in color of the material. We first calibrate precisely the chromatic change in uniaxial tension. We then demonstrate that the nominal stress around a loaded crack can be detected for each pixel and that the measured values match quantitatively finite element simulations. This direct method to quantify stresses in soft materials with an internal force probe is an innovative tool that holds great potential to compare quantitatively stresses in different materials with simple optical observations.

Cyclic aromatic imides as a potential class of molecules for supramolecular interactions

CrystEngComm ◽  
2015 ◽  
Vol 17 (45) ◽  
pp. 8575-8595 ◽  
Author(s):  
Jayanta K. Nath ◽  
Jubaraj B. Baruah
Keyword(s):  
Molecular Level ◽  
Soft Materials ◽  
Building Blocks ◽  
Supramolecular Interactions ◽  
Stacking Interactions

Prospects of stacking interactions of imides beneficial to generation of new soft materials are projected by analysing examples of primary building blocks that provide a basis for understanding at the molecular level.

scholarly journals Control of extrinsic porosities in linked metal-organic polyhedra gels by imparting coordination-driven self-assembly with electrostatic repulsion

2022 ◽  
Author(s):  
Zaoming Wang ◽  
Takuma Aoyama ◽  
Eli Sanchez-Gonzales ◽  
Tomoko Inose ◽  
Kenji Urayama ◽  
...  
Keyword(s):  
Self Assembly ◽  
Molecular Level ◽  
Amorphous State ◽  
Soft Materials ◽  
Internal Cavity ◽  
Hydroxyl Groups ◽  
Electrostatic Repulsion ◽  
Outer Periphery ◽  
Metal Organic

The linkage of metal-organic polyhedra (MOPs) for the synthesis of porous soft materials is one of the promising strategies to combine processability with permanent porosity. Compared to the defined internal cavity of MOPs, it is still difficult to control the extrinsic porosities generated between crosslinked MOPs because of their random arrangements in their networks. Herein, we report a method to form linked MOP gels with controllable extrinsic porosities by introducing negative charges on the surface of MOPs that facilitates electrostatic repulsion between them. A hydrophilic rhodium-based cuboctahedral MOP (OHRhMOP) with 24 hydroxyl groups on its outer periphery can be controllably deprotonated to impart the MOP with tunable electrostatic repulsion in solution. This electrostatic repulsion between MOPs stabilizes the kinetically trapped state, in which a MOP is coordinated with various bisimidazole linkers in a monodentate fashion at a controllable link-er/MOP ratio. The heating of the kinetically trapped molecules leads to the formation of gels with similar colloidal networks but different extrinsic porosity. This strategy allows us to design the molecular-level networks and the resulting porosities even in the amorphous state.

scholarly journals Increasing silk fibre strength through heterogeneity of bundled fibrils

2013 ◽  
Vol 10 (82) ◽  
pp. 20130148 ◽  
Author(s):  
Steven W. Cranford
Keyword(s):  
Spider Silk ◽  
Mechanical Performance ◽  
Molecular Level ◽  
Three Dimensional ◽  
Stress Transfer ◽  
Variable Density ◽  
Fibre Strength ◽  
Silk Fibre ◽  
Spider Webs ◽  
Grain Model

Can naturally arising disorder in biological materials be beneficial? Materials scientists are continuously attempting to replicate the exemplary performance of materials such as spider silk, with detailed techniques and assembly procedures. At the same time, a spider does not precisely machine silk—imaging indicates that its fibrils are heterogeneous and irregular in cross section. While past investigations either focused on the building material (e.g. the molecular scale protein sequence and behaviour) or on the ultimate structural component (e.g. silk threads and spider webs), the bundled structure of fibrils that compose spider threads has been frequently overlooked. Herein, I exploit a molecular dynamics-based coarse-grain model to construct a fully three-dimensional fibril bundle, with a length on the order of micrometres. I probe the mechanical behaviour of bundled silk fibrils with variable density of heterogenic protrusions or globules, ranging from ideally homogeneous to a saturated distribution. Subject to stretching, the model indicates that cooperativity is enhanced by contact through low-force deformation and shear ‘locking’ between globules, increasing shear stress transfer by up to 200 per cent. In effect, introduction of a random and disordered structure can serve to improve mechanical performance. Moreover, addition of globules allows a tuning of free volume, and thus the wettability of silk (with implications for supercontraction) . These findings support the ability of silk to maintain near-molecular-level strength at the scale of silk threads, and the mechanism could be easily adopted as a strategy for synthetic fibres.

Preparatory Procedures for Electron Microscopic Analysis at the Molecular Level of Resolution

1978 ◽  
Vol 36 (3) ◽  
pp. 516-520
Author(s):  
F.J. Sjostrand
Keyword(s):  
Electron Microscope ◽  
Molecular Level ◽  
Microscopic Analysis ◽  
Resolving Power ◽  
Cellular Structures ◽  
Electron Microscopic ◽  
Systematic Analysis ◽  
Technical Developments ◽  
Thin Sectioning ◽  
Obvious Reason

In the 1940's and 1950's electron microscopy conferences were attended with everybody interested in learning about the latest technical developments for one very obvious reason. There was the electron microscope with its outstanding performance but nobody could make very much use of it because we were lacking proper techniques to prepare biological specimens. The development of the thin sectioning technique with its perfectioning in 1952 changed the situation and systematic analysis of the structure of cells could now be pursued. Since then electron microscopists have in general become satisfied with the level of resolution at which cellular structures can be analyzed when applying this technique. There has been little interest in trying to push the limit of resolution closer to that determined by the resolving power of the electron microscope.

RNA polymerase: Preparation and structural analysis of helical polymers

1984 ◽  
Vol 42 ◽  
pp. 152-153
Author(s):  
E. Loren Buhle ◽  
Pamela Rew ◽  
Ueli Aebi
Keyword(s):  
Structural Analysis ◽  
Rna Polymerase ◽  
Molecular Level ◽  
X Ray Diffraction ◽  
Helical Polymers ◽  
X Ray ◽  
E Coli ◽  
The Past ◽  
Ordered Arrays ◽  
Low Ionic Strength

While DNA-dependent RNA polymerase represents one of the key enzymes involved in transcription and ultimately in gene expression in procaryotic and eucaryotic cells, little progress has been made towards elucidation of its 3-D structure at the molecular level over the past few years. This is mainly because to date no 3-D crystals suitable for X-ray diffraction analysis have been obtained with this rather large (MW ~500 kd) multi-subunit (α2ββ'ζ). As an alternative, we have been trying to form ordered arrays of RNA polymerase from E. coli suitable for structural analysis in the electron microscope combined with image processing. Here we report about helical polymers induced from holoenzyme (α2ββ'ζ) at low ionic strength with 5-7 mM MnCl2 (see Fig. 1a). The presence of the ζ-subunit (MW 86 kd) is required to form these polymers, since the core enzyme (α2ββ') does fail to assemble into such structures under these conditions.

The Current Situation in Chemical Stabilization of Biological Materials

1972 ◽  
Vol 30 ◽  
pp. 132-133
Author(s):  
John H. Luft
Keyword(s):  
Electron Microscopy ◽  
Electron Microscope ◽  
Osmium Tetroxide ◽  
Molecular Level ◽  
Cross Linking ◽  
Chemical Stabilization ◽  
Specimen Preparation ◽  
Sufficient Condition ◽  
Radio Telescopes

With information processing devices such as radio telescopes, microscopes or hi-fi systems, the quality of the output often is limited by distortion or noise introduced at the input stage of the device. This analogy can be extended usefully to specimen preparation for the electron microscope; fixation, which initiates the processing sequence, is the single most important step and, unfortunately, is the least well understood. Although there is an abundance of fixation mixtures recommended in the light microscopy literature, osmium tetroxide and glutaraldehyde are favored for electron microscopy. These fixatives react vigorously with proteins at the molecular level. There is clear evidence for the cross-linking of proteins both by osmium tetroxide and glutaraldehyde and cross-linking may be a necessary if not sufficient condition to define fixatives as a class.

Atom-probe analysis of the solid-liquid interface

1995 ◽  
Vol 53 ◽  
pp. 676-677
Author(s):  
J.A. Panitz
Keyword(s):  
Molecular Level ◽  
Selective Adsorption ◽  
Electronic Devices ◽  
Atom Probe ◽  
Chemical Agent ◽  
Hostile Environment ◽  
Solid Interface ◽  
Solid Liquid Interface ◽  
Solid Liquid ◽  
Chemically Selective

The first few atomic layers of a solid can form a barrier between its interior and an often hostile environment. Although adsorption at the vacuum-solid interface has been studied in great detail, little is known about adsorption at the liquid-solid interface. Adsorption at a liquid-solid interface is of intrinsic interest, and is of technological importance because it provides a way to coat a surface with monolayer or multilayer structures. A pinhole free monolayer (with a reasonable dielectric constant) could lead to the development of nanoscale capacitors with unique characteristics and lithographic resists that surpass the resolution of their conventional counterparts. Chemically selective adsorption is of particular interest because it can be used to passivate a surface from external modification or change the wear and the lubrication properties of a surface to reflect new and useful properties. Immunochemical adsorption could be used to fabricate novel molecular electronic devices or to construct small, “smart”, unobtrusive sensors with the potential to detect a wide variety of preselected species at the molecular level. These might include a particular carcinogen in the environment, a specific type of explosive, a chemical agent, a virus, or even a tumor in the human body.

Shot-noise simulations of HREM images of polymer crystals

1989 ◽  
Vol 47 ◽  
pp. 342-343
Author(s):  
Philippe Pradère ◽  
Edwin L. Thomas
Keyword(s):  
Low Dose ◽  
Molecular Level ◽  
High Resolution Electron Microscopy ◽  
Crystal Defects ◽  
Inorganic Materials ◽  
Photographic Emulsion ◽  
Polymer Crystals ◽  
Resolution Electron ◽  
Recent Developments ◽  
Lattice Images

High Resolution Electron Microscopy (HREM) is a very powerful technique for the study of crystal defects at the molecular level. Unfortunately polymer crystals are beam sensitive and are destroyed almost instantly under the typical HREM imaging conditions used for inorganic materials. Recent developments of low dose imaging at low magnification have nevertheless permitted the attainment of lattice images of very radiation sensitive polymers such as poly-4-methylpentene-1 and enabled molecular level studies of crystal defects in somewhat more resistant ones such as polyparaxylylene (PPX) [2].With low dose conditions the images obtained are very noisy. Noise arises from the support film, photographic emulsion granularity and in particular, the statistical distribution of electrons at the typical doses of only few electrons per unit resolution area. Figure 1 shows the shapes of electron distribution, according to the Poisson formula :

Morphology of High-Performance Rigid-Rod Polymer Fibers and Molecular Composites

1989 ◽  
Vol 47 ◽  
pp. 338-339
Author(s):  
W.W. Adams ◽  
S. J. Krause
Keyword(s):  
Tensile Strength ◽  
High Performance ◽  
Liquid Crystalline ◽  
Molecular Level ◽  
Synergistic Effects ◽  
Tensile Modulus ◽  
Commercial Development ◽  
The Matrix ◽  
Molecular Composites ◽  
Rigid Rod

Rigid-rod polymers such as PBO, poly(paraphenylene benzobisoxazole), Figure 1a, are now in commercial development for use as high-performance fibers and for reinforcement at the molecular level in molecular composites. Spinning of liquid crystalline polyphosphoric acid solutions of PBO, followed by washing, drying, and tension heat treatment produces fibers which have the following properties: density of 1.59 g/cm3; tensile strength of 820 kpsi; tensile modulus of 52 Mpsi; compressive strength of 50 kpsi; they are electrically insulating; they do not absorb moisture; and they are insensitive to radiation, including ultraviolet. Since the chain modulus of PBO is estimated to be 730 GPa, the high stiffness also affords the opportunity to reinforce a flexible coil polymer at the molecular level, in analogy to a chopped fiber reinforced composite. The objectives of the molecular composite concept are to eliminate the thermal expansion coefficient mismatch between the fiber and the matrix, as occurs in conventional composites, to eliminate the interface between the fiber and the matrix, and, hopefully, to obtain synergistic effects from the exceptional stiffness of the rigid-rod molecule. These expectations have been confirmed in the case of blending rigid-rod PBZT, poly(paraphenylene benzobisthiazole), Figure 1b, with stiff-chain ABPBI, poly 2,5(6) benzimidazole, Fig. 1c A film with 30% PBZT/70% ABPBI had tensile strength 190 kpsi and tensile modulus of 13 Mpsi when solution spun from a 3% methane sulfonic acid solution into a film. The modulus, as predicted by rule of mixtures, for a film with this composition and with planar isotropic orientation, should be 16 Mpsi. The experimental value is 80% of the theoretical value indicating that the concept of a molecular composite is valid.

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