scholarly journals Excellent Stability in Water of Single-Chain Nanoparticles against Chain Scission by Sonication

2018 ◽  
Vol 39 (6) ◽  
pp. 1700675 ◽  
Author(s):  
Marina González-Burgos ◽  
Edurne González ◽  
José A. Pomposo
Keyword(s):  
Chain Scission ◽  
Single Chain ◽  
Excellent Stability

scholarly journals Fracture of Elastomeric Materials by Crosslink Failure

2018 ◽  
Vol 85 (8) ◽  
Author(s):  
Yunwei Mao ◽  
Lallit Anand
Keyword(s):  
Free Energy ◽  
Failure Mode ◽  
Chain Scission ◽  
Progressive Damage ◽  
Central Feature ◽  
Single Chain ◽  
Elastomeric Material ◽  
Damage And Fracture ◽  
Elastomeric Materials ◽  
Covalent Crosslinks

If an elastomeric material is subjected to sufficiently large deformations, it eventually fractures. There are two typical micromechanisms of failure in such materials: chain scission and crosslink failure. The chain scission failure mode is mainly observed in polymers with strong covalent crosslinks, while the crosslink failure mode is observed in polymers with weak crosslinks. In two recent papers, we have proposed a theory for progressive damage and rupture of polymers with strong covalent crosslinks. In this paper, we extend our previous framework and formulate a theory for modeling failure of elastomeric materials with weak crosslinks. We first introduce a model for the deformation of a single chain with weak crosslinks at each of its two ends using statistical mechanics arguments, and then upscale the model from a single chain to the continuum level for a polymer network. Finally, we introduce a damage variable to describe the progressive damage and failure of polymer networks. A central feature of our theory is the recognition that the free energy of elastomers is not entirely entropic in nature; there is also an energetic contribution from the deformation of the backbone bonds in a chain and/or the crosslinks. For polymers with weak crosslinks, this energetic contribution is mainly from the deformation of the crosslinks. It is this energetic part of the free energy which is the driving force for progressive damage and fracture of elastomeric materials. Moreover, we show that for elastomeric materials in which fracture occurs by crosslink stretching and scission, the classical Lake–Thomas scaling—that the toughness Gc of an elastomeric material is proportional to 1/G0, with G0=NkBϑ the ground-state shear modulus of the material—does not hold. A new scaling is proposed, and some important consequences of this scaling are remarked upon.

scholarly journals Enhanced polymer mechanical degradation through mechanochemically unveiled lactonization

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Yangju Lin ◽  
Tatiana B. Kouznetsova ◽  
Chia-Chih Chang ◽  
Stephen L. Craig
Keyword(s):  
Single Molecule ◽  
Ring Opening ◽  
Stress Transfer ◽  
Polymeric Materials ◽  
Chain Scission ◽  
Mechanical Degradation ◽  
Single Chain ◽  
Single Molecule Force Spectroscopy ◽  
Polymer Backbone ◽  
Single Polymer Chain

Abstract The mechanical degradation of polymers is typically limited to a single chain scission per triggering chain stretching event, and the loss of stress transfer that results from the scission limits the extent of degradation that can be achieved. Here, we report that the mechanically triggered ring-opening of a [4.2.0]bicyclooctene (BCOE) mechanophore sets up a delayed, force-free cascade lactonization that results in chain scission. Delayed chain scission allows many eventual scission events to be initiated within a single polymer chain. Ultrasonication of a 120 kDa BCOE copolymer mechanically remodels the polymer backbone, and subsequent lactonization slowly (~days) degrades the molecular weight to 4.4 kDa, > 10× smaller than control polymers in which lactonization is blocked. The force-coupled kinetics of ring-opening are probed by single molecule force spectroscopy, and mechanical degradation in the bulk is demonstrated. Delayed scission offers a strategy to enhanced mechanical degradation and programmed obsolescence in structural polymeric materials.

Biosynthesis of mollisin by Mollisiacaesia

1990 ◽  
Vol 68 (1) ◽  
pp. 1-4 ◽  
Author(s):  
A. Gavin McInnes ◽  
John A. Walter ◽  
Jeffrey L. C. Wright ◽  
Leo C. Vining ◽  
Neelima Ranade ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nuclear Magnetic Resonance Spectrum ◽  
Resonance Spectrum ◽  
Chain Scission ◽  
Nmr Analysis ◽  
Deuterium Labeling ◽  
Single Chain ◽  
Deuterium Labelling ◽  
Methylene Group

The 2H nuclear magnetic resonance spectrum of mollisin from cultures of the fungus Mollisiacaesia supplemented with [2-2H3]acetate was consistent with biosynthesis of the metabolite via a single-chain polyketide. The presumption that chain scission accompanies dichlorination of a reactive methylene group in such a polyketide was supported by the detection of chloroperoxidase activity with monochlorodimedone as a substrate, and failure to detect chlorinating activity when the substrate was acetoacetyl coenzyme A. However, a decisive choice between single-chain and two-chain polyketide intermediates cannot be made with information provided by the techniques used so far. Keywords: biosynthesis, mollisin, deuterium labelling and NMR; deuterium labelling and NMR, mollisin biosynthesis; labeling of mollisin by deuterium, NMR analysis; mollisin biosynthesis, deuterium, labeling and NMR; NMR deuterium, mollisin biosynthesis.

Cryo-electron microscopy of two-dimensional crystals of reduced type B botulinum neurotoxin

1992 ◽  
Vol 50 (1) ◽  
pp. 530-531
Author(s):  
P. F. Flicker ◽  
V.S. Kulkarni ◽  
J. P. Robinson ◽  
G. Stubbs ◽  
B. R. DasGupta
Keyword(s):  
Disulfide Bonds ◽  
Clostridium Botulinum ◽  
Structural Changes ◽  
Two Dimensional ◽  
Type B ◽  
Single Chain ◽  
Muscle Paralysis ◽  
Cryo Electron Microscopy ◽  
Disulfide Linkages ◽  
Intracellular Action

Botulinum toxin is a potent neurotoxin produced by Clostridium botulinum. The toxin inhibits release of neurotransmitter, causing muscle paralysis. There are several serotypes, A to G, all of molecular weight about 150,000. The protein exists as a single chain or or as two chains, with two disulfide linkages. In a recent investigation on intracellular action of neurotoxins it was reported that type B neurotoxin can inhibit the release of Ca++-activated [3H] norepinephrine only if the disulfide bonds are reduced. In order to investigate possible structural changes in the toxin upon reduction of the disulfide bonds, we have prepared two-dimensional crystals of reduced type B neurotoxin. These two-dimensional crystals will be compared with those of the native (unreduced) type B toxin.

Fine structure and properties of defects in naturally occurring silicates and oxides

1990 ◽  
Vol 48 (4) ◽  
pp. 460-461
Author(s):  
David R. Veblen
Keyword(s):  
Chemical Reactions ◽  
High Resolution Electron Microscopy ◽  
Extended Defects ◽  
Single Chain ◽  
Naturally Occurring ◽  
Resolution Electron ◽  
Fine Structures ◽  
Image Simulations ◽  
Similar Crystal Structure

Extended defects and interfaces control many processes in rock-forming minerals, from chemical reactions to rock deformation. In many cases, it is not the average structure of a defect or interface that is most important, but rather the structure of defect terminations or offsets in an interface. One of the major thrusts of high-resolution electron microscopy in the earth sciences has been to identify the role of defect fine structures in reactions and to determine the structures of such features. This paper will review studies using HREM and image simulations to determine the structures of defects in silicate and oxide minerals and present several examples of the role of defects in mineral chemical reactions. In some cases, the geological occurrence can be used to constrain the diffusional properties of defects.The simplest reactions in minerals involve exsolution (precipitation) of one mineral from another with a similar crystal structure, and pyroxenes (single-chain silicates) provide a good example. Although conventional TEM studies have led to a basic understanding of this sort of phase separation in pyroxenes via spinodal decomposition or nucleation and growth, HREM has provided a much more detailed appreciation of the processes involved.

Elemental mass loss in silicate minerals during x-ray analysis

1990 ◽  
Vol 48 (4) ◽  
pp. 804-805
Author(s):  
P.E. Champness ◽  
R.W. Devenish
Keyword(s):  
Mass Loss ◽  
Current Density ◽  
Damage Mechanism ◽  
Beam Current ◽  
Single Chain ◽  
Plagioclase Feldspar ◽  
X Ray ◽  
Alkali Ions ◽  
Structural Order ◽  
Sheet Silicate

It has long been recognised that silicates can suffer extensive beam damage in electron-beam instruments. The predominant damage mechanism is radiolysis. For instance, damage in quartz, SiO2, results in loss of structural order without mass loss whereas feldspars (framework silicates containing Ca, Na, K) suffer loss of structural order with accompanying mass loss. In the latter case, the alkali ions, particularly Na, are found to migrate away from the area of the beam. The aim of the present study was to investigate the loss of various elements from the common silicate structures during electron irradiation at 100 kV over a range of current densities of 104 - 109 A m−2. (The current density is defined in terms of 50% of total current in the FWHM probe). The silicates so far ivestigated are:- olivine [(Mg, Fe)SiO4], a structure that has isolated Si-O tetrahedra, garnet [(Mg, Ca, Fe)3Al2Si3AO12 another silicate with isolated tetrahedra, pyroxene [-Ca(Mg, Fe)Si2O6 a single-chain silicate; mica [margarite, -Ca2Al4Si4Al4O2O(OH)4], a sheet silicate, and plagioclase feldspar [-NaCaAl3Si5O16]. Ion- thinned samples of each mineral were examined in a VG Microscopes UHV HB501 field- emission STEM. The beam current used was typically - 0.5 nA and the current density was varied by defocussing the electron probe. Energy-dispersive X-ray spectra were collected every 10 seconds for a total of 200 seconds using a Link Systems windowless detector. The thickness of the samples in the area of analysis was normally 50-150 nm.

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