scholarly journals Interactions between shape-persistent macromolecules as probed by AFM

2017 ◽  
Vol 13 ◽  
pp. 938-951 ◽  
Author(s):  
Johanna Blass ◽  
Jessica Brunke ◽  
Franziska Emmerich ◽  
Cédric Przybylski ◽  
Vasil M Garamus ◽  
...  
Keyword(s):  
Polymer System ◽  
Water Soluble ◽  
Polymer Chains ◽  
Contour Length ◽  
Polymer Backbone ◽  
Guest Molecules ◽  
Apparent Contour ◽  
Multiple Inclusion ◽  
Regular Configuration ◽  
Shearing Mechanism

Water-soluble shape-persistent cyclodextrin (CD) polymers with amino-functionalized end groups were prepared starting from diacetylene-modified cyclodextrin monomers by a combined Glaser coupling/click chemistry approach. Structural perfection of the neutral CD polymers and inclusion complex formation with ditopic and monotopic guest molecules were proven by MALDI–TOF and UV–vis measurements. Small-angle neutron and X-ray (SANS/SAXS) scattering experiments confirm the stiffness of the polymer chains with an apparent contour length of about 130 Å. Surface modification of planar silicon wafers as well as AFM tips was realized by covalent bound formation between the terminal amino groups of the CD polymer and a reactive isothiocyanate–silane monolayer. Atomic force measurements of CD polymer decorated surfaces show enhanced supramolecular interaction energies which can be attributed to multiple inclusion complexes based on the rigidity of the polymer backbone and the regular configuration of the CD moieties. Depending on the geometrical configuration of attachment anisotropic adhesion characteristics of the polymer system can be distinguished between a peeling and a shearing mechanism.

SuFExable Polymers with Helical Structures Derived from Thionyl Tetrafluoride (SOF4)

2019 ◽  
Author(s):  
Suhua Li ◽  
Gencheng Li ◽  
Bing Gao ◽  
Sidharam P. Pujari ◽  
Xiaoyan Chen ◽  
...  
Keyword(s):  
Functional Polymers ◽  
Polymer Chains ◽  
New Materials ◽  
Helical Structures ◽  
Polymer Backbone ◽  
Silyl Ethers ◽  
Helical Polymer ◽  
Key Characteristics ◽  
Post Modification ◽  
Individual Polymer

The first SuFEx click chemistry synthesis of SOF<sub>4</sub>-derived copolymers based upon the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers) is described. This novel class of SuFEx polymer presents two key characteristics: First, the newly created [-N=S(=O)F-O-] polymer backbone linkages are themselves SuFExable and primed to undergo further high-yielding and precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate the presence of helical polymer structures, which itself suggests a preferential approach of new monomers onto the growing polymer chain upon the formation of the stereogenic linking moiety.

Functional Poly(p-Xylylene)s via Chemical Reduction of Poly(p-Phenylene Vinylene)s

2019 ◽  
Author(s):  
Ain Uddin ◽  
Weifan Sang ◽  
Yong Gao ◽  
Kyle Plunkett
Keyword(s):  
Film Formation ◽  
Chemical Reduction ◽  
Water Soluble ◽  
Phenylene Vinylene ◽  
Polymer Modification ◽  
Polymer Backbone ◽  
Crosslinking Process ◽  
Conducting Membranes ◽  
In Situ Crosslinking

The synthesis of poly(p-xylylene)s (PPXs) with sidechains containing alkyl bromide functionality, and their post-polymer modification, is described. The PPXs were prepared by a diimide hydrogenation of poly(p-phenylene vinylene)s (PPVs) that were originally synthesized by a Gilch polymerization. The polymer backbone reduction was carried out with hydrazine hydrate in toluene at 80 °C to provide polymers with the sidechain-containing bromide functionality intact. To demonstrate post-polymer modification of the sidechains, the resulting PPX polymers were modified with trimethylamine to form tetraalkylammonium ion functionality and were evaluated as anion conducting membranes. While PPX homopolymers containing tetralkylammonium ions were completely water soluble and not able to form valuable films, PPX copolymers containing mixed tetraalkylammonium ions and hydrophobic chains were capable of film formation and alkaline stability. In addition, an in situ crosslinking process that used N,N,N',N'-tetramethyl-1,6-hexanediamine during the tetraalkylammonium formation of brominated PPX polymers was also evaluated and gave reasonable films with conductivities of ~10 mS-cm-1.

Functional Poly(p-Xylylene)s via Chemical Reduction of Poly(p-Phenylene Vinylene)s

2019 ◽  
Author(s):  
Ain Uddin ◽  
Weifan Sang ◽  
Yong Gao ◽  
Kyle Plunkett
Keyword(s):  
Film Formation ◽  
Chemical Reduction ◽  
Water Soluble ◽  
Phenylene Vinylene ◽  
Polymer Modification ◽  
Polymer Backbone ◽  
Crosslinking Process ◽  
Conducting Membranes ◽  
In Situ Crosslinking

The synthesis of poly(p-xylylene)s (PPXs) with sidechains containing alkyl bromide functionality, and their post-polymer modification, is described. The PPXs were prepared by a diimide hydrogenation of poly(p-phenylene vinylene)s (PPVs) that were originally synthesized by a Gilch polymerization. The polymer backbone reduction was carried out with hydrazine hydrate in toluene at 80 °C to provide polymers with the sidechain-containing bromide functionality intact. To demonstrate post-polymer modification of the sidechains, the resulting PPX polymers were modified with trimethylamine to form tetraalkylammonium ion functionality and were evaluated as anion conducting membranes. While PPX homopolymers containing tetralkylammonium ions were completely water soluble and not able to form valuable films, PPX copolymers containing mixed tetraalkylammonium ions and hydrophobic chains were capable of film formation and alkaline stability. In addition, an in situ crosslinking process that used N,N,N',N'-tetramethyl-1,6-hexanediamine during the tetraalkylammonium formation of brominated PPX polymers was also evaluated and gave reasonable films with conductivities of ~10 mS-cm-1.

scholarly journals Interactions between 4-thiothymidine and water-soluble cyclodextrins: Evidence for supramolecular structures in aqueous solutions

2016 ◽  
Vol 12 ◽  
pp. 549-563 ◽  
Author(s):  
Vito Rizzi ◽  
Sergio Matera ◽  
Paola Semeraro ◽  
Paola Fini ◽  
Pinalysa Cosma
Keyword(s):  
Inclusion Complexes ◽  
Pyrimidine Ring ◽  
Protective Role ◽  
Supramolecular Structures ◽  
Water Soluble ◽  
Aqueous Environment ◽  
Spectroscopic Techniques ◽  
Guest Molecules ◽  
H Nmr ◽  
Cv Measurements

Since several years the inclusion of organic compounds (guests) within the hydrophobic cavity (host) of cyclodextrins (CDs) has been the subject of many investigations. Interestingly, the formation of inclusion complexes could affect the properties of the guest molecules and, for example, the influence of the delivery system can be a method to improve/change the photochemical behavior of the guest. In particular, very recent studies have shown the protective role of CDs preventing the degradation of the encapsulated guest. Starting from this consideration, in this work, only the structure and complexation mode of the inclusion complexes involving 4-thiothymidine (S4TdR, a known photosensitizer) and five CDs, namely 2-hydroxypropyl-α-cyclodextrin (2-HP-α-CD), 2-hydroxypropyl-β-cyclodextrin (2-HP-β-CD), 2-hydroxypropyl-γ-cyclodextrin (2-HP-γ-CD), heptakis-(2,6-di-O-methyl)-β-cyclodextrin (DIMEB CD) and heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (TRIMEB CD) were investigated by different spectroscopic techniques (UV–vis, FTIR–ATR, 1H NMR) and cyclic voltammetry analysis (CV). This work is necessary for a prospective research on the photoreactivity of S4TdR in aqueous environment and in the presence of CDs to prevent its degradation under irradiation. UV–vis, FTIR–ATR and CV measurements suggested the formation of supramolecular structures involving the employed CDs and mainly the pyrimidine ring of S4TdR. 1H NMR analyses confirmed such indication, unveiling the presence of inclusion complexes. The strongest and deepest interactions were suggested when TRIMEB and DIMEB CDs were studied. The S4TdR affinity towards CDs was also evaluated by using the Benesi–Hildebrand (B–H) equation at 25 °C employing CV and 1H NMR methods. The stoichiometry of the interaction was also inferred and it appears to be 1:1 for all examined CDs.

scholarly journals Synthesis and Guest-Binding Properties of pH/Reduction Dual-Responsive Cyclophane Dimer

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3097
Author(s):  
Osamu Hayashida ◽  
Yudai Tanaka ◽  
Takaaki Miyazaki
Keyword(s):  
Electrostatic Interaction ◽  
Disulfide Bonds ◽  
Water Soluble ◽  
Guest Molecules ◽  
Binding Behavior ◽  
Dual Responsive ◽  
Guest Binding ◽  
Basic Solutions ◽  
Ph Conditions ◽  
Almost All

A water-soluble cyclophane dimer having two disulfide groups as a reduction-responsive cleavable bond as well as several acidic and basic functional groups as a pH-responsive ionizable group 1 was successfully synthesized. It was found that 1 showed pH-dependent guest-binding behavior. That is, 1 strongly bound an anionic guest, 6-p-toluidinonaphthalene-2-sulfonate (TNS) with binding constant (K/M−1) for 1:1 host-guest complexes of 9.6 × 104 M−1 at pH 3.8, which was larger than those at pH 7.4 and 10.7 (6.0 × 104 and 2.4 × 104 M−1, respectively), indicating a favorable electrostatic interaction between anionic guest and net cationic 1. What is more, release of the entrapped guest molecules by 1 was easily controlled by pH stimulus. Large favorable enthalpies (ΔH) for formation of host-guest complexes were obtained under the pH conditions employed, suggesting that electrostatic interaction between anionic TNS and 1 was the most important driving force for host-guest complexation. Such contributions of ΔH for formation of host-guest complexes decreased along with increased pH values from acidic to basic solutions. Upon addition of dithiothreitol (DTT) as a reducing reagent to an aqueous PBS buffer (pH 7.4) containing 1 and TNS, the fluorescence intensity originating from the bound guest molecules decreased gradually. A treatment of 1 with DTT gave 2, having less guest-binding affinity by the cleavage of disulfide bonds of 1. Consequently, almost all entrapped guest molecules by 1 were released from the host. Moreover, such reduction-responsive cleavage of 1 and release of bound guest molecules was performed more rapidly in aqueous buffer at pH 10.7.

scholarly journals Linear Viscoelasticity and Flow of Self-Assembled Vitrimers: The Case of a Polyethylene/dioxaborolane System

2020 ◽  
Author(s):  
RALM RICARTE ◽  
François Tournilhac ◽  
Michel Cloître ◽  
Ludwik Leibler
Keyword(s):  
Self Assembly ◽  
Linear Viscoelasticity ◽  
Microphase Separation ◽  
Flow Behavior ◽  
Wide Distribution ◽  
Polymer Chains ◽  
Melt Fracture ◽  
Polymer Backbone ◽  
Cross Links ◽  
Insoluble Portion

For vitrimer systems obtained by dynamic cross-linking of polymer chains, incompatibility effects between the cross-links and polymer backbone can lead to microphase separation, resulting in a network made of cross-linked aggregates. Additionally, when there is a wide distribution of the number of cross-links per chain, macrophase separation can occur. Here, we investigate the linear viscoelasticity and flow of a polyethylene (PE) vitrimer that has cross-linkable dioxaborolane maleimide grafts, which aggregate into a hierarchical nanostructure. To elucidate the role of self-assembly, noncross-linked graft functionalized PE was first studied. It had a terminal relaxation time that was orders of magnitude larger than both neat PE and partially peroxide cross-linked PE. When dioxaborolane cross-linker was added to form the vitrimer, the resulting material could not achieve terminal relaxation within 8 hr. The graft-poor soluble and graft-rich insoluble portions of the PE vitrimer were then isolated and characterized. The soluble portion expressed similar flow behavior as neat PE, while the insoluble portion – which is a network of cross-linked aggregates – relaxed very little over 8 hr. When the insoluble and soluble portions were blended, the rheological behavior of the original vitrimer was basically recovered, showing that the soluble portion acts as a lubricant. When the insoluble portion was blended with neat PE, the material relaxed much more stress, but still did not reach steady-state flow within 8 hr. When high stresses were applied, however, PE vitrimer flowed. Nonlinear rheology experiments revealed melt fracture at high strains and suggested that flow is enabled by rapid healing, which follows fracture events. The presence of macroscopic phase separation facilitated flow.

scholarly journals Linear Viscoelasticity and Flow of Self-Assembled Vitrimers: The Case of a Polyethylene/dioxaborolane System

2019 ◽  
Author(s):  
RALM RICARTE ◽  
François Tournilhac ◽  
Michel Cloître ◽  
Ludwik Leibler
Keyword(s):  
Self Assembly ◽  
Linear Viscoelasticity ◽  
Microphase Separation ◽  
Flow Behavior ◽  
Wide Distribution ◽  
Polymer Chains ◽  
Melt Fracture ◽  
Polymer Backbone ◽  
Cross Links ◽  
Insoluble Portion

For vitrimer systems obtained by dynamic cross-linking of polymer chains, incompatibility effects between the cross-links and polymer backbone can lead to microphase separation, resulting in a network made of cross-linked aggregates. Additionally, when there is a wide distribution of the number of cross-links per chain, macrophase separation can occur. Here, we investigate the linear viscoelasticity and flow of a polyethylene (PE) vitrimer that has cross-linkable dioxaborolane maleimide grafts, which aggregate into a hierarchical nanostructure. To elucidate the role of self-assembly, noncross-linked graft functionalized PE was first studied. It had a terminal relaxation time that was orders of magnitude larger than both neat PE and partially peroxide cross-linked PE. When dioxaborolane cross-linker was added to form the vitrimer, the resulting material could not achieve terminal relaxation within 8 hr. The graft-poor soluble and graft-rich insoluble portions of the PE vitrimer were then isolated and characterized. The soluble portion expressed similar flow behavior as neat PE, while the insoluble portion – which is a network of cross-linked aggregates – relaxed very little over 8 hr. When the insoluble and soluble portions were blended, the rheological behavior of the original vitrimer was basically recovered, showing that the soluble portion acts as a lubricant. When the insoluble portion was blended with neat PE, the material relaxed much more stress, but still did not reach steady-state flow within 8 hr. When high stresses were applied, however, PE vitrimer flowed. Nonlinear rheology experiments revealed melt fracture at high strains and suggested that flow is enabled by rapid healing, which follows fracture events. The presence of macroscopic phase separation facilitated flow.

Theory of the stabilization of colloids by adsorbed polymer

1974 ◽  
Vol 337 (1611) ◽  
pp. 509-516 ◽  
Keyword(s):  
Plane Surface ◽  
Analytic Form ◽  
Polymer Chains ◽  
Contour Length ◽  
Link Length ◽  
Excluded Volume Effects ◽  
Adsorbed Polymer ◽  
Random Flight ◽  
The Stability ◽  
Simple Analytic Form

The configurational free energy of random flight polymer chains adsorbed by one end onto a plane surface as a function of the distance from a parallel plane surface is expressed to a good approximation in simple analytic form. The result is used to discuss the stabilization of a colloid suspension by adsorbed polymer. According to this theory two types of aggregation of colloid particles may occur. If LI < AS/2π 3 NkT , where l is the link length and L the contour length of a polymer chain, A is the Hamaker constant, N /S is the number of adsorbed polymer chains per unit area and kT is the Boltzman constant multiplied by temperature, the particles adhere closely, but if AS/2π 3 kT < IL < AS/nkT lg 2N a looser association is formed. It is expected that the presence of excluded volume effects would greatly increase the stability against the looser association.

Unusual Incorporation of Neutral and Low Water-Soluble Guest Molecules into Layered Double Hydroxides: The Case of Cucurbit[6 and 7]uril Inclusion Hosts

2011 ◽  
Vol 23 (6) ◽  
pp. 1350-1352 ◽  
Author(s):  
Luis Fernando Stucchi da Silva ◽  
Grégoire Jean-François Demets ◽  
Christine Taviot-Guého ◽  
Fabrice Leroux ◽  
João Barros Valim
Keyword(s):  
Layered Double Hydroxides ◽  
Water Soluble ◽  
Guest Molecules ◽  
Double Hydroxides
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