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Lamellar mesoscopic organization of supramolecular polymers: a necessary pre-ordering secondary structure
- Source :
- Polymer Chemistry, Polymer Chemistry, Royal Society of Chemistry-RSC, 2017, 8 (38), pp.5954-5961. ⟨10.1039/C7PY01219E⟩, Polymer Chemistry, 2017, 8 (38), pp.5954-5961. ⟨10.1039/C7PY01219E⟩
- Publication Year :
- 2017
- Publisher :
- HAL CCSD, 2017.
-
Abstract
- Thymine-functionalized telechelic poly(propylene glycol) (PPG) chains of 460–4000 g mol−1 present a long-range ordered lamellar microphase separation due to thymine crystallization. This organization is lost if the difference of polarity between the H-bonding units and the chain is not sufficiently high to induce segregation, as with a poly(ethylene glycol) (PEG) chain. Moreover, the mesoscopic order is gradually lost with the longest PPG chains i.e. with the smallest volume fractions of supramolecular units limiting their clusterization/crystallization. Methylated thymine (MeThy) end-functionalized PPG presents the same lamellar mesoscopic organization, proving that Thy/Thy H-bonding self-association does not drive their crystallization. Infrared spectroscopy evidences that the amide functions linking MeThy motifs to PPG chains interact with each other through H-bonds, forming either a random or an aligned pattern, just like protein secondary structures. On cooling from the melt, disordered H-bonded amides align and pre-order the supramolecular units just prior to the disorder–order transition driven by the MeThy crystallization. The close packing, necessary to induce crystallization, is no longer possible with bulky neo-pentyl functionalized thymines (tBuCH2Thy), preventing mesoscopic organization. Hence, the pattern formed by H-bonded amide links plays a major role in the long-range organization of the telechelic supramolecular polymer in helping supramolecular units to crystallize. Indeed, replacing the amide by an ester link suppresses their crystallization and thus the mesoscopic order.
- Subjects :
- Materials science
Polymers and Plastics
Supramolecular chemistry
Bioengineering
02 engineering and technology
010402 general chemistry
01 natural sciences
Biochemistry
law.invention
chemistry.chemical_compound
law
Amide
Polymer chemistry
[CHIM]Chemical Sciences
Lamellar structure
Crystallization
Protein secondary structure
ComputingMilieux_MISCELLANEOUS
chemistry.chemical_classification
[PHYS]Physics [physics]
Mesoscopic physics
Organic Chemistry
021001 nanoscience & nanotechnology
0104 chemical sciences
Supramolecular polymers
chemistry
0210 nano-technology
Ethylene glycol
Subjects
Details
- Language :
- English
- ISSN :
- 17599954 and 17599962
- Database :
- OpenAIRE
- Journal :
- Polymer Chemistry, Polymer Chemistry, Royal Society of Chemistry-RSC, 2017, 8 (38), pp.5954-5961. ⟨10.1039/C7PY01219E⟩, Polymer Chemistry, 2017, 8 (38), pp.5954-5961. ⟨10.1039/C7PY01219E⟩
- Accession number :
- edsair.doi.dedup.....c6bc95c5639cdd0422d712aed9faca0c