Local Orientational Mobility of Collapsed Dendrimers

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Local Orientational Mobility of Collapsed Dendrimers. / Sheveleva, Nadezhda N.; Bezrodnyi, Valeriy V.; Mikhtaniuk, Sofia E.; Shavykin, Oleg V.; Neelov, Igor M.; Tarasenko, Irina I.; Vovk, Mikhail A.; Mikhailova, Mariya E.; Penkova, Anastasia V.; Markelov, Denis A.

In: Macromolecules, Vol. 54, No. 23, 2021, p. 11083-11092.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{8ec30820cc474133bac76061deb728d3,

title = "Local Orientational Mobility of Collapsed Dendrimers",

abstract = "Dendrimers are regular hyperbranched macromolecules. The complex structure of the relaxation spectrum is one of the many features of dendrimers that does not fit into the classical concepts of polymers. The relaxation spectrum is manifested in various dynamic processes, including NMR relaxation. In this work, we study the collapsed and swollen dendrimers using NMR relaxation experiments and atomistic simulations of the modified lysine-based dendrimer with double histidine insertions (Lys-2His). This dendrimer is considered most suitable because the imidazole groups are not charged at a normal pH and become protonated at a low pH. We found that the orientational mobilities of segments and CH2 groups inside a collapsed dendrimer are opposite to those in the swollen conformation. Volume interactions suppress the internal local mobility, and reorientation occurs due to the rotation of the dendrimer as a whole. A comparison of the orientational mobility of the segments and CH2 groups for these conformations reveals that taking the segmental mobility into account gives an interpretation pitfall of the mobility of CH2 groups observed in NMR experiments. The studies of the Lys-2His dendrimers are of independent interest for biomedical research. However, our findings should be general for other collapsed dendrimer macromolecules. ",

author = "Sheveleva, {Nadezhda N.} and Bezrodnyi, {Valeriy V.} and Mikhtaniuk, {Sofia E.} and Shavykin, {Oleg V.} and Neelov, {Igor M.} and Tarasenko, {Irina I.} and Vovk, {Mikhail A.} and Mikhailova, {Mariya E.} and Penkova, {Anastasia V.} and Markelov, {Denis A.}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

doi = "10.1021/acs.macromol.1c01835",

language = "English",

volume = "54",

pages = "11083--11092",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "23",

}

RIS

TY - JOUR

T1 - Local Orientational Mobility of Collapsed Dendrimers

AU - Sheveleva, Nadezhda N.

AU - Bezrodnyi, Valeriy V.

AU - Mikhtaniuk, Sofia E.

AU - Shavykin, Oleg V.

AU - Neelov, Igor M.

AU - Tarasenko, Irina I.

AU - Vovk, Mikhail A.

AU - Mikhailova, Mariya E.

AU - Penkova, Anastasia V.

AU - Markelov, Denis A.

PY - 2021

Y1 - 2021

N2 - Dendrimers are regular hyperbranched macromolecules. The complex structure of the relaxation spectrum is one of the many features of dendrimers that does not fit into the classical concepts of polymers. The relaxation spectrum is manifested in various dynamic processes, including NMR relaxation. In this work, we study the collapsed and swollen dendrimers using NMR relaxation experiments and atomistic simulations of the modified lysine-based dendrimer with double histidine insertions (Lys-2His). This dendrimer is considered most suitable because the imidazole groups are not charged at a normal pH and become protonated at a low pH. We found that the orientational mobilities of segments and CH2 groups inside a collapsed dendrimer are opposite to those in the swollen conformation. Volume interactions suppress the internal local mobility, and reorientation occurs due to the rotation of the dendrimer as a whole. A comparison of the orientational mobility of the segments and CH2 groups for these conformations reveals that taking the segmental mobility into account gives an interpretation pitfall of the mobility of CH2 groups observed in NMR experiments. The studies of the Lys-2His dendrimers are of independent interest for biomedical research. However, our findings should be general for other collapsed dendrimer macromolecules.

AB - Dendrimers are regular hyperbranched macromolecules. The complex structure of the relaxation spectrum is one of the many features of dendrimers that does not fit into the classical concepts of polymers. The relaxation spectrum is manifested in various dynamic processes, including NMR relaxation. In this work, we study the collapsed and swollen dendrimers using NMR relaxation experiments and atomistic simulations of the modified lysine-based dendrimer with double histidine insertions (Lys-2His). This dendrimer is considered most suitable because the imidazole groups are not charged at a normal pH and become protonated at a low pH. We found that the orientational mobilities of segments and CH2 groups inside a collapsed dendrimer are opposite to those in the swollen conformation. Volume interactions suppress the internal local mobility, and reorientation occurs due to the rotation of the dendrimer as a whole. A comparison of the orientational mobility of the segments and CH2 groups for these conformations reveals that taking the segmental mobility into account gives an interpretation pitfall of the mobility of CH2 groups observed in NMR experiments. The studies of the Lys-2His dendrimers are of independent interest for biomedical research. However, our findings should be general for other collapsed dendrimer macromolecules.

UR - http://www.scopus.com/inward/record.url?scp=85120543874&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/413e4b17-1fb3-338d-88fa-420b1fb680da/

U2 - 10.1021/acs.macromol.1c01835

DO - 10.1021/acs.macromol.1c01835

M3 - Article

AN - SCOPUS:85120543874

VL - 54

SP - 11083

EP - 11092

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 23

ER -

ID: 89532172