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Thermoresponsive properties of polyacrylamides in physiological solutions
Polymer solutions with a lower critical solution temperature (LCST) undergo reversible phase separation when heated above their cloud point temperature ( T CP or CPT). As such, they have been proposed for a wide range of biomedical applications, from injectable drug depots to switchable coatings for...
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| Published in: | Polymer chemistry 2021-09, Vol.12 (35), p.577-584 |
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| creator | Kolouchová, Kristýna Lobaz, Volodymyr Beneš, Hynek de la Rosa, Victor R Babuka, David Švec, Pavel ernoch, Peter Hrubý, Martin Hoogenboom, Richard Št pánek, Petr Groborz, Ond ej |
| description | Polymer solutions with a lower critical solution temperature (LCST) undergo reversible phase separation when heated above their cloud point temperature (
T
CP
or CPT). As such, they have been proposed for a wide range of biomedical applications, from injectable drug depots to switchable coatings for cell adhesion. However, in systematic studies, the
T
CP
of these thermoresponsive polymers has been mostly measured in non-physiological solutions, thereby hindering the development of their medicinal applications. Here, we analysed the thermoresponsive properties of four acrylamide-based polymers with LCST, namely poly[(
N
-2,2-difluoroethyl)acrylamide] (
pDFEA
), poly[(
N
-isopropyl)acrylamide] (
pNIPAM
), poly[(
N
,
N
-diethyl)acrylamide] (
pDEA
), and poly[(
N
-acryloyl)pyrrolidine] (
pAP
). As shown by turbidimetry, their
T
CP
in phosphate saline buffer (PBS) and foetal bovine serum (FBS) were consistently lower than those reported in the literature, typically assessed in pure water, even when using the same setup. In addition, these physiological solutions affected the variation of
T
CP
as a function of polymer concentration (1.25 to 10.0 mg mL
−1
) and molar mass (20 to 50 kg mol
−1
). As shown by isothermal calorimetry, interactions between proteins in FBS and polymer aggregates were predominantly exothermic, which indicates that protein-polymer complexes are formed through enthalpically driven processes. In conclusion, the
T
CP
of thermoresponsive polymers strongly depends on solvent composition and therefore should be measured under physiological conditions for future medicinal applications.
We show that the cloud point temperature (
T
CP
) of thermoresponsive polyacrylamides is considerably lower in physiologically relevant solvents (phosphate-buffered saline, serum) than in pure water. This decrease of
T
CP
may be critical for some biomedical applications. |
| doi_str_mv | 10.1039/d1py00843a |
| format | article |
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T
CP
or CPT). As such, they have been proposed for a wide range of biomedical applications, from injectable drug depots to switchable coatings for cell adhesion. However, in systematic studies, the
T
CP
of these thermoresponsive polymers has been mostly measured in non-physiological solutions, thereby hindering the development of their medicinal applications. Here, we analysed the thermoresponsive properties of four acrylamide-based polymers with LCST, namely poly[(
N
-2,2-difluoroethyl)acrylamide] (
pDFEA
), poly[(
N
-isopropyl)acrylamide] (
pNIPAM
), poly[(
N
,
N
-diethyl)acrylamide] (
pDEA
), and poly[(
N
-acryloyl)pyrrolidine] (
pAP
). As shown by turbidimetry, their
T
CP
in phosphate saline buffer (PBS) and foetal bovine serum (FBS) were consistently lower than those reported in the literature, typically assessed in pure water, even when using the same setup. In addition, these physiological solutions affected the variation of
T
CP
as a function of polymer concentration (1.25 to 10.0 mg mL
−1
) and molar mass (20 to 50 kg mol
−1
). As shown by isothermal calorimetry, interactions between proteins in FBS and polymer aggregates were predominantly exothermic, which indicates that protein-polymer complexes are formed through enthalpically driven processes. In conclusion, the
T
CP
of thermoresponsive polymers strongly depends on solvent composition and therefore should be measured under physiological conditions for future medicinal applications.
We show that the cloud point temperature (
T
CP
) of thermoresponsive polyacrylamides is considerably lower in physiologically relevant solvents (phosphate-buffered saline, serum) than in pure water. This decrease of
T
CP
may be critical for some biomedical applications.</description><identifier>ISSN: 1759-9954</identifier><identifier>EISSN: 1759-9962</identifier><identifier>DOI: 10.1039/d1py00843a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Abbreviations ; Acrylamide ; Biomedical materials ; Cell adhesion ; Heat measurement ; NMR ; Nuclear magnetic resonance ; Phase separation ; Photon correlation spectroscopy ; Physiology ; Polyacrylamide ; Polyisopropyl acrylamide ; Polymer chemistry ; Polymers ; Proteins ; Refractivity</subject><ispartof>Polymer chemistry, 2021-09, Vol.12 (35), p.577-584</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c383t-c314a9fc43b7d3cdbb6d11ee5181bbc283b1196d5d17fb75b0c3087a542c537b3</citedby><cites>FETCH-LOGICAL-c383t-c314a9fc43b7d3cdbb6d11ee5181bbc283b1196d5d17fb75b0c3087a542c537b3</cites><orcidid>0000-0002-5075-261X ; 0000-0003-1433-678X ; 0000-0003-0479-2837 ; 0000-0002-8874-8632 ; 0000-0003-1817-3818 ; 0000-0001-7398-2058 ; 0000-0002-3164-6168 ; 0000-0002-1136-2280 ; 0000-0002-6604-2815</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Kolouchová, Kristýna</creatorcontrib><creatorcontrib>Lobaz, Volodymyr</creatorcontrib><creatorcontrib>Beneš, Hynek</creatorcontrib><creatorcontrib>de la Rosa, Victor R</creatorcontrib><creatorcontrib>Babuka, David</creatorcontrib><creatorcontrib>Švec, Pavel</creatorcontrib><creatorcontrib>ernoch, Peter</creatorcontrib><creatorcontrib>Hrubý, Martin</creatorcontrib><creatorcontrib>Hoogenboom, Richard</creatorcontrib><creatorcontrib>Št pánek, Petr</creatorcontrib><creatorcontrib>Groborz, Ond ej</creatorcontrib><title>Thermoresponsive properties of polyacrylamides in physiological solutions</title><title>Polymer chemistry</title><description>Polymer solutions with a lower critical solution temperature (LCST) undergo reversible phase separation when heated above their cloud point temperature (
T
CP
or CPT). As such, they have been proposed for a wide range of biomedical applications, from injectable drug depots to switchable coatings for cell adhesion. However, in systematic studies, the
T
CP
of these thermoresponsive polymers has been mostly measured in non-physiological solutions, thereby hindering the development of their medicinal applications. Here, we analysed the thermoresponsive properties of four acrylamide-based polymers with LCST, namely poly[(
N
-2,2-difluoroethyl)acrylamide] (
pDFEA
), poly[(
N
-isopropyl)acrylamide] (
pNIPAM
), poly[(
N
,
N
-diethyl)acrylamide] (
pDEA
), and poly[(
N
-acryloyl)pyrrolidine] (
pAP
). As shown by turbidimetry, their
T
CP
in phosphate saline buffer (PBS) and foetal bovine serum (FBS) were consistently lower than those reported in the literature, typically assessed in pure water, even when using the same setup. In addition, these physiological solutions affected the variation of
T
CP
as a function of polymer concentration (1.25 to 10.0 mg mL
−1
) and molar mass (20 to 50 kg mol
−1
). As shown by isothermal calorimetry, interactions between proteins in FBS and polymer aggregates were predominantly exothermic, which indicates that protein-polymer complexes are formed through enthalpically driven processes. In conclusion, the
T
CP
of thermoresponsive polymers strongly depends on solvent composition and therefore should be measured under physiological conditions for future medicinal applications.
We show that the cloud point temperature (
T
CP
) of thermoresponsive polyacrylamides is considerably lower in physiologically relevant solvents (phosphate-buffered saline, serum) than in pure water. This decrease of
T
CP
may be critical for some biomedical applications.</description><subject>Abbreviations</subject><subject>Acrylamide</subject><subject>Biomedical materials</subject><subject>Cell adhesion</subject><subject>Heat measurement</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Phase separation</subject><subject>Photon correlation spectroscopy</subject><subject>Physiology</subject><subject>Polyacrylamide</subject><subject>Polyisopropyl acrylamide</subject><subject>Polymer chemistry</subject><subject>Polymers</subject><subject>Proteins</subject><subject>Refractivity</subject><issn>1759-9954</issn><issn>1759-9962</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpFkE1LAzEQhoMoWGov3oUFb0I1k2w2u8dSvwoFPdSDpyVfa1N2NzHZCvvvjVbqHGaG4Zl3hhehS8C3gGl1p8GPGJc5FSdoApxV86oqyOmxZ_k5msW4wyko5IQWE7TabE3oXDDRuz7aL5P54LwJgzUxc03mXTsKFcZWdFanke0zvx2jda37sEq0WXTtfrBp9wKdNaKNZvZXp-jt8WGzfJ6vX55Wy8V6rmhJh5QhF1Wjciq5pkpLWWgAYxiUIKUiJZUAVaGZBt5IziRWFJdcsJwoRrmkU3R90E2Pfu5NHOqd24c-nawJ4wSAkyQyRTcHSgUXYzBN7YPtRBhrwPWPW_U9vL7_urVI8NUBDlEduX836TeNwWgZ</recordid><startdate>20210921</startdate><enddate>20210921</enddate><creator>Kolouchová, Kristýna</creator><creator>Lobaz, Volodymyr</creator><creator>Beneš, Hynek</creator><creator>de la Rosa, Victor R</creator><creator>Babuka, David</creator><creator>Švec, Pavel</creator><creator>ernoch, Peter</creator><creator>Hrubý, Martin</creator><creator>Hoogenboom, Richard</creator><creator>Št pánek, Petr</creator><creator>Groborz, Ond ej</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-5075-261X</orcidid><orcidid>https://orcid.org/0000-0003-1433-678X</orcidid><orcidid>https://orcid.org/0000-0003-0479-2837</orcidid><orcidid>https://orcid.org/0000-0002-8874-8632</orcidid><orcidid>https://orcid.org/0000-0003-1817-3818</orcidid><orcidid>https://orcid.org/0000-0001-7398-2058</orcidid><orcidid>https://orcid.org/0000-0002-3164-6168</orcidid><orcidid>https://orcid.org/0000-0002-1136-2280</orcidid><orcidid>https://orcid.org/0000-0002-6604-2815</orcidid></search><sort><creationdate>20210921</creationdate><title>Thermoresponsive properties of polyacrylamides in physiological solutions</title><author>Kolouchová, Kristýna ; Lobaz, Volodymyr ; Beneš, Hynek ; de la Rosa, Victor R ; Babuka, David ; Švec, Pavel ; ernoch, Peter ; Hrubý, Martin ; Hoogenboom, Richard ; Št pánek, Petr ; Groborz, Ond ej</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c383t-c314a9fc43b7d3cdbb6d11ee5181bbc283b1196d5d17fb75b0c3087a542c537b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Abbreviations</topic><topic>Acrylamide</topic><topic>Biomedical materials</topic><topic>Cell adhesion</topic><topic>Heat measurement</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Phase separation</topic><topic>Photon correlation spectroscopy</topic><topic>Physiology</topic><topic>Polyacrylamide</topic><topic>Polyisopropyl acrylamide</topic><topic>Polymer chemistry</topic><topic>Polymers</topic><topic>Proteins</topic><topic>Refractivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kolouchová, Kristýna</creatorcontrib><creatorcontrib>Lobaz, Volodymyr</creatorcontrib><creatorcontrib>Beneš, Hynek</creatorcontrib><creatorcontrib>de la Rosa, Victor R</creatorcontrib><creatorcontrib>Babuka, David</creatorcontrib><creatorcontrib>Švec, Pavel</creatorcontrib><creatorcontrib>ernoch, Peter</creatorcontrib><creatorcontrib>Hrubý, Martin</creatorcontrib><creatorcontrib>Hoogenboom, Richard</creatorcontrib><creatorcontrib>Št pánek, Petr</creatorcontrib><creatorcontrib>Groborz, Ond ej</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kolouchová, Kristýna</au><au>Lobaz, Volodymyr</au><au>Beneš, Hynek</au><au>de la Rosa, Victor R</au><au>Babuka, David</au><au>Švec, Pavel</au><au>ernoch, Peter</au><au>Hrubý, Martin</au><au>Hoogenboom, Richard</au><au>Št pánek, Petr</au><au>Groborz, Ond ej</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Thermoresponsive properties of polyacrylamides in physiological solutions</atitle><jtitle>Polymer chemistry</jtitle><date>2021-09-21</date><risdate>2021</risdate><volume>12</volume><issue>35</issue><spage>577</spage><epage>584</epage><pages>577-584</pages><issn>1759-9954</issn><eissn>1759-9962</eissn><notes>13</notes><notes>C</notes><notes>d</notes><notes>H-</notes><notes>F</notes><notes>C HSQC), size exclusion chromatograms (SEC traces) of the study polymers; raw and processed turbidimetric data, raw and processed isothermal calorimetry data, dynamic light scattering data, refractive index increment (d</notes><notes>10.1039/d1py00843a</notes><notes>H</notes><notes>19</notes><notes>n</notes><notes>Electronic supplementary information (ESI) available: Material section, experimental & instrumental section (detailed description of monomer and polymer syntheses); processed NMR spectra</notes><notes>1</notes><notes>additional information, list of abbreviations and symbols used in this article, and author contributions (CRediT). See DOI</notes><abstract>Polymer solutions with a lower critical solution temperature (LCST) undergo reversible phase separation when heated above their cloud point temperature (
T
CP
or CPT). As such, they have been proposed for a wide range of biomedical applications, from injectable drug depots to switchable coatings for cell adhesion. However, in systematic studies, the
T
CP
of these thermoresponsive polymers has been mostly measured in non-physiological solutions, thereby hindering the development of their medicinal applications. Here, we analysed the thermoresponsive properties of four acrylamide-based polymers with LCST, namely poly[(
N
-2,2-difluoroethyl)acrylamide] (
pDFEA
), poly[(
N
-isopropyl)acrylamide] (
pNIPAM
), poly[(
N
,
N
-diethyl)acrylamide] (
pDEA
), and poly[(
N
-acryloyl)pyrrolidine] (
pAP
). As shown by turbidimetry, their
T
CP
in phosphate saline buffer (PBS) and foetal bovine serum (FBS) were consistently lower than those reported in the literature, typically assessed in pure water, even when using the same setup. In addition, these physiological solutions affected the variation of
T
CP
as a function of polymer concentration (1.25 to 10.0 mg mL
−1
) and molar mass (20 to 50 kg mol
−1
). As shown by isothermal calorimetry, interactions between proteins in FBS and polymer aggregates were predominantly exothermic, which indicates that protein-polymer complexes are formed through enthalpically driven processes. In conclusion, the
T
CP
of thermoresponsive polymers strongly depends on solvent composition and therefore should be measured under physiological conditions for future medicinal applications.
We show that the cloud point temperature (
T
CP
) of thermoresponsive polyacrylamides is considerably lower in physiologically relevant solvents (phosphate-buffered saline, serum) than in pure water. This decrease of
T
CP
may be critical for some biomedical applications.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d1py00843a</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-5075-261X</orcidid><orcidid>https://orcid.org/0000-0003-1433-678X</orcidid><orcidid>https://orcid.org/0000-0003-0479-2837</orcidid><orcidid>https://orcid.org/0000-0002-8874-8632</orcidid><orcidid>https://orcid.org/0000-0003-1817-3818</orcidid><orcidid>https://orcid.org/0000-0001-7398-2058</orcidid><orcidid>https://orcid.org/0000-0002-3164-6168</orcidid><orcidid>https://orcid.org/0000-0002-1136-2280</orcidid><orcidid>https://orcid.org/0000-0002-6604-2815</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Polymer chemistry, 2021-09, Vol.12 (35), p.577-584 |
| issn | 1759-9954 1759-9962 |
| language | eng |
| recordid | cdi_crossref_primary_10_1039_D1PY00843A |
| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| subjects | Abbreviations Acrylamide Biomedical materials Cell adhesion Heat measurement NMR Nuclear magnetic resonance Phase separation Photon correlation spectroscopy Physiology Polyacrylamide Polyisopropyl acrylamide Polymer chemistry Polymers Proteins Refractivity |
| title | Thermoresponsive properties of polyacrylamides in physiological solutions |
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