Chiara Perrino, Seunghwan Lee and Nicholas D. Spencer*,
{"title":"定量比较表面结合葡聚糖和聚乙二醇的水合能力","authors":"Chiara Perrino, Seunghwan Lee and Nicholas D. Spencer*, ","doi":"10.1021/acs.langmuir.4c01582","DOIUrl":null,"url":null,"abstract":"<p >We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(<span>l</span>-lysine)-<i>graft</i>-dextran (PLL-<i>g</i>-dex) and poly(<span>l</span>-lysine)-<i>graft</i>-poly(ethylene glycol) (PLL-<i>g</i>-PEG), respectively. The copolymers were attached to a negatively charged silica–titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-<i>g</i>-PEG(5) and PLL(20)-<i>g</i>-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as <i>g</i> decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the −CH<sub>2</sub>CH<sub>2</sub>O– units that make up the PEG chains form a cage-like structure with 2–3 water molecules, these “strongly bound” water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7000,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.langmuir.4c01582","citationCount":"0","resultStr":"{\"title\":\"Quantitative Comparison of the Hydration Capacity of Surface-Bound Dextran and Polyethylene Glycol\",\"authors\":\"Chiara Perrino, Seunghwan Lee and Nicholas D. Spencer*, \",\"doi\":\"10.1021/acs.langmuir.4c01582\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(<span>l</span>-lysine)-<i>graft</i>-dextran (PLL-<i>g</i>-dex) and poly(<span>l</span>-lysine)-<i>graft</i>-poly(ethylene glycol) (PLL-<i>g</i>-PEG), respectively. The copolymers were attached to a negatively charged silica–titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-<i>g</i>-PEG(5) and PLL(20)-<i>g</i>-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as <i>g</i> decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the −CH<sub>2</sub>CH<sub>2</sub>O– units that make up the PEG chains form a cage-like structure with 2–3 water molecules, these “strongly bound” water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.</p>\",\"PeriodicalId\":50,\"journal\":{\"name\":\"Langmuir\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2024-06-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.langmuir.4c01582\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Langmuir\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.langmuir.4c01582\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Langmuir","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.langmuir.4c01582","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Quantitative Comparison of the Hydration Capacity of Surface-Bound Dextran and Polyethylene Glycol
We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(l-lysine)-graft-dextran (PLL-g-dex) and poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG), respectively. The copolymers were attached to a negatively charged silica–titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-g-PEG(5) and PLL(20)-g-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as g decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the −CH2CH2O– units that make up the PEG chains form a cage-like structure with 2–3 water molecules, these “strongly bound” water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.
期刊介绍:
Langmuir is an interdisciplinary journal publishing articles in the following subject categories:
Colloids: surfactants and self-assembly, dispersions, emulsions, foams
Interfaces: adsorption, reactions, films, forces
Biological Interfaces: biocolloids, biomolecular and biomimetic materials
Materials: nano- and mesostructured materials, polymers, gels, liquid crystals
Electrochemistry: interfacial charge transfer, charge transport, electrocatalysis, electrokinetic phenomena, bioelectrochemistry
Devices and Applications: sensors, fluidics, patterning, catalysis, photonic crystals
However, when high-impact, original work is submitted that does not fit within the above categories, decisions to accept or decline such papers will be based on one criteria: What Would Irving Do?
Langmuir ranks #2 in citations out of 136 journals in the category of Physical Chemistry with 113,157 total citations. The journal received an Impact Factor of 4.384*.
This journal is also indexed in the categories of Materials Science (ranked #1) and Multidisciplinary Chemistry (ranked #5).