Aggregation behavior of triblock terpolymer poly[<scp>n</scp>‐butyl acrylate‐<scp>block</scp>‐<scp>N</scp>‐isopropylacrylamide‐<scp>block</scp>‐2‐(dimethylamino)ethyl acrylate] at the air/water interface

Liu, Dongxue; Wen, Gangyao; Skandalis, Athanasios; Pispas, Stergios; He, Guanying; Zhang, Wang

doi:10.1002/app.52989

Cited by 4 publications

(1 citation statement)

References 27 publications

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“…Many researchers have demonstrated the ability of amphiphilic block copolymers to self-assemble into various monolayers at the air–water interface, − and the formation of nanoaggregates can be primarily controlled by modifying the polymer composition. Some common linear copolymers, such as polystyrene- block -poly(ethylene oxide) (PS- b -PEO), − polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA), − and polystyrene- block -poly(2-vinylpyridine) (PS- b -P2VP), , have been comprehensively studied.…”

Section: Introductionmentioning

confidence: 99%

Closely Packed Core–Shell Micelle Structures of Double Hydrophilic Miktoarm Star Copolymers at the Air–Water Interface

Zhang,

Wen,

Giaouzi

et al. 2024

Langmuir

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The aggregation behavior of amphiphilic block copolymers at the air−water interface has been extensively studied, but less attention was given to that of star copolymers. In this work, we studied the interfacial aggregation behavior of two double hydrophilic pH-and temperatureresponsive miktoarm star copolymers of poly[di(ethylene glycol) methyl ether methacrylate]-poly [2-(dimethylamino)ethyl methacrylate] (PDEG-MA 3 -PDMAEMA 3 and PDEGMA 4 -PDMAEMA 7 , the subscripts denote arm numbers) with different molecular weights. The effects of subphase pH and temperature on the monolayer isotherms and hysteresis curves of the two star copolymers and the morphologies of their Langmuir−Blodgett (LB) films were studied by the Langmuir film balance technique and atomic force microscopy, respectively. At the air−water interface, the two star copolymers tend to form closely packed micelles. These micelles exhibit a core−shell structure, where the small hydrophobic core consists of cross-linker of ethylene glycol dimethacrylate (EGDMA) and the carbon backbones of PDEGMA and PDMAEMA arms and the short hydrophilic shell is composed of di(ethylene glycol) and tertiary amine side groups. With increasing subphase pH, the surface pressure versus molecular area isotherms shift toward larger mean molecular areas as a result of the enhanced interface adsorption of nonprotonated tertiary amine groups. The isotherm shift of PDEGMA 3 -PDMAEMA 3 monolayers is primarily attributed to high density of tertiary amine groups in the shells, while that of PDEGMA 4 -PDMAEMA 7 is mainly attributed to high density of di(ethylene glycol) groups in the shells. The hysteresis degrees in the monolayers of the two copolymers under alkaline and neutral conditions are greater than those under acidic conditions due to the decreased protonation degree of the tertiary amine groups. At 10 °C, the mobility of the shells is poor and the isotherms are located on the right. Above the lower critical solution temperature, di(ethylene glycol) groups contract, which causes a slight shift of the isotherms toward smaller mean molecular areas.

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Section: Introductionmentioning

confidence: 99%

Closely Packed Core–Shell Micelle Structures of Double Hydrophilic Miktoarm Star Copolymers at the Air–Water Interface

Zhang,

Wen,

Giaouzi

et al. 2024

Langmuir

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Effects of subphase pH and temperature on the interfacial behavior of double hydrophilic diblock copolymer PDEGMA‐b‐PDIPAEMA

Li,

Wen,

Selianitis

et al. 2023

J of Applied Polymer Sci

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The aggregation behavior of two pH‐ and temperature‐responsive diblock copolymers of poly[di‐(ethylene glycol) methyl ether methacrylate]‐block‐poly[2‐(diisopropylamino) ethyl methacrylate] (PDEGMA‐b‐PDIPAEMA) at the air/water interface and the structures of their Langmuir–Blodgett (LB) films were studied by the Langmuir monolayer technique and atomic force microscopy, respectively. At the air/water interface, PDEGMA‐b‐PDIPAEMA tends to form the core‐shell‐corona micellar structure composed of a PDIPAEMA main chain core, an amino ethyl ester shell, and a PDEGMA corona. Under acidic, neutral, and alkaline conditions, PDIPAEMA blocks are completely protonated, partially protonated, and completely non‐protonated, respectively, and the protonated amino ethyl ester groups are immersed in water before monolayer compression, whereas PDEGMA coronas are adsorbed at the interface. At pH 3, 7, and 10, the limiting areas (A0) for PDEGMA42%‐PDIPAEMA58% (weight percents) and PDEGMA55%‐PDIPAEMA45% are 8.2/10.2/14.0 and 6.7/8.3/8.4 nm2, respectively. The A0 values of the former copolymer are larger than those of the latter. This is because the shells in the former copolymer are denser due to the higher polymerization degree of PDIPAEMA blocks, providing greater steric hindrance for PDEGMA coronas and making the latter more extended at the interface. In contrast to other copolymer systems, the effect of temperature on the isotherms of PDEGMA‐b‐PDIPAEMA is less obvious.

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Ionic strength and anion‐specificity effects on the interfacial behavior of double hydrophilic block copolymer PNIPAM‐b‐POEGA

Pan,

Wen,

Giaouzi

et al. 2024

J of Applied Polymer Sci

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In our prior paper, surface micelles with the core‐shell‐petal structure of the double hydrophilic block copolymer poly(N‐isopropylacrylamide)‐block‐poly[oligo(ethylene glycol) acrylate] (PNIPAM‐b‐POEGA) were successfully evaluated. In this work, ionic strength (under acidic conditions) and anion‐specificity effects (under neutral conditions) on the aggregation behavior of PNIPAM‐b‐POEGA at the air/water interface and the morphologies of its Langmuir–Blodgett (LB) films were systematically studied. Under acidic conditions, the salting‐out effect prevails over the electrostatic shielding effect, and the amide group shells with a slight protonation degree are covered up by the large POEGA petals. Under neutral conditions, the stretching degrees of POEGA blocks at low/moderate salt concentrations are close. At high salt concentrations, the isotherms gradually shift to large molecular areas in the order of the NaCl, Na2SO4, NaNO3, and NaSCN cases. The hysteresis degrees of the monolayers increase with the increase of salt concentrations due to the gradually increased interfacial stretching degree and compression‐induced underwater solubility of POEGA blocks. All the initial LB films of PNIPAM‐b‐POEGA exhibit isolated circular micelles with small cores. Upon compression, the LB films exhibit slightly large micelles because of the possible coalescence of some neighboring cores.

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Aggregation behavior of triblock terpolymer poly[n‐butyl acrylate‐block‐N‐isopropylacrylamide‐block‐2‐(dimethylamino)ethyl acrylate] at the air/water interface

Cited by 4 publications

References 27 publications

Closely Packed Core–Shell Micelle Structures of Double Hydrophilic Miktoarm Star Copolymers at the Air–Water Interface

Closely Packed Core–Shell Micelle Structures of Double Hydrophilic Miktoarm Star Copolymers at the Air–Water Interface

Effects of subphase pH and temperature on the interfacial behavior of double hydrophilic diblock copolymer PDEGMA‐b‐PDIPAEMA

Ionic strength and anion‐specificity effects on the interfacial behavior of double hydrophilic block copolymer PNIPAM‐b‐POEGA

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