Enzymatically degradable star polypeptides with tunable UCST transitions in solution and within layer-by-layer films

Zhou, Qing; Palanisamy, Anbazhagan; Albright, Victoria; Sukhishvili, Svetlana A.

doi:10.1039/c8py00939b

Cited by 12 publications

(26 citation statements)

References 30 publications

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“…previously, the UCST of this enzymatically degradable star polymer is tunable through degree of ureido modification and by change length of polypeptide arms [51]. Ureido groups containing polymer i.e.…”

Section: Figure 12mentioning

confidence: 99%

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Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

Bansal¹,

Upadhyay²,

Saraogi³

et al. 2019

Express Polym. Lett.

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Immense work has been conducted in the field of thermoresponsive polymers specifically of lower critical solution temperature (LCST) type, but upper critical solution temperature (UCST) type polymers remain a significantly unexplored domain. However, in recent years, UCST polymers have attracted increased attention as evidenced by the rise in publications in the same domain, and therefore, this review is an attempt to compile the reported UCST-type polymers. Unlike LCST, UCST polymers are insoluble at low temperature but solubilize in a given solvent as the temperature increases. The synthesis approaches and applications of reported UCST polymers are discussed in this article. Emphasis has been given to the polymers exhibiting UCST behavior in aqueous medium, due to the obvious advantage of their wide applicability. It is quite apparent from this study that the attempts to synthesize novel polymers and copolymers exhibiting UCST has faced an upsurge, but their application part still requires considerable attention. Figure 4. (a) Representative structure of poly(acrylamide-co-acrylonitrile) and (b) turbidity cooling curves of poly(AAmco-AN) with different acrylonitrile content in mole% (numbers in graph). Reproduced with permission from [33],

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Section: Figure 12mentioning

confidence: 99%

“…Synthesis scheme for dendritic SPOC polymers using G4-PAMAM dendrimer as initiator (core) and protected NCA as monomer via ROP (KOCN -potassium cyanate). Reproduced with permission from [51], Copyright © 2018, The Royal Society of Chemistry.…”

Section: Figure 12mentioning

confidence: 99%

Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

Bansal¹,

Upadhyay²,

Saraogi³

et al. 2019

Express Polym. Lett.

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“…One might speculate as well that the sterically restricted geometry of the star polymer hampers the formation of intermolecular hydrogen bonds, which are crucial for the UCST-type response. However, Zhou et al demonstrate that in the case of star-shaped polypeptides (star-poly(ʟ-ornithin- co -ʟ-citrullin) (SPOC), the increase in arm length from ≈60 kDa to ≈100 kDa results in an increase in the UCST-type phase transition temperature from 18 °C to 31 °C [ 314 ] ( Figure 9 , part C). Although analogous to the star-shaped P(PAAm- co -AN) of Qi et al, the UCST behavior is based on hydrogen bonding, the steric confinement of the polypeptide chains does not seem to hamper attractive intermolecular interactions in this case [ 313 ].…”

Section: Reviewmentioning

confidence: 99%

“…Although analogous to the star-shaped P(PAAm- co -AN) of Qi et al, the UCST behavior is based on hydrogen bonding, the steric confinement of the polypeptide chains does not seem to hamper attractive intermolecular interactions in this case [ 313 ]. Moreover, it is demonstrated that the high local concentration of functional groups and therefore strong polymer–polymer interactions lead to a higher T c of the star polypeptide compared to a linear analogue with matching polymer chain length and similar composition [ 314 ]. Interestingly, the dendritic topology of the star polypeptide revealed a very low concentration dependency of the phase transition temperature.…”

Section: Reviewmentioning

confidence: 99%

“…Interestingly, the dendritic topology of the star polypeptide revealed a very low concentration dependency of the phase transition temperature. While a T c shift of more than 10 °C was detected for linear ureido-based polymers when the concentration was increased from 0.5 mg/mL to 2.5 mg/mL [ 315 ], the T c varied only by a few degrees Celsius for the star polypeptides (<3 °C) [ 314 ]. The phase transition itself occurs within a remarkably small temperature window (<5 °C).…”

Section: Reviewmentioning

confidence: 99%

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Constrained thermoresponsive polymers – new insights into fundamentals and applications

Flemming¹,

Münch²,

Fery³

et al. 2021

Beilstein J. Org. Chem.

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In the last decades, numerous stimuli-responsive polymers have been developed and investigated regarding their switching properties. In particular, thermoresponsive polymers, which form a miscibility gap with the ambient solvent with a lower or upper critical demixing point depending on the temperature, have been intensively studied in solution. For the application of such polymers in novel sensors, drug delivery systems or as multifunctional coatings, they typically have to be transferred into specific arrangements, such as micelles, polymer films or grafted nanoparticles. However, it turns out that the thermodynamic concept for the phase transition of free polymer chains fails, when thermoresponsive polymers are assembled into such sterically confined architectures. Whereas many published studies focus on synthetic aspects as well as individual applications of thermoresponsive polymers, the underlying structure–property relationships governing the thermoresponse of sterically constrained assemblies, are still poorly understood. Furthermore, the clear majority of publications deals with polymers that exhibit a lower critical solution temperature (LCST) behavior, with PNIPAAM as their main representative. In contrast, for polymer arrangements with an upper critical solution temperature (UCST), there is only limited knowledge about preparation, application and precise physical understanding of the phase transition. This review article provides an overview about the current knowledge of thermoresponsive polymers with limited mobility focusing on UCST behavior and the possibilities for influencing their thermoresponsive switching characteristics. It comprises star polymers, micelles as well as polymer chains grafted to flat substrates and particulate inorganic surfaces. The elaboration of the physicochemical interplay between the architecture of the polymer assembly and the resulting thermoresponsive switching behavior will be in the foreground of this consideration.

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Polyelectrolyte multilayers for drug delivery

Andreeva

2020

Advances and Avenues in the Development of Novel Carriers for Bioactives and Biological Agents

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Enzymatically degradable star polypeptides with tunable UCST transitions in solution and within layer-by-layer films

Abstract: Enzymatically degradable star polypeptides exhibit robust UCST-type transitions in aqueous solution and within layer-by-layer assembled films.

Cited by 12 publications

References 30 publications

Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

Constrained thermoresponsive polymers – new insights into fundamentals and applications

Polyelectrolyte multilayers for drug delivery

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