Tunable Thermoresponsive Polymers by Molecular Design

Hoogenboom, Richard

doi:10.1002/9780470825150.ch22

Cited by 13 publications

(10 citation statements)

References 139 publications

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“…The oligomer states were characterized by the distance between the oligomer ends, while the oligomer conformation was additionally controlled by the gyration radius. The low critical solution temperature of the oligo-30s-NIPAm was specified to be close to 305 K [ 29 , 30 , 31 , 32 ], so a temperature equal to 290 K was chosen for the preparation of samples in the open state, while it was equal to 320 K for samples in the close state. Figure 1 a shows the shapes of the open and closed states of oligo-30s-NIPAm equilibrated at 290 K and 320 K, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Detection of Single Molecules Using Stochastic Resonance of Bistable Oligomers

et al. 2020

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Ultra-sensitive elements for nanoscale devices capable of detecting single molecules are in demand for many important applications. It is generally accepted that the inevitable stochastic disturbance of a sensing element by its surroundings will limit detection at the molecular level. However, a phenomenon exists (stochastic resonance) in which the environmental noise acts abnormally: it amplifies, rather than distorts, a weak signal. Stochastic resonance is inherent in non-linear bistable systems with criticality at which the bistability emerges. Our computer simulations have shown that the large-scale conformational dynamics of a short oligomeric fragment of thermosrespective polymer, poly-N-isopropylmethacrylamid, resemble the mechanical movement of nonlinear bistable systems. The oligomers we have studied demonstrate spontaneous vibrations and stochastic resonance activated by conventional thermal noise. We have observed reasonable shifts of the spontaneous vibrations and stochastic resonance modes when attaching an analyte molecule to the oligomer. Our simulations have shown that spontaneous vibrations and stochastic resonance of the bistable thermoresponsive oligomers are sensitive to both the analyte molecular mass and the binding affinity. All these effects indicate that the oligomers with mechanic-like bistability may be utilized as ultrasensitive operational units capable of detecting single molecules.

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Section: Resultsmentioning

confidence: 99%

“…The oligo-30s-NIPMAm and the environmental water were modeled in a fully atomistic representation in a box sized 6.0 × 8.0 × 8.0 nm with a time step of 1 fs. The temperature was set at 290 K, i.e.,sufficiently below the low critical solution temperature of the poly-NIPMAm [ 29 , 30 , 31 , 32 ].…”

Section: Materials and Simulation Methodsmentioning

confidence: 99%

Detection of Single Molecules Using Stochastic Resonance of Bistable Oligomers

et al. 2020

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“…In particular, thermoresponsive polymers, with the ability to respond to changes in temperature, have led to the development of a vast number of applications in areas spanning construction [25,26], water management [27], separation sciences [28,29], shape memory materials [30], and biomedicine [31], and allow the development of smart soluble materials or smart fluids. Most of such polymeric materials that undergo a solubility phase transition in response to a change in temperature exhibit a lower critical solution temperature (LCST) [32].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular control over thermoresponsive polymers

2016

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Thermoresponsive polymers facilitate the development of a wide range of applications in multiple areas spanning from construction or water management to lab-on-a-chip technologies and biomedical sciences. The combination of thermoresponsive polymers with supramolecular chemistry, inspired by the molecular mechanisms behind natural systems, is resulting in adaptive and smart materials with unprecedented properties. This work reviews the past advances on the combination of this young field of research with polymer chemistry that is enabling a high level of control on polymer architecture and stimuli-responsiveness in solution. We will discuss how such polymer systems are able to store thermal information, respond to multiple stimuli in a reversible manner, or adapt their morphology on demand, all powered by the synergy between polymer chemistry and supramolecular chemistry

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“…Upon heating above certain temperatures the polymers transition from a hydrophilic to a hydrophobic state, as evidenced by their structural transition from a random coil to a globule state and accompanying phase separation. 17,18 This behaviour is characteristic of the lower critical solution temperature (LCST) phenomenon, an entropy driven process which is dened as the temperature at the minimum of the bimodal of the polymer phase diagram. 19 At different polymer concentrations this transition is visually observed as a clouding of the otherwise transparent polymerwater solution at a particular temperature (cloud point temperature; T CP ).…”

Section: Introductionmentioning

confidence: 99%

“…20 As cloud temperatures are specic to each individual polymer, they can be modulated to higher or lower temperatures simply by changing the polymer composition to be more hydrophilic or hydrophobic, respectively. 18 The cloud point of a polymer in solution can also be modied by including charged moieties that are inherently responsive to changes in pH or salt concentrations. 21,22 Our research group is focussing on the novel separation of analytes from aqueous food or food by-product streams.…”

Section: Introductionmentioning

confidence: 99%