Wavelength‐Gated Adaptation of Hydrogel Properties via Photo‐Dynamic Multivalency in Associative Star Polymers

Ludwanowski, Simon; Skarsetz, Oliver; Creusen, Guido; Hoenders, Daniel; Straub, Paula; Walther, Andreas

doi:10.1002/anie.202011592

Cited by 19 publications

(24 citation statements)

References 40 publications

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“…The amount of cis - PI present at the 365 nm photostationary state depends strongly on the applied photon flux, and variation in light intensity therefore introduces an easy route to modulate the effective inhibitor strength. Thus, similar to the recently described light engineering of the PSS for wavelength-gated adaptation of hydrogel properties, a wide range of enzymatic activity can be accessed by utilizing PIs, which enables fine-tuning the kinetics of enzyme-catalyzed reactions using light. Figure C shows how irradiation with 365 and 460 nm light is translated into a well-controlled temporal pattern of Cr activity.…”

Section: Resultsmentioning

confidence: 98%

Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions

2021

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Ultrasensitivity is a ubiquitous emergent property of biochemical reaction networks. The design and construction of synthetic reaction networks exhibiting ultrasensitivity has been challenging, but would greatly expand the potential properties of life-like materials. Herein, we exploit a general and modular strategy to reversibly regulate the activity of enzymes using light and show how ultrasensitivity arises in simple out-of-equilibrium enzymatic systems upon incorporation of reversible photoswitchable inhibitors (PIs). Utilizing a chromophore/warhead strategy, PIs of the protease α-chymotrypsin were synthesized, which led to the discovery of inhibitors with large differences in inhibition constants ( K i ) for the different photoisomers. A microfluidic flow setup was used to study enzymatic reactions under out-of-equilibrium conditions by continuous addition and removal of reagents. Upon irradiation of the continuously stirred tank reactor with different light pulse sequences, i.e., varying the pulse duration or frequency of UV and blue light irradiation, reversible switching between photoisomers resulted in ultrasensitive responses in enzymatic activity as well as frequency filtering of input signals. This general and modular strategy enables reversible and tunable control over the kinetic rates of individual enzyme-catalyzed reactions and makes a programmable linkage of enzymes to a wide range of network topologies feasible.

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Section: Resultsmentioning

confidence: 98%

Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions

2021

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“…Importantly, by varying the light intensity, the effective inhibitor strength can be gradually altered, thereby enabling fine-tuning of the kinetics of enzyme-catalyzed reactions using light as external stimuli. [35] By installing 390 and 460 nm light pulses with different intensities and durations, the output of the enzymatic system can be precisely and reproducibly regulated (see 8.2.2 of Supporting Information for experimental results and details). In the absence of a 460 nm light pulse for photoinduced cis to trans isomerization of Tr-PI, an exponential decay in AMC concentration with time was observed (Figure 3B, green curve).…”

Section: Resultsmentioning

confidence: 99%

Reversible Photoswitchable Inhibitors Enable Wavelength‐Selective Regulation of Out‐of‐Equilibrium Bi‐enzymatic Systems

2021

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The construction of synthetic enzymatic reaction networks can provide new insights into the design principles of living systems. However, the programmable connection of enzymes into a wide range of network topologies has been challenging due to the lack of a general strategy enabling a reversible activity regulation of individual network enzymes. Here, we exploit a general and modular strategy based on the external regulation of enzymes using light and photoswitchable inhibitors (PIs) that enables the bottom-up construction and control of enzymatic systems studied under out-of-equilibrium conditions. Upon synthesis and incorporation of potent photoswitchable trypsin inhibitors (Tr-PIs), the output of several functional enzymatic systems could be photoregulated using 390/460 nm light as a trigger signal. In addition, the wavelength-selective control over the activity of two enzymes within a functional bi-enzymatic system was achieved using a suitable combination of two PIs.

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“…At the same time, the presence of methyl groups on the heterocyclic moiety (structure I vs structure II , Figure ) was found to accelerate the isomerization process . Furthermore, dimethyl-substituted pyrazole-based azoheteroarenes of type I (Figure ) were recognized for their suitability in biological applications, and slight structural modifications aiming to improve water solubility yielded photoswitches with appropriate properties, stability against glutathione or utility for reversible control of DNA hybridization, or as efficient enzyme inhibitors. , In addition, they were found to be useful in the construction of solar thermal fuels or generation of hydrogels. , …”

Section: Introductionmentioning

confidence: 99%

Exploring Arylazo-3,5-Bis(trifluoromethyl)pyrazole Switches

et al. 2022

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Arylazopyrazoles stand out among the azoheteroarene photoswitches due to their excellent properties in terms of stability of the least stable isomer and conversion between isomers, leading to their use in several interesting applications. We report herein the synthesis of arylazo-trifluoromethyl-substituted pyrazoles and their switching behavior under light irradiation. UV−vis and NMR experiments showed that arylazo-1H-3,5-bis(trifluoromethyl)pyrazoles displayed very long half-lives in DMSO (days), along with reasonable values of other parameters that characterize a photoswitch. Inclusion of naphthyl moieties as aryl counterparts of the arylazopyrazoles is beneficial only in combination with trifluoromethyl groups, while extending the conjugation by grafting the pyrazole moiety with electron-donating or -withdrawing substituents positively affects the photoswitching behavior, in terms of isomerization yield and half-lives of the least stable isomer. The experimental values were correlated with theoretical calculations indicating the valuable influence of the trifluoromethyl groups onto the photoswitching behavior.

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Wavelength‐Gated Adaptation of Hydrogel Properties via Photo‐Dynamic Multivalency in Associative Star Polymers

Cited by 19 publications

References 40 publications

Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions

Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions

Reversible Photoswitchable Inhibitors Enable Wavelength‐Selective Regulation of Out‐of‐Equilibrium Bi‐enzymatic Systems

Exploring Arylazo-3,5-Bis(trifluoromethyl)pyrazole Switches

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