Wellenlängengesteuerte Adaption der Hydrogeleigenschaften durch Photodynamische Multivalenz in Assoziierenden Sternpolymeren

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

doi:10.1002/ange.202011592

Cited by 3 publications

(1 citation statement)

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, 48 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, 50 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 3 C shows how irradiation with 365 and 460 nm light is translated into a well-controlled temporal pattern of Cr activity.…”

Section: Resultsmentioning

confidence: 91%

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: 91%

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

2021

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An Amino Acid‐Based Thixotropic Hydrogel: Tuning of Gel Recovery Time by Mechanical Shaking

Bassan

Varshney²,

Roy

2023

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Fmoc-Trp-OH (Fmoc: N-fluorenylmethoxycarbonyl; Trp-OH: L-Tryptophan) undergone hydrogelation at 50 mM phosphate buffer saline of pH 7.4 with a minimum gelation concentration (MGC) of 0.25 % w/v after 12 to 15 hours. However, the hydrogel formation kinetics can be faster just by mechanical hand shaking of the hydrogelator solution during the hydrogel preparation procedure. The shake hydrogel is thermally and mechanically more stable than the non-shake hydrogel. These hydrogels have been characterized thoroughly by Tgel estimations, UV-Vis spectroscopy, Fluorescence spectroscopy, Fourier Transform-Infra Red (FT-IR) Spectroscopy, X-ray diffractions (XRD), Field Emission Scanning Electron Microscopy (FE-SEM) and rheology. This amino acid-based hydrogel is thixotropic in nature and interestingly without doping any foreign materials into the hydrogel, the gel reformation kinetics can be faster just by number of times breaking of the hydrogel by mechanical hand shaking followed by keeping the hydrogel glass vial at rest. This holds future promise to develop supramolecular mechanocatalyst for various functional group transformation reactions in water through green and sustainable chemistry pathways.

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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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Wellenlängengesteuerte Adaption der Hydrogeleigenschaften durch Photodynamische Multivalenz in Assoziierenden Sternpolymeren

Cited by 3 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

An Amino Acid‐Based Thixotropic Hydrogel: Tuning of Gel Recovery Time by Mechanical Shaking

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

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