- Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions
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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 (Ki) 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.
- Teders, Michael,Pogodaev, Aleksandr A.,Bojanov, Glenn,Huck, Wilhelm T. S.
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- Highly selective reduction of nitroarenes by iron(0) nanoparticles in water
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Highly selective reduction of nitroarenes has been achieved using iron metal nanoparticles in water at room temperature. A wide spectrum of reducible functionalities remained inert under the reaction conditions. During the reaction a change in shape of Fe nanoparticles was observed.
- Dey, Raju,Mukherjee, Nirmalya,Ahammed, Sabir,Ranu, Brindaban C.
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- Azo aryl urea derivative, and preparation method and application thereof
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The invention relates to an azo aryl urea derivative, and a preparation and an application thereof, and concretely discloses a compound represented by formula (I), or an optical isomer, a cis-trans-isomer or a pharmaceutically acceptable salt thereof, and a preparation method thereof. Definitions of substituent groups in the general formula are described in the specification and claims. The invention further discloses a composition containing the above compound, and an application thereof. The compound has excellent anticancer activity on HepG2 liver cancer cells, MGC803 gastric cancer cells,HCT116 colon cancer and the like.
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Paragraph 0087-0088; 0089-0090; 0145-0148; 0201-0204
(2020/06/17)
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- Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
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The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.
- Roscales, Silvia,Csák?, Aurelio G.
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supporting information
p. 1667 - 1671
(2018/03/23)
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- Nitrosation of aryl and heteroaryltrifluoroborates with nitrosonium tetrafluoroborate
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Organotrifluoroborates have emerged as an alternative to toxic and air- and moisture-sensitive organometallic species for the synthesis of functionalized aryl and heteroaryl compounds. It has been shown that the trifluoroborate moiety can be easily converted into a variety of different substituents in a late synthetic stage. In this paper, we disclose a mild, selective, and convenient method for the ipso-nitrosation of organotrifluoroborates using nitrosonium tetrafluoroborate (NOBF4). Aryl- and heteroaryltrifluoroborates were converted into the corresponding nitroso products in good to excellent yields. This method proved to be tolerant of a broad range of functional groups.
- Molander, Gary A.,Cavalcanti, Livia N.
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experimental part
p. 4402 - 4413
(2012/06/18)
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- Behavior of organic compounds confined in monoliths of sol-gel silica glass. Effects of guest-host hydrogen bonding on uptake, release, and isomerization of the guest compounds
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Various proteins, catalysts, and other compounds can be encapsulated or diffused into porous sol-gel glasses, but little is known about their interactions with the glass matrix. We report unexpectedly large effects that hydrogen bonding between organic co
- Badjic,Kostic
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p. 408 - 418
(2007/10/03)
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