The trifluoromethylation of aromatic and heteroaromatic cores has attracted considerable interest... more The trifluoromethylation of aromatic and heteroaromatic cores has attracted considerable interest in recent years due to its pharmacological relevance. We studied the extension of a simple copper-catalyzed trifluoromethylation protocol to alkoxy-substituted iodopyridines and their benzologs. The trifluoromethylation proceeded smoothly in all cases, and the desired compounds were isolated and characterized. In the trifluoromethylation of 3-iodo-4-methoxyquinoline, we observed a concomitant O-N methyl migration, resulting in the trifluoromethylated quinolone as a product. Overall, the described procedure should facilitate the broader use of copper-catalyzed trifluoromethylation in medicinal chemistry.
Oscillations are one of the intrinsic features of many animate and inanimate systems. The oscilla... more Oscillations are one of the intrinsic features of many animate and inanimate systems. The oscillations manifest in the temporal periodic change of one or several physical quantities describing the systems. In chemistry and biology, this physical quantity is the concentration of the chemical species. In most chemical oscillatory systems operating in batch or open reactors, the oscillations persist because of the sophisticated chemical reaction networks incorporating autocatalysis and negative feedback. However, similar oscillations can be generated by periodically changing the environment providing non-autonomous oscillatory systems. Here we present a new strategy for designing a non-autonomous chemical oscillatory system for the zinc–methylimidazole. The oscillations manifested in the periodic change of the turbidity utilizing the precipitation reaction between the zinc ions and 2-methylimidazole (2-met) followed by a partial dissolution of the formed precipitate due to a synergetic...
A methylene glycol–sulfite chemical clock was used to synthesize zeolitic imidazole framework-8 i... more A methylene glycol–sulfite chemical clock was used to synthesize zeolitic imidazole framework-8 in a time-programmed and autonomous way.
In the past decade, much effort has been devoted to using chemical clock-type reactions in materi... more In the past decade, much effort has been devoted to using chemical clock-type reactions in material design and driving the self-assembly of various building blocks. Urea-urease enzymatic reaction has chemical pH clock behavior in an unbuffered medium, in which the induction time and the final pH can be programmed by the concentrations of the reagents. The urea-urease reaction can offer a new alternative in material synthesis, where the pH and its course in time are crucial factors in the synthesis. However, before using it in any synthesis method, it is important to investigate the possible effects of the reagents on the enzymatic reaction. Here we investigate the effect of the reagents of the zeolite imidazole framework-8 (zinc ions and 2-methylimidazole) on the urea-urease reaction. We have chosen the zeolite imidazole framework-8 because its formation serves as a model reaction for the formation of other metal–organic frameworks. We found that, besides the inhibition effect of th...
Strategies for designing autonomous oscillatory systems have gained much attention in the past fe... more Strategies for designing autonomous oscillatory systems have gained much attention in the past few decades. A broadly accepted and used strategy for the generation of forced oscillations in the originally non-oscillatory subsystems is to couple a pH (driving) oscillator to a pH-sensitive substance (forced oscillatory subsystem) in a one-compartment system. The forced oscillatory subsystem comprises pH-sensitive components, which inevitably generate negative feedback and affect the characteristics of the driving oscillatory system. Here, we present a different approach by separating the driving and forced oscillatory systems into a two-compartment system using a silicone membrane, and the forced oscillations of the absorbance of a pH-sensitive chemical species (methyl red dye) were realized by the transport of carbon dioxide through the membrane generated periodically by the driving pH oscillator. The transported carbon dioxide produced the pH change in the separated compartment by c...
The beat in physical systems is a transparent and well-understood phenomenon. It may occur in for... more The beat in physical systems is a transparent and well-understood phenomenon. It may occur in forced oscillatory systems and as a result of the interference of two waves of slightly different frequencies. However, in chemical systems, the realization of the latter type of the beat phenomenon has been lacking. Here we show that a periodic titration of acid and alkaline solutions with each other using programmable syringe pumps in a continuous stirred-tank reactor exhibits the beat phenomenon in the temporal pH oscillation pattern if the time periods of sinusoidal inflow rates of the reagents are slightly different. Interestingly, the frequency of the chemical beat pattern follows the well-known relationship from physics, namely the frequency of the beat is equal to the absolute value of the difference of the two wave frequencies. Based on our strategy, we can design and engineer non-autonomous pH oscillatory systems, in which the characteristics of the temporal oscillations (amplitud...
The trifluoromethylation of aromatic and heteroaromatic cores has attracted considerable interest... more The trifluoromethylation of aromatic and heteroaromatic cores has attracted considerable interest in recent years due to its pharmacological relevance. We studied the extension of a simple copper-catalyzed trifluoromethylation protocol to alkoxy-substituted iodopyridines and their benzologs. The trifluoromethylation proceeded smoothly in all cases, and the desired compounds were isolated and characterized. In the trifluoromethylation of 3-iodo-4-methoxyquinoline, we observed a concomitant O-N methyl migration, resulting in the trifluoromethylated quinolone as a product. Overall, the described procedure should facilitate the broader use of copper-catalyzed trifluoromethylation in medicinal chemistry.
Oscillations are one of the intrinsic features of many animate and inanimate systems. The oscilla... more Oscillations are one of the intrinsic features of many animate and inanimate systems. The oscillations manifest in the temporal periodic change of one or several physical quantities describing the systems. In chemistry and biology, this physical quantity is the concentration of the chemical species. In most chemical oscillatory systems operating in batch or open reactors, the oscillations persist because of the sophisticated chemical reaction networks incorporating autocatalysis and negative feedback. However, similar oscillations can be generated by periodically changing the environment providing non-autonomous oscillatory systems. Here we present a new strategy for designing a non-autonomous chemical oscillatory system for the zinc–methylimidazole. The oscillations manifested in the periodic change of the turbidity utilizing the precipitation reaction between the zinc ions and 2-methylimidazole (2-met) followed by a partial dissolution of the formed precipitate due to a synergetic...
A methylene glycol–sulfite chemical clock was used to synthesize zeolitic imidazole framework-8 i... more A methylene glycol–sulfite chemical clock was used to synthesize zeolitic imidazole framework-8 in a time-programmed and autonomous way.
In the past decade, much effort has been devoted to using chemical clock-type reactions in materi... more In the past decade, much effort has been devoted to using chemical clock-type reactions in material design and driving the self-assembly of various building blocks. Urea-urease enzymatic reaction has chemical pH clock behavior in an unbuffered medium, in which the induction time and the final pH can be programmed by the concentrations of the reagents. The urea-urease reaction can offer a new alternative in material synthesis, where the pH and its course in time are crucial factors in the synthesis. However, before using it in any synthesis method, it is important to investigate the possible effects of the reagents on the enzymatic reaction. Here we investigate the effect of the reagents of the zeolite imidazole framework-8 (zinc ions and 2-methylimidazole) on the urea-urease reaction. We have chosen the zeolite imidazole framework-8 because its formation serves as a model reaction for the formation of other metal–organic frameworks. We found that, besides the inhibition effect of th...
Strategies for designing autonomous oscillatory systems have gained much attention in the past fe... more Strategies for designing autonomous oscillatory systems have gained much attention in the past few decades. A broadly accepted and used strategy for the generation of forced oscillations in the originally non-oscillatory subsystems is to couple a pH (driving) oscillator to a pH-sensitive substance (forced oscillatory subsystem) in a one-compartment system. The forced oscillatory subsystem comprises pH-sensitive components, which inevitably generate negative feedback and affect the characteristics of the driving oscillatory system. Here, we present a different approach by separating the driving and forced oscillatory systems into a two-compartment system using a silicone membrane, and the forced oscillations of the absorbance of a pH-sensitive chemical species (methyl red dye) were realized by the transport of carbon dioxide through the membrane generated periodically by the driving pH oscillator. The transported carbon dioxide produced the pH change in the separated compartment by c...
The beat in physical systems is a transparent and well-understood phenomenon. It may occur in for... more The beat in physical systems is a transparent and well-understood phenomenon. It may occur in forced oscillatory systems and as a result of the interference of two waves of slightly different frequencies. However, in chemical systems, the realization of the latter type of the beat phenomenon has been lacking. Here we show that a periodic titration of acid and alkaline solutions with each other using programmable syringe pumps in a continuous stirred-tank reactor exhibits the beat phenomenon in the temporal pH oscillation pattern if the time periods of sinusoidal inflow rates of the reagents are slightly different. Interestingly, the frequency of the chemical beat pattern follows the well-known relationship from physics, namely the frequency of the beat is equal to the absolute value of the difference of the two wave frequencies. Based on our strategy, we can design and engineer non-autonomous pH oscillatory systems, in which the characteristics of the temporal oscillations (amplitud...
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