Chemical engines: driving systems away from equilibrium through catalyst reaction cycles

Nature uses catalysis as an indispensable tool to control assembly and reaction cycles in vital non-equilibrium supramolecular processes. For instance, enzymatic methionine oxidation regulates actin (dis)assembly, and catalytic guanosine triphosphate hydrolysis is found in tubulin (dis)assembly. Here we present a completely artificial reaction cycle which is driven by a chemical fuel that is catalytically obtained from a ‘pre-fuel’. The reaction cycle controls the disassembly and re-assembly of a hydrogel, where the rate of pre-fuel turnover dictates the morphology as well as the mechanical properties. By adding additional fresh aliquots of fuel and removing waste, the hydrogels can be re-programmed time after time. Overall, we show how catalysis can control fuel generation to control reaction / assembly kinetics and materials properties in life-like non-equilibrium systems.

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Parasitic Behavior in Competing Chemically Fueled Reaction Cycles

Chemical Science ◽

10.1039/d1sc01106e ◽

2021 ◽

Author(s):

Patrick S. Schwarz ◽

Sudarshana Laha ◽

Jacqueline Janssen ◽

Tabea Huss ◽

Job Boekhoven ◽

...

Keyword(s):

Dynamic Behavior ◽

Model Systems ◽

Reaction Networks ◽

Reaction Cycles ◽

Non Equilibrium

Non-equilibrium, fuel-driven reaction cycles serve as model systems of the intricate reaction networks of life. Rich and dynamic behavior is observed when reaction cycles regulate assembly processes, such as phase...

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Rhodathiaborane reaction cycles driven by C2H4 and H2: synthesis and characterization of [(H)2(PPh3)RhSB8H7(PPh3)] and [(η2-C2H4)(PPh3)RhSB8H7(PPh3)]

Dalton Transactions ◽

10.1039/c4dt03677h ◽

2015 ◽

Vol 44 (11) ◽

pp. 5041-5044 ◽

Cited By ~ 3

Author(s):

Susana Luaces ◽

Ramón Macías ◽

María José Artigas ◽

Fernando J. Lahoz ◽

Luis A. Oro

Keyword(s):

Reversible Reaction ◽

Synthesis And Characterization ◽

Reaction Cycles

New 10-vertex rhodathiaboranes are reported to exhibit reversible reaction chemistry leading to the formation of stoichiometric cycles driven by the hydrogenation of the alkene ligand.

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CHEMICAL REACTION CYCLES FOR THE RECOVERY OF LOW-LEVEL THERMAL ENERGY

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN ◽

10.1252/jcej.10.224 ◽

1977 ◽

Vol 10 (3) ◽

pp. 224-228 ◽

Cited By ~ 19

Author(s):

SHIGETAKA FUJII ◽

HIDEO KAMEYAMA ◽

KUNIO YOSHIDA ◽

DAIZO KUNII

Keyword(s):

Chemical Reaction ◽

Thermal Energy ◽

Low Level ◽

Reaction Cycles

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Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization

Molecules ◽

10.3390/molecules26092404 ◽

2021 ◽

Vol 26 (9) ◽

pp. 2404

Author(s):

Fátima Mirante ◽

Ricardo F. Mendes ◽

Rui G. Faria ◽

Luís Cunha-Silva ◽

Filipe A. Almeida Paz ◽

...

Keyword(s):

Coordination Polymer ◽

Oxidative Desulfurization ◽

Liquid System ◽

Catalytic Membrane ◽

Extraction Solvent ◽

Acrylic Glass ◽

Drying Procedures ◽

Cost Efficient ◽

Model Diesel ◽

Reaction Cycles

The application of a catalytic membrane in the oxidative desulfurization of a multicomponent model diesel formed by most refractory sulfur compounds present in fuel is reported here for the first time. The catalytic membrane was prepared by the impregnation of the active lamellar [Gd(H4nmp)(H2O)2]Cl·2H2O (UAV-59) coordination polymer (CP) into a polymethyl methacrylate (PMMA, acrylic glass) supporting membrane. The use of the catalytic membrane in the liquid–liquid system instead of a powder catalyst arises as an enormous advantage associated with the facility of catalyst handling while avoiding catalyst mass loss. The optimization of various parameters allowed to achieve a near complete desulfurization after 3 h under sustainable conditions, i.e., using an aqueous H2O2 as oxidant and an ionic liquid as extraction solvent ([BMIM]PF6, 1:0.5 ratio diesel:[BMIM]PF6). The performance of the catalytic membrane and of the powdered UAV-59 catalyst was comparable, with the advantage that the former could be recycled successfully for a higher number of desulfurization cycles without the need of washing and drying procedures between reaction cycles, turning the catalytic membrane process more cost-efficient and suitable for future industrial application.

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Enzymatic synthesis and characterization of novel terpolymers from renewable sources

Pure and Applied Chemistry ◽

10.1515/pac-2018-1015 ◽

2019 ◽

Vol 91 (3) ◽

pp. 397-408

Author(s):

Diana Aparaschivei ◽

Anamaria Todea ◽

August E. Frissen ◽

Valentin Badea ◽

Gerlinde Rusu ◽

...

Keyword(s):

Polymerization Reaction ◽

Molar Ratio ◽

Condensation Polymerization ◽

Average Molecular Mass ◽

New Class ◽

Platform Chemicals ◽

Starting Point ◽

Reaction Cycles ◽

Methylene Group

Abstract 2,5-Furandicarboxylic acid and itaconic acid are both important biobased platform chemicals and their terpolymer with 1,6-hexanediol (HDO) can be the starting point for a new class of reactive polyesters, with important applications. The green synthetic route developed in this study involves a biocatalytic condensation polymerization reaction of dimethyl furan-2,5-dicarboxylate (DMFDC) and dimethyl itaconate (DMI) with HDO in toluene at 80°C, using commercial immobilized lipases from Candida antarctica B. In the best conditions, the formed polymer product was isolated with more than 80% yield, containing about 85% terpolymer with average molecular mass of about 1200 (Mn, calculated from MALDI-TOF MS data) and 15% DMFDC_HDO copolymer. Considering the higher reactivity of DMFDC, the composition of the synthesized polymer can be directed by adjusting the molar ratio of DMFDC and DMI, as well as by extending the reaction time. Structural analysis by NMR demonstrated the regioselective preference for the carbonyl group from DMI adjacent to the methylene group. The biocatalyst was successfully reused in multiple reaction cycles.

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Preparation of a Flower-Like Immobilized D-Psicose 3-Epimerase with Enhanced Catalytic Performance

Catalysts ◽

10.3390/catal8100468 ◽

2018 ◽

Vol 8 (10) ◽

pp. 468 ◽

Cited By ~ 7

Author(s):

Lu Zheng ◽

Yining Sun ◽

Jing Wang ◽

He Huang ◽

Xin Geng ◽

...

Keyword(s):

Catalytic Performance ◽

Maximum Activity ◽

Organic Component ◽

Inorganic Component ◽

Optimum Conditions ◽

Thermal Stabilities ◽

Nanometer Size ◽

Cobalt Phosphate ◽

Reaction Cycles

In this present study, we proposed a smart biomineralization method for creating hybrid organic–inorganic nanoflowers using a Co2+-dependent enzyme (D-psicose 3-epimerase; DPEase) as the organic component and cobalt phosphate as the inorganic component. The prepared nanoflowers have many separated petals that have a nanometer size. Under optimum conditions (60 °C and pH of 8.5), the nanoflower can display its maximum activity (36.2 U/mg), which is about 7.2-fold higher than free DPEase. Furthermore, the immobilized DPEase presents enhanced pH and thermal stabilities. The DPEase-nanoflower maintained about 90% of its activity after six reaction cycles, highlighting its excellent reusability.

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Preparation, Characterization, and Catalytic Property of a Cu(II) Complex with 2-Carboxybenzaldehyde-p-Toluenesulfonyl Hydrazone Ligand

BULLETIN OF CHEMICAL REACTION ENGINEERING AND CATALYSIS ◽

10.9767/bcrec.13.1.1012.7-13 ◽

2018 ◽

Vol 13 (1) ◽

pp. 7 ◽

Cited By ~ 2

Author(s):

Xi Shi Tai ◽

Peng Fei Li ◽

Li Li Liu

Keyword(s):

Catalytic Property ◽

Elemental Analysis ◽

Coupling Reaction ◽

Uv Spectra ◽

Organic Complex ◽

Hydrazone Ligand ◽

Metal Organic ◽

Group 2 ◽

A3 Coupling ◽

Reaction Cycles

Metal-organic complex hybrid materials constructed from carboxylate ligands and hydrazone ligands have exhibited potential application in many fields. In order to enrich the applications of the metai-organic complex materials, a new hydrazone ligand contains carboxylate group, 2-carboxybenzaldehyde-p-toluenesulfonyl hydrazone (L1), and its Cu(II) complex (C2), have been prepared. The structure of L1 was determined by elemental analysis, IR spectra and single crystal X-ray diffraction, and the composition of Cu(II) complex (C2) has also been determined by elemental analysis, IR and UV spectra. The catalytic activity for A3 coupling reaction of benzaldehyde, piperidine, and phenylacetylene has been investigated. The results show that Cu(II) complex displays a 100 % selectivity to the product of propargylamine during A3 coupling reaction and benzaldehyde conversions were 95.3, 94.2, and 93.4 % at 120 °C for 12 h in the first, second, and third reaction cycles, respectively. Copyright © 2018 BCREC Group. All rights reservedReceived: 16th March 2017; Revised: 17th July 2017; Accepted: 18th July 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018How to Cite: Tai, X.S., Li, P.F., Liu, L.L. (2018). Preparation, Characterization, and Catalytic Property of a Cu(II) Complex with 2-Carboxybenzaldehyde-p-Toluenesulfonyl Hydrazone Ligand. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1): 7-13 (doi:10.9767/bcrec.13.1.1012.7-13)

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Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus

Nature Communications ◽

10.1038/s41467-021-26002-7 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Stephan Reichl ◽

Eric Mädl ◽

Felix Riedlberger ◽

Martin Piesch ◽

Gábor Balázs ◽

...

Keyword(s):

Transition Metal ◽

Alkali Metal ◽

White Phosphorus ◽

Starting Material ◽

Efficient Manner ◽

Subsequent Step ◽

Reaction Cycles

AbstractThe synthesis of phosphines is based on white phosphorus, which is usually converted to PCl3, to be afterwards substituted step by step in a non-atomic efficient manner. Herein, we describe an alternative efficient transition metal-mediated process to form asymmetrically substituted phosphines directly from white phosphorus (P4). Thereby, P4 is converted to [Cp*Fe(η5-P5)] (1) (Cp* = η5-C5(CH3)5) in which one of the phosphorus atoms is selectively functionalized to the 1,1-diorgano-substituted complex [Cp*Fe(η4-P5R′R″)] (3). In a subsequent step, the phosphine PR′R″R‴ (R′ ≠ R″ ≠ R‴ = alky, aryl) (4) is released by reacting it with a nucleophile R‴M (M = alkali metal) as racemates. The starting material 1 can be regenerated with P4 and can be reused in multiple reaction cycles without isolation of the intermediates, and only the phosphine is distilled off.

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Taming Combinatorial Explosion of the Formose Reaction via Recursion within Mineral Environments

10.26434/chemrxiv.7712225.v1 ◽

2019 ◽

Author(s):

Leroy Cronin ◽

Stephanie Colón-Santos ◽

Geoffrey Cooper

Keyword(s):

Building Blocks ◽

Complex Mixtures ◽

Mineral Surfaces ◽

One Pot ◽

Combinatorial Explosion ◽

Formose Reaction ◽

Product Mixture ◽

Number Of Cycles ◽

Reaction Cycles

One-pot reactions of simple precursors, such as those found in the formose reaction or formamide condensation, continuously lead to combinatorial explosions in which simple building blocks capable of function exist, but are in insufficient concentration to self-organize, adapt, and thus generate complexity. We set out to explore the effect of recursion on such complex mixtures by ‘seeding’ the product mixture into a fresh version of the reaction, with the inclusion of different mineral environments, over a number of reaction cycles. Through untargeted UPLC-HRMS analysis of the mixtures<a> we found that the overall number of products detected reduces as the number of cycles increases, as a result of recursively enhanced mineral environment selectivity, </a>thus limiting the combinatorial explosion. This discovery demonstrates how the involvement of mineral surfaces with simple reactions could lead to the emergence of some building blocks found in RNA, Ribose and Uracil, under much simpler conditions that originally thought.

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