A key goal of chemistry is to develop synthetic systems that mimic biology, such as selfassembling, self-replicating models of minimal life forms. Oscillations are often observed in complex biological networks, but oscillating, self-replicating species are unknown, and how to

Self-reproducing molecules abound in nature where they support growth and motion of living systems. In artificial settings, chemical reactions can also show complex kinetics of reproduction, however integrating self-reproducing molecules into larger chemical systems remains a challenge towards achieving higher order functionality. Here, we show that self-reproducing lipids can initiate, sustain and accelerate the movement of octanol droplets in water. Reciprocally, the chemotactic movement of the octanol droplets increases the rate of lipid reproduction substantially. Reciprocal coupling between bond-forming chemistry and droplet motility is thus established as an effect of the interplay between molecular-scale events (the self-reproduction of lipid molecules) and microscopic events (the chemotactic movement of the droplets). This coupling between molecular chemistry and microscopic motility offers alternative means of performing work and catalysis in micro-heterogeneous environments.

We report chemically fuelled out-of-equilibrium selfreplicating vesicles based on surfactant formation. We studied the vesicles autocatalytic formation using UPLC to determine monomer concentration and interferometric scattering microscopy at the nanoparticle level. Unlike related reports of chemically fuelled self-replicating micelles, our vesicular system was too stable to surfactant degradation to be maintained out of equilibrium. The introduction of a catalyst, which introduces a second catalytic cycle into the metabolic network, was used to close the first cycle. This shows how coupled catalytic cycles can create a metabolic network that allows the creation and perseverance of fuel-driven, out-of-equilibrium self-replicating vesicles. One of the great challenges in chemistry is to mimic the complex living structures found in nature by designing artificial out-of-equilibrium systems. [1] These structures involve functional, dynamic states which require a continuous supply of energy to be sustained. [2] This energy can be supplied as a chemical fuel, or another energy source such as light. [3] Systems that use an energy supply to maintain behaviour that would otherwise not persist, are known as dissipative systems. [4] Upon depletion or removal of the energy source, the rates of destruction and formation become unbalanced and the system moves to thermodynamic equilibrium. By maintaining complex systems in an out-ofequilibrium state different behaviour can be observed compared to systems in equilibrium. This includes novel selfassembly processes, [5] material properties [6] and functionality. [7] Out-of-equilibrium systems are frequently encountered in phase-separated systems, where functionalities such as product selection [8] or self-regulation [9] can be observed. Especially interesting is the creation of synthetic supramolecular vesicles, since these resemble cellular structures found in nature. [10] Both functional transient vesicles, [11] and thermo-[*] Dr. A

Models of chemical evolution are central to advancing origins of life research. To design more lifelike systems, we must expand our understanding of molecular selection mechanisms. Here, we show two selection modes that produce evolving populations of self-reproducing species, formed through thiol–disulfide exchange. Competition between thiol precursors can give clear succession patterns based on steric factors, an intrinsic property. A separate, emergent selection mechanism—dynamic activating metathesis—was found when exploring competing disulfide precursors. These experiments reveal that additional species generated in the mixture open up alternative reaction pathways to form self-reproducing products. Thus, increased compositional complexity provides certain species with a unique competitive advantage at the expense of others.

The enantioselective intramolecular Rauhut-Currier reaction has been developed using a bifunctional dipeptidic phosphane catalyst, providing a direct access to biologically active α-methylene-δ-valerolactones in high yields and enantiomeric excesses. The novel catalyst is accessible in only four steps from commercial sources and exhibits unusual binding selectivities for a small molecule, suggesting the possibility for long-range interactions between the catalyst and the substrate.

<p>Self-reproducing chemical systems are essential for organic matter to reproduce, move and grow. In artificial settings, chemical reactions can show rich dynamics and auto-catalytic characteristics, however achieving higher order functionality from self-reproducing chemical systems remains a current challenge. Here, we show that <a></a><a>self-reproducing lipids can initiate, sustain and accelerate the movement of microscopic oil droplets in water and, in return, the chemotactic movement of these droplets significantly accelerates the autocatalytic production of the lipids</a>. As droplet motion accelerates the chemical reaction through active chemotactic movement, a reciprocal, two-way interplay is established across length scales, between bond-forming chemistry at the molecular scale, and droplet motility at the near macroscopic level. This chemo-motile coupling between the self-reproducing chemistry of lipids and the microscopic movement of droplets offers new means of performing work and catalysis in micro-heterogeneous environments. </p> <p> <br></p>

We report chemically fuelled out-of-equilibrium selfreplicating vesicles based on surfactant formation. We studied the vesicles autocatalytic formation using UPLC to determine monomer concentration and interferometric scattering microscopy at the nanoparticle level. Unlike related reports of chemically fuelled self-replicating micelles, our vesicular system was too stable to surfactant degradation to be maintained out of equilibrium. The introduction of a catalyst, which introduces a second catalytic cycle into the metabolic network, was used to close the first cycle. This shows how coupled catalytic cycles can create a metabolic network that allows the creation and perseverance of fuel-driven, out-of-equilibrium self-replicating vesicles. One of the great challenges in chemistry is to mimic the complex living structures found in nature by designing artificial out-of-equilibrium systems. [1] These structures involve functional, dynamic states which require a continuous supply of energy to be sustained. [2] This energy can be supplied as a chemical fuel, or another energy source such as light. [3] Systems that use an energy supply to maintain behaviour that would otherwise not persist, are known as dissipative systems. [4] Upon depletion or removal of the energy source, the rates of destruction and formation become unbalanced and the system moves to thermodynamic equilibrium. By maintaining complex systems in an out-ofequilibrium state different behaviour can be observed compared to systems in equilibrium. This includes novel selfassembly processes, [5] material properties [6] and functionality. [7] Out-of-equilibrium systems are frequently encountered in phase-separated systems, where functionalities such as product selection [8] or self-regulation [9] can be observed. Especially interesting is the creation of synthetic supramolecular vesicles, since these resemble cellular structures found in nature. [10] Both functional transient vesicles, [11] and thermo-[*] Dr. A

<p>Self-reproducing chemical systems are essential for organic matter to reproduce, move and grow. In artificial settings, chemical reactions can show rich dynamics and auto-catalytic characteristics, however achieving higher order functionality from self-reproducing chemical systems remains a current challenge. Here, we show that <a></a><a>self-reproducing lipids can initiate, sustain and accelerate the movement of microscopic oil droplets in water and, in return, the chemotactic movement of these droplets significantly accelerates the autocatalytic production of the lipids</a>. As droplet motion accelerates the chemical reaction through active chemotactic movement, a reciprocal, two-way interplay is established across length scales, between bond-forming chemistry at the molecular scale, and droplet motility at the near macroscopic level. This chemo-motile coupling between the self-reproducing chemistry of lipids and the microscopic movement of droplets offers new means of performing work and catalysis in micro-heterogeneous environments. </p> <p> <br></p>