Small-molecule autocatalysis drives compartment growth, competition and reproduction.

Sustained autocatalysis coupled to compartment growth and division is a key step in the origin of life, but an experimental demonstration of this phenomenon in an artificial system has previously proven elusive. We show that autocatalytic reactions within compartments-when autocatalysis, and reactant and solvent exchange outpace product exchange-drive osmosis and diffusion, resulting in compartment growth. We demonstrate, using the formose reaction compartmentalized in aqueous droplets in an emulsion, that compartment volume can more than double. Competition for a common reactant (formaldehyde) causes variation in droplet growth rate based on the composition of the surrounding droplets. These growth rate variations are partially transmitted after selective division of the largest droplets by shearing, which converts growth-rate differences into differences in droplet frequency. This shows how a combination of properties of living systems (growth, division, variation, competition, rudimentary heredity and selection) can arise from simple physical-chemical processes and may have paved the way for the emergence of evolution by natural selection.

Microfluidic-assisted fiber production: Potentials, limitations, and prospects.

Besides the conventional fiber production methods, microfluidics has emerged as a promising approach for the engineered spinning of fibrous materials and offers excellent potential for fiber manufacturing in a controlled and straightforward manner. This method facilitates low-speed prototype synthesis of fibers for diverse applications while providing superior control over reaction conditions, efficient use of precursor solutions, reagent mixing, and process parameters. This article reviews recent advances in microfluidic technology for the fabrication of fibrous materials with different morphologies and a variety of properties aimed at various applications. First, the basic principles, as well as the latest developments and achievements of microfluidic-based techniques for fiber production, are introduced. Specifically, microfluidic platforms made of glass, polymers, and/or metals, including but not limited to microfluidic chips, capillary-based devices, and three-dimensional printed devices are summarized. Then, fiber production from various materials, such as alginate, gelatin, silk, collagen, and chitosan, using different microfluidic platforms with a broad range of cross-linking agents and mechanisms is described. Therefore, microfluidic spun fibers with diverse diameters ranging from submicrometer scales to hundreds of micrometers and structures, such as cylindrical, hollow, grooved, flat, core-shell, heterogeneous, helical, and peapod-like morphologies, with tunable sizes and mechanical properties are discussed in detail. Subsequently, the practical applications of microfluidic spun fibers are highlighted in sensors for biomedical or optical purposes, scaffolds for culture or encapsulation of cells in tissue engineering, and drug delivery. Finally, different limitations and challenges of the current microfluidic technologies, as well as the future perspectives and concluding remarks, are presented.

Exploiting Reaction-Diffusion Conditions to Trigger Pathway Complexity in the Growth of a MOF.

Coordination polymers (CPs), including metal-organic frameworks (MOFs), are crystalline materials with promising applications in electronics, magnetism, catalysis, and gas storage/separation. However, the mechanisms and pathways underlying their formation remain largely undisclosed. Herein, we demonstrate that diffusion-controlled mixing of reagents at the very early stages of the crystallization process (i.e., within ≈40 ms), achieved by using continuous-flow microfluidic devices, can be used to enable novel crystallization pathways of a prototypical spin-crossover MOF towards its thermodynamic product. In particular, two distinct and unprecedented nucleation-growth pathways were experimentally observed when crystallization was triggered under microfluidic mixing. Full-atom molecular dynamics simulations also confirm the occurrence of these two distinct pathways during crystal growth. In sharp contrast, a crystallization by particle attachment was observed under bulk (turbulent) mixing. These unprecedented results provide a sound basis for understanding the growth of CPs and open up new avenues for the engineering of porous materials by using out-of-equilibrium conditions.

Microfluidic-based Synthesis of Covalent Organic Frameworks (COFs): A Tool for Continuous Production of COF Fibers and Direct Printing on a Surface.

Covalent Organic Frameworks (COFs) are a class of porous covalent materials which are frequently synthesized as unprocessable crystalline powders. The first COF was reported in 2005 with much effort centered on the establishment of new synthetic routes for its preparation. To date, most available synthetic methods for COF synthesis are based on bulk mixing under solvothermal conditions. Therefore, there is increasing interest in developing systematic protocols for COF synthesis that provide for fine control over reaction conditions and improve COF processability on surfaces, which is essential for their use in practical applications. Herein, we present a novel microfluidic-based method for COF synthesis where the reaction between two constituent building blocks, 1,3,5-benzenetricarbaldehyde (BTCA) and 1,3,5-tris(4-aminophenyl)benzene (TAPB), takes place under controlled diffusion conditions and at room temperature. Using such an approach yields sponge-like, crystalline fibers of a COF material, hereafter called MF-COF. The mechanical properties of MF-COF and the dynamic nature of the approach allow the continuous production of MF-COF fibers and their direct printing onto surfaces. The general method opens new potential applications requiring advanced printing of 2D or 3D COF structures on flexible or rigid surfaces.

Microfluidic Pneumatic Cages: A Novel Approach for In-chip Crystal Trapping, Manipulation and Controlled Chemical Treatment.

The precise localization and controlled chemical treatment of structures on a surface are significant challenges for common laboratory technologies. Herein, we introduce a microfluidic-based technology, employing a double-layer microfluidic device, which can trap and localize in situ and ex situ synthesized structures on microfluidic channel surfaces. Crucially, we show how such a device can be used to conduct controlled chemical reactions onto on-chip trapped structures and we demonstrate how the synthetic pathway of a crystalline molecular material and its positioning inside a microfluidic channel can be precisely modified with this technology. This approach provides new opportunities for the controlled assembly of structures on surface and for their subsequent treatment.

Freezing the Nonclassical Crystal Growth of a Coordination Polymer Using Controlled Dynamic Gradients.

A methodology that can be efficiently used to synthesize, isolate, and study out-of-equilibrium crystal structures employing controlled and diffusion-limited microfluidic environments is demonstrated. Unlike studies conducted with conventional mixing procedures in a flask, it is proven experimentally and with numerical simulations that microfluidic technologies can undoubtedly fine-tune reaction times and reagents concentration profiles; factors that enable out-of-equilibrium crystal forms to be obtained.

Crystalline fibres of a covalent organic framework through bottom-up microfluidic synthesis.

A microfluidic chip has been used to prepare fibres of a porous polymer with high structural order, setting a precedent for the generation of a wide variety of materials using this reagent mixing approach that provides unique materials not accessible easily through bulk processes. The reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde in acetic acid under continuous microfluidic flow conditions leads to the formation of a highly crystalline and porous covalent organic framework (hereafter denoted as MF-COF-1), consisting of fibrillar micro-structures, which have mechanical stability that allows for direct drawing of objects on a surface.