Energy consumption in chemical fuel-driven self-assembly

Abstract

Nature extensively exploits high-energy transient self-assembly structures that are able to perform work through a dissipative process. Often, self-assembly relies on the use of molecules as fuel that is consumed to drive thermodynamically unfavourable reactions away from equilibrium. Implementing this kind of non-equilibrium self-assembly process in synthetic systems is bound to profoundly impact the fields of chemistry, materials science and synthetic biology, leading to innovative dissipative structures able to convert and store chemical energy. Yet, despite increasing efforts, the basic principles underlying chemical fuel-driven dissipative self-assembly are often overlooked, generating confusion around the meaning and definition of scientific terms, which does not favour progress in the field. The scope of this Perspective is to bring closer together current experimental approaches and conceptual frameworks. From our analysis it also emerges that chemically fuelled dissipative processes may have played a crucial role in evolutionary processes.

Fuel‐Driven Transient Crystallization of a Cucurbit[8]uril‐Based Host–Guest Complex

“…Non‐equilibrium systems are ubiquitous in biological systems, where a constant flow of matter or energy is required. A relevant example is the formation of microtubules via the self‐assembly of tubulin proteins through a continuous supply of guanosine‐5′‐triphosphate (GTP) . The mitochondria continuously refuels the cytosol to carry on this energy‐consuming processes, while other mechanisms operate to excrete the waste products generated in parallel .…”

A Chiral Bis‐Naphthylated Tetrandrine Dibromide: Synthesis, Self‐Assembly into an Organic Framework Based On Nanosized Spherical Cages, and Inclusion Studies

“…According to the literature, this assembly might be the largest among the purely synthetic organic molecular crystals reported to date, since the unit cell has dimensions comparable to that of proteins with a size of about 50 kDa. Molecular crystals are usually maintained by stronger intermolecular interactions such as hydrogen bonds or electrostatic forces …”

“…Molecular crystals are usually maintained by stronger intermolecular interactions such as hydrogen bonds or electrostatic forces. [8][9][10][14][15][16][17][18][19][20][21][22][23][34][35][36][37][38] The methanol content in DNT-MeOH ( Figure S6, Supporting Information) was estimated from the number of diffuse electrons determined by the SQUEEZE routine [39] within the solvent accessible voids, after eliminating the contribution of the bromide anions (96 × 36 e). The determined electrons correspond to approx.…”

Individual‐Molecule Perspective Analysis of Chemical Reaction Networks: The Case of a Light‐Driven Supramolecular Pump

“…Living organisms exist away from equilibrium, and so operate naturally occurring molecular machines, [1][2][3] wherein an energy supply is exploited to drive and sustain specific functions at the nanoscale.C onsidering the complexity of natural systems,a rtificial molecular motors [4,5] constitute ap latform to gain insights on nonequilibrium systems, although only af ew advanced prototypes have been shown to operate away from equilibrium. [4][5][6][7][8][9][10][11][12] Amolecular motor can be rationally described by means of an etwork of chemical processes [13][14][15][16] in which structural transitions are coupled to chemical reactions. [17,18] In suitably engineered systems,t he supply of chemicals at af ixed rate (that is,e nforcement of chemostats), or the external control on some of the kinetic constants (for example,v ia photoexcitation), can cause the violation of detailed balance and, ultimately,t he emergence of the directed motion at the basis of the function of the machine.…”