Chemical Pathways to the Origin of Life

doi:10.6023/cjoc202605021

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3293-3316.DOI: 10.6023/cjoc202605021 Previous Articles Next Articles

REVIEW

通往生命起源的化学之路

朱山辉^a, 刘天飞^a^,^b^,^*()

^a 南开大学化学学院有机新物质创造前沿科学中心天津 300071
^b 物质绿色创造与制造海河实验室天津 300192

收稿日期:2026-05-19 修回日期:2026-07-04 发布日期:2026-07-23
通讯作者: 刘天飞
基金资助:
国家重点研发计划(2022YFB4101800); 国家自然科学基金(22171141); 国家自然科学基金(22193010); 国家自然科学基金(22193014); 全国重点实验室天津市重大专项(25ZXZSSS00700); 及中央高校基本科研业务费(020-63263149)

Chemical Pathways to the Origin of Life

Shanhui Zhu^a, Tianfei Liu^a^,^b^,^*()

^a State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071
^b Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192

Received:2026-05-19 Revised:2026-07-04 Published:2026-07-23
Contact: Tianfei Liu
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Key Research and Development Program of China(2022YFB4101800); National Natural Science Foundation of China(22171141); National Natural Science Foundation of China(22193010); National Natural Science Foundation of China(22193014); Tianjin Major Science and Technology Project for National Key Laboratories(25ZXZSSS00700); Fundamental Research Funds for the Central Universities(020-63263149)

Current popular academic viewpoints on the chemical evolutionary pathways to the origin of life are summarized. It contains possible pathways revealed by exploration of deep-sea geological samples, deep-space observations, and artificial laboratory simulations and experiments, revealing the synthesis of fatty acids, fatty alcohols, hydrocarbons, and nitrogen-, sulfur-, and phosphorus-containing organic compounds from inorganic matters in Earth’s initial environments. It also contains the latest advances in the theory of protocell and experiments for its functional construction based on the theory of the organic molecular aggregation and self-coiling developed by Prof. Xi-Kui Jiang et al., the emergence of rhythmic and periodic orders, self-replication and evolution, and the assembly theory. Finally, the theory of last universal common ancestor and experimental attempts at artificially synthesized cells are also reviewed. It can provide important references for future research on the origin of life and the search for extraterrestrial life.

Key words: the origin of life, hydrophobic-lipophilic interaction, assembly theory, protocell, artificial synthetic cell

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Shanhui Zhu, Tianfei Liu. Chemical Pathways to the Origin of Life[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3293-3316.

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Fig. & Tab. 50

Scheme 1. Synthesis of basic building blocks of life from simple molecules

Figure 1. Schematic diagram of the Miller-Urey experimental apparatus[30] A: the classic apparatus; B: the simplified apparatus.

Figure 2. Schematic diagrams of the structures of fatty alcohol derivatives in archaeal cell membranes and fatty acid derivatives in bacterial and eukaryotic cell membranes[40]

Figure 3. Prebiotic synthesis model at submarine hydrothermal vents In deep-sea hydrothermal vent systems, electrons generated from the oxidation of H2 and H2S in hydrothermal fluids are transported through porous and conductive metal sulfide chimney minerals toward the seawater-rock interface. At this interface, the reduction of molecules such as CO2, ${\text{NO}}_{\text{3}}^{－}$, ${\text{NO}}_{\text{2}}^{－}$ proceeds under the catalysis of metal sulfides, leading to the formation of diverse building blocks of life. These molecular precursors subsequently undergo condensation and polymerization reactions to produce biologically essential polymer.

Scheme 2. Chemical reactions in highly serpentinized peridotite that result in the formation of high-concentration hydrogen gas through hydration

Figure 4. Sediment from the active hydrothermal vent of the Lost City, as documented by Kelley et al. (A) Aragonite-rich sample collected near the summit of Poseidon; (B) Close-up of the typical brittle intergrowth between aragonite and natrolite within the sample (carbonate chimneys and vein materials in the active vent area are snow-white, highly porous, and easily fragmented); (C) Micrograph showing a reticulated, interwoven aragonite intergrowth, whose morphology resembles filamentous bacteria in diffuse-flow zones. The sample was collected from a several-centimeters-wide carbonate “artery” traversing the flank of the Poseidon massif, from which centimeter-long carbonate feather-like growths protrude from the vein

Scheme 3. Fischer-Tropsch reaction under hydrothermal conditions from the dissolved CO2 in the aqueous phase[45]

Figure 5. Possible pathways for the formation of fatty acids and fatty alcohols in submarine hydrothermal environments

Figure 6. In an alkaline hydrothermal vent environment, the process of reducing carbon dioxide to organic molecules via hydrogen through the reduction of iron-nickel sulfide minerals and formate pathways relies on the natural pH gradient[53]

Figure 7. (a) Schematic diagram of the reactor, with a microscopic view of the reaction process embedded, showing the presence of precipitates at the interface; (B) 1H NMR and 13C NMR spectra of the formic acid produced (The single peaks in the 1H NMR (a) and 13C NMR (b) spectra indicate that formic acid was formed in this system); (c) Expected doublet signal produced by the coupling between 1H and 13C nuclei in the 1H NMR spectrum when the isotopically labeled 13CO2 was used; (d) Observed coupling between 2H and 13C nuclei after replacing ordinary water with deuterated water 2H2O); (e, f) No formate was detected when N2 was used to substitute H2 as the hydrothermal‑vent driving gas [55]

Figure 8. Regulation of the PCET reaction mechanism by high pressure (1 bar=100 kPa)

Figure 9. Process of synthesizing long-chain carboxylic acids that can assemble into droplets using cobalt-nickel minerals and simple substances such as formic acid, which were already present in the early hydrothermal environment of Earth, under mild hydrothermal conditions

Figure 10. A set of primitive metabolic reaction networks developed by He Daoping and colleagues that uses hydrogen as a reducing agent to directly convert carbon dioxide

Figure 11. (A) HRTEM image, (B) HAADF-STEM image, and (C) EDS mapping of NiFe2O4/Fe2O3

Scheme 4. Mechanism of the Formose reaction proposed by Breslow.

Scheme 5. Pathways for the formation of formic acid and formaldehyde under alkaline seafloor hydrothermal conditions

Scheme 6. Reaction equation for the synthesis of monosaccharides from formaldehyde

Figure 12. Overview of the Formose reaction and analytical workflow[74] The central circle illustrates the formation of target monosaccharide products through the Breslow cycle. The surrounding ring represents various non-target products, with the colored regions highlighting the major side-reaction pathways: reduction (blue), dehydration (green), and oxidation (red).

Scheme 7. Synthesis of AICA, a precursor of purine nucleotides, starting from hydrogen cyanide

Figure 13. Mass spectrometry data of iron oxides in rocks catalyzing the formation of acetylene fragments (A) and cyano fragments (B)

Figure 14. Conversion of atmospheric carbon dioxide to methanol catalyzed by ferrous sulfide under light mediation and in the presence of hydrogen

Figure 15. Two proposed competing reaction pathways for sodium bicarbonate under hydrothermal conditions, leading to the formation of formate (left) and long-chain hydrocarbons (right)

Scheme 8. Lightening and atmospheric discharges can cause the reaction between dinitrogen and dioxygen

Figure 16. (a) Typical reaction pathways for ${\text{NO}}_{\text{3}}^{－}$ and ${\text{NO}}_{\text{2}}^{－}$ reduction; (b) Relationship between pH and the driving force for proton and electron transfer for an elementary proton-coupled electron transfer step; (c) Rate of two competing reactions as a function of the pH at a constant potential on the RHE scale [The relative reaction rate of two CPET pathways is pH independent (solid and broken black lines), whereas the relative reaction rate of two SPET pathways shows a strong pH dependence (solid and broken green lines)]

Scheme 9. Conversion of nitrites and ammonium salts into nitrogen gas by copper sulfide minerals via a hydrazine intermediate without enzymes

Scheme 10. Formation of corresponding α-amino acids from α-keto acids, cyanide and ammonia sources via the Bucherer-Bergs pathway (an extension of the Strecker reaction)

Scheme 11. Reaction equations for synthetic glycine (top) and alanine (bottom)

Scheme 12. Prebiotic synthetic pathway for the formation of N-formylaminocarbonitrile in formamide medium, under the action of hydrogen cyanide (HCN), water, and photoelectrons

Scheme 13. Synthesis of adenine from HCN molecules

Scheme 14. Process for synthesizing purine and pyrimidine nucleobases by heating formamide at 160 ℃ for 48 h with man- ganese oxide as catalyst

Figure 17. Schematic diagrams of clusters, self-coiled conformations, and micelles[1]

Figure 18. Schematic illustration of the hydrophobic lipophilic interactions between hydrocarbon molecules A and B (the circles represent water molecules)[1]

Figure 19. Schematic diagram of cyclic multilamellar vesicle growth and division

Scheme 15. General RNA-peptide synthesis cycle based on 5-Methylaminomethyl uridine (mnm5U) and the amino acid-modified carbamoyl adenosine [(m6)aa6A. aa, amino acid][137]

Figure 20. Pathway proposed by Szostak's team for the de novo synthesis of the simplest protocells

Figure 21. Schematic diagram of the cyclicity of life processes

Figure 22. Fatty acid membranes maintaining adequate proton gradients to support ATP synthesis by ATP synthase under steep pH and temperature gradients of hydrothermal vent systems[150]

Figure 23. Photographs of the BZ reaction system in a reaction vessel over time[152]

Figure 24. Rayleigh-Bénard convection cells in a gravitational field[160]

Figure 25. Organic oscillation reactions reported by ter Harmsel et al.[161]

Figure 26. Experimental system for replication-degradation cycles enabling competitive dominance of complex stable replicators under nonequilibrium[168]

Figure 27. Coevolutionary mechanism of replicator-environ- ment interactions with environmental feedback on replicator population evolution

Figure 28. Features of high replication numbers and high complexity indicative of the existence of non-random selection (A) Schematic representation of the formation of a combinatorial object space, which is constrained by building blocks and physical constraints; (B) Observed copy number distributions of objects under different assembly indices, with and without selection; (C) Schematic diagram of physical pathways for object construction, where undirected pathways and directed (selected) pathways lead to low and high observed copy numbers of objects, respectively.

Figure 29. Concept of assembly space (A) Assembly observations of the three objects (P1, P2, and P3), which share a minimal construction process referred to as their “joint assembly space”; (B) Expanded schematic representation of the assembly universe, possible assemblies, contingent assemblies, and observed assemblies. The assembly universe is non-dynamic and is organized along assembly steps as a temporal axis

Figure 30. A comparison of assembly theory and computational complexity theory[172]

Figure 31. Diversification of bacteria and archaea in ancient alkaline hydrothermal vents on the seafloor[177]

Figure 32. Schematic diagram of the molecular structure of phospholipid derivatives that can form liposomes, micelles and bilayers

Figure 33. (a) Bilayer cell membrane structures of bacteria and eukaryotes and (b) tetraether monolayer cell membrane structure of archaea.

Figure 34. Possible pathways for protocell formation Hollow arrows indicate the traditionally recognized pathways, while solid arrows represent the novel pathways proposed by Black et al.

Figure 35. Inscription by Prof. Xi-Kui Jiang on March 12, 2004

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通往生命起源的化学之路

Chemical Pathways to the Origin of Life

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