Element variation in a clam shell and its implications for cold seep irregular eruptions: Calyptogena sp. in the Haima cold seep.

Cold seep is characterized by methane-rich fluids released from subsurface reservoirs, and it sustains the chemosynthetic ecosystems on the seafloor. Previous studies suggest that the activity of cold seep could affect the seawater chemistry and ambient temperature. However, the short-term seep activity was hardly reconstructed due to the focus of studies on carbonate or sediment. Vent macrofauna provide such an opportunity by recording in shells the immediate environment in which they grow. The carbonate skeleton of organisms could theoretically preserve environmental variation. Therefore, high-resolution archives are urgently required to understand the influence of cold seep activity on biogeochemistry. In this study, SEM, EDS mapping, EBSD mapping, and LA-ICP-MS analyses were conducted on a clam (Calyptogena sp.) shell collected alive in 2018 from the Haima cold seep in South China Sea. The CaCO3, Na, Mg, Sr, and Ba contents and the Sr/Ca, Ba/Ca, and Na/Ca ratios in the hinge plate were measured on LA-ICP-MS by spot analysis and line scanning. The element contents in the hinge are as follows: Mg (38.5-109 µg/g), Na (3117-5246 µg/g), Sr (970-5371 µg/g), and Ba (2.9-11.5 µg/g). The results show that Sr, Re, and Ba content vary synchronously along the direction of growth, but Na has an opposite trend. The element analyses indicate that the eruption of the Haima cold seep was irregular, causing temperature, redox state, and pH changes in the cold seep ecosystem. These findings show that the irregular cold seep activities exert vital influences on the biogeochemistry of the cold seep ecosystem, which shed a light on cold seep biomonitoring.

Kinetic Selection in the Out-of-Equilibrium Autocatalytic Reaction Networks that Produce Macrocyclic Peptides.

Autocatalytic reaction networks are instrumental for validating scenarios for the emergence of life on Earth and for synthesizing life de novo. Here, we demonstrate that dimeric thioesters of tripeptides with the general structure (Cys-Xxx-Gly-SEt)2 form strongly interconnected autocatalytic reaction networks that predominantly generate macrocyclic peptides up to 69 amino acids long. Some macrocycles of 6-12 amino acids were isolated from the product pool and were characterized by NMR spectroscopy and single-crystal X-ray analysis. We studied the autocatalytic formation of macrocycles in a flow reactor in the presence of acrylamide, whose conjugate addition to thiols served as a model "removal" reaction. These results indicate that even not template-assisted autocatalytic production combined with competing removal of molecular species in an open compartment could be a feasible route for selecting functional molecules during the pre-Darwinian stages of molecular evolution.

Autocatalytic and oscillatory reaction networks that form guanidines and products of their cyclization.

Autocatalytic and oscillatory networks of organic reactions are important for designing life-inspired materials and for better understanding the emergence of life on Earth; however, the diversity of the chemistries of these reactions is limited. In this work, we present the thiol-assisted formation of guanidines, which has a mechanism analogous to that of native chemical ligation. Using this reaction, we designed autocatalytic and oscillatory reaction networks that form substituted guanidines from thiouronium salts. The thiouronium salt-based oscillator show good stability of oscillations within a broad range of experimental conditions. By using nitrile-containing starting materials, we constructed an oscillator where the concentration of a bicyclic derivative of dihydropyrimidine oscillates. Moreover, the mixed thioester and thiouronium salt-based oscillator show unique responsiveness to chemical cues. The reactions developed in this work expand our toolbox for designing out-of-equilibrium chemical systems and link autocatalytic and oscillatory chemistry to the synthesis of guanidinium derivatives and the products of their transformations including analogs of nucleobases.

Emergence of low-symmetry foldamers from single monomers.

Self-assembly is a powerful method to obtain large discrete functional molecular architectures. When using a single building block, self-assembly generally yields symmetrical objects in which all the subunits relate similarly to their neighbours. Here we report the discovery of a family of self-constructing cyclic macromolecules with stable folded conformations of low symmetry, which include some with a prime number (13, 17 and 23) of units, despite being formed from a single component. The formation of these objects amounts to the production of polymers with a perfectly uniform length. Design rules for the spontaneous emergence of such macromolecules include endowing monomers with a strong potential for non-covalent interactions that remain frustrated in competing entropically favoured yet conformationally restrained smaller cycles. The process can also be templated by a guest molecule that itself has an asymmetrical structure, which paves the way to molecular imprinting techniques at the level of single polymer chains.

Probing the Anticancer Action of Oridonin with Fluorescent Analogues: Visualizing Subcellular Localization to Mitochondria.

Oridonin (1) is a complex ent-kaurane diterpenoid exhibiting remarkable antitumor activity. However, the detailed mechanism or cellular target that underlies this activity has not yet been identified. Herein, we report an efficient approach for exploring the anticancer mechanism of oridonin through development of the potent fluorescent analogues. A series of novel fluorescent oridonin probes linked with coumarin moieties were designed, synthesized, and characterized. Fluorescence microscopy and confocal imaging studies suggested that fluorescent oridonin probe 17d was rapidly taken up into tumor cells and the mitochondrion was the main site of its accumulation. Moreover, we confirmed that cytochrome c played an important role in oridonin induced mitochondrion-mediated apoptosis and α,ß-unsaturated ketone is the active moiety of oridonin, which is crucial to its uptake, localization, and cytotoxicity. Our results provide new insights on the molecular mechanism of oridonin and would be useful for its further development into an antitumor agent.

Switchable catalytic activity: selenium-containing peptides with redox-controllable self-assembly properties.

Mimicking nature: The reversible formation of self-assembled nanostructures of selenium-containing peptides can be controlled by redox triggers (see scheme, VC = vitamin C). As a consequence, the catalytic activity of these peptides is switchable. These results should lead to the development of nature-mimicking smart materials with promising properties.