Although it is generally accepted that amino acids were present on the prebiotic Earth, the mechanism by which α‐amino acids were condensed into polypeptides before the emergence of enzymes remains unsolved. Here, we demonstrate a prebiotically plausible mechanism for peptide (amide) bond formation that is enabled by α‐hydroxy acids, which were likely present along with amino acids on the early Earth. Together, α‐hydroxy acids and α‐amino acids form depsipeptides—oligomers with a combination of ester and amide linkages—in model prebiotic reactions that are driven by wet–cool/dry–hot cycles. Through a combination of ester–amide bond exchange and ester bond hydrolysis, depsipeptides are enriched with amino acids over time. These results support a long‐standing hypothesis that peptides might have arisen from ester‐based precursors.

Significance: Peptides and proteins are essential for life as we know it, and likely played a critical role in the origins of life as well. In recent years, much progress has been made in understanding plausible routes from amino acids to peptides. However, little is known about the diversity of sequences that could have been produced by abiotic condensation reactions on the prebiotic earth. In this study, multidimensional separations were coupled with mass spectrometry to detect and sequence mixtures of model proto-peptides. It was observed that, starting with a few monomers, proto-peptide diversity increased rapidly following cycling. Experimental proto-peptide sequences were compared with theoretically random sequences, revealing a high sequence diversity of plausible monomer combinations.

Hydrogel ionotronics are intriguing soft materials that have been applied in wearable electronics and artificial muscles. These applications often require the hydrogels to be tough, transparent, and 3D printable. Renewable materials like cellulose nanocrystals (CNCs) with tunable surface chemistry provide a means to prepare tough nanocomposite hydrogels. Here, we designed ink for 3D printable sensors with cationic cellulose nanocrystals (CCNCs) and zwitterionic hydrogels. CCNCs were first dispersed in an aqueous solution of monomers to prepare the ink with a reversible physical network. Subsequent photopolymerization and the introduction of Al³⁺ ion led to strong hydrogels with multiple physical cross-links. When compared to the hydrogels using conventional CNCs, CCNCs formed a stronger physical network in water that greatly reduced the concentration of nanocrystals needed for reinforcing and 3D printing. In addition, the low concentration of nanofillers enhanced the transparency of the hydrogels for wearable electronics. We then assembled the CCNC-reinforced nanocomposite hydrogels with stretchable dielectrics into capacitive sensors for the monitoring of various human activities. 3D printing further enabled a facile design of tactile sensors with enhanced sensitivity. By harnessing the surface chemistry of the nanocrystals, our nanocomposite hydrogels simultaneously achieved good mechanical strength, high transparency, and 3D printability.

Metal-organic frameworks (MOFs) have attracted great attention for their applications in chemical sensors mainly due to their high porosity resulting in high density of spatially accessible active sites, which can interact with the aimed analyte. Among various MOFs, frameworks constructed from group 4 metal-based (e.g., zirconium, titanium, hafnium, and cerium) MOFs, have become especially of interest for the sensors requiring the operations in aqueous media owing to their remarkable chemical stability in water. Research efforts have been made to utilize these group 4 metal-based MOFs in chemosensors such as luminescent sensors, colorimetric sensors, electrochemical sensors, and resistive sensors for a range of analytes since 2013. Though several studies in this subfield have been published especially over the past 3–5 years, some challenges and concerns are still there and sometimes they might be overlooked. In this review, we aim to highlight the recent progress in the use of group 4 metal-based MOFs in chemical sensors, and focus on the challenges, potential concerns, and opportunities in future studies regarding the developments of such chemically robust MOFs for sensing applications.