Mechanochemical synthesis of glycine oligomers in a virtual rotational diamond anvil cell

Steele, Brad A.; Goldman, Nir; Kuo, I‐Feng W.; Kroonblawd, Matthew P.

doi:10.1039/d0sc00755b

Cited by 28 publications

(33 citation statements)

References 83 publications

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“…In summary, until now, the mechanochemical formation of higher‐order structures such as peptides from amino acids had mostly only been hypothesized, [52] or required hypervelocity impacts and high compressive loads and shear rates [31–33] . In this work, we show that the mechanical activation achieved by ball milling induces peptide bond formation from inactivated glycine in the absence of water.…”

Section: Methodsmentioning

confidence: 64%

“…36 However, the formation of higher-order structures such as peptides from amino acids by mechanical forces had mostly only been hypothesized, 49 and mechanochemical oligomerization of amino acids has been predicted to require high compressive loads and shear rates. 50 In this work, we show that the mechanical activation achieved by ball milling is enough to induce peptide bond formation in a sample of unactivated glycine in the absence of bulk liquids. The oligomerization of glycine into linear oligomers Gly≥2 improves in the presence of prebiotically plausible additives such as TiO2, 51,52 and even proceeds in the presence of water.…”

Section: Discussionmentioning

confidence: 76%

“…For example, studies simulating impact events in aqueous solutions of amino acids, [31] and experiments mimicking natural comet impacts under cryogenic conditions (up to 1.4 km s −1 , 25.8 GPa, at 77 K) have revealed that amino acids such as glycine and alanine undergo oligomerization due to the shock impact yielding mostly linear dipeptides and tripeptides [32] . Additionally, recent simulations of glycine subjected to shear stress have shown that mechanochemical formation of linear Gly 2 could occur under compressive loads of about 10 GPa at RT, indicating the possibility for impact‐based and tectonic shearing prebiotic scenarios [33] . However, extreme mechanical stress can also cause peptide cleavage as demonstrated in hypervelocity impacts (2.4–5.8 km s −1 ), [34] which might explain the relatively short peptides formed under harsh mechanical conditions.…”

Section: Methodsmentioning

confidence: 99%

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Mechanochemical Prebiotic Peptide Bond Formation**

et al. 2021

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The presence of amino acids on the prebiotic Earth, either stemming from endogenous chemical routes or delivered by meteorites, is consensually accepted. In contrast, prebiotically plausible pathways to achieve peptides from unactivated amino acids are still unclear since most oligomerization approaches rely on thermodynamically disfavored reactions in solution. Alternative hypotheses such as the prebiotic impact scenario postulate that the mechanical impacts from meteorites and geochemical phenomena played an important role in delivering exogenous material to Earth, thus providing the geochemical, mechanical, and thermal conditions to synthesize small prebiotic organic compounds in the absence of bulk liquid media. In this context, here we evaluate the applicability of mechanochemistry by ball milling for peptide bond formation under a prebiotic impact scenario. We found that the combination of mechanical forces and prebiotically plausible and ubiquitous minerals as activators enable the oligomerization of amino acids such as glycine in the absence of bulk water (or solvents) and at ambient temperature. Increasing the mechanochemical reactor's temperature is shown to favor the degree of polymerization concomitantly with the formation of cyclic glycine dimer [cyclo(Gly 2 ) or DKP], a product commonly considered as a dead-end in solution peptide bond formation. However, our study shows that DKP can be mechanochemically activated and used as a source for glycine oligomers. The findings of this research provide alternative mechanochemical routes towards oligopeptides and establish new synthetic approaches for prebiotic chemistry that are not limited by poor diffusion of the reactants, thus complementing the current alternating wetting and drying prebiotic environment strategy. File list (2) download file view on ChemRxiv Peptide paper.pdf (816.75 KiB) download file view on ChemRxiv Peptide paper-SI.pdf (1.79 MiB)

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Section: Methodsmentioning

confidence: 64%

Section: Discussionmentioning

confidence: 76%

Section: Methodsmentioning

confidence: 99%

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Mechanochemical Prebiotic Peptide Bond Formation**

et al. 2021

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“…In summary, until now, the mechanochemical formation of higher-order structures such as peptides from amino acids had mostly only been hypothesized, [52] or required hypervelocity impacts and high compressive loads and shear rates. [31][32][33] In this work, we show that the mechanical activation achieved by ball milling induces peptide bond formation from inactivated glycine in the absence of water. The oligomerization of inactivated glycine into linear oligomers Gly !2 improves significantly in the presence of prebiotically plausible minerals such as TiO 2 , [61,69] and even proceeds under moisture.…”

Section: Communications 12728 Wwwangewandteorgmentioning

confidence: 66%

“…[32] Additionally, recent simulations of glycine subjected to shear stress have shown that mechanochemical formation of linear Gly 2 could occur under compressive loads of about 10 GPa at RT, indicating the possibility for impact-based and tectonic shearing prebiotic scenarios. [33] However, extreme mechanical stress can Scheme 1. The mechanical energy in prebiotic impact scenarios could have been provided by impact, compression, and shear forces: a) extraterrestrial and terrestrial collisions and b) plate tectonic movement.…”

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confidence: 99%

Mechanochemical Prebiotic Peptide Bond Formation**

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Mechanochemical milling experimentsAll milling experiments were conducted using InSolido Technologies vibratory ball mill and in 14 mL hardened stainless steel (SS) containers specifically designed for high temperature milling reactions. Three 1 g SS balls (6 mm in diameter) were used as milling media, reactions were conducted at 30 Hz frequency and all reactions were performed for the duration of 18h. ATR-FTIR & PXRDSpectra were recorded on PerkinElmer SpectrumTwo spectrometer equipped with a diamond cell in a 4000-400 cm -1 range. PXRD patterns were collected on PanAlytical Aeris diffractometer (Cu Kα radiation and Ni filter) and zero background sample holder. IP-HPLCOligopeptides were analyzed by IP-HPLC on an Agilent 1290 Infinity instrument equipped with a Phenomenex Luna C18 column (250 mm long, 4.6 mm diameter and 3 µm particle size). The mobile phase was an aqueous solution of 50 mM KH2PO4 and 7.2 mM sodium hexanesulfonate adjusted to pH 2.5 by the addition of 85% H3PO4 (HPLC grade). The mobile phase was used isocratically with 1 mL/min flow rate. Sample injection volume of 1 µL was used, the total method time was 20 min and the column was equilibrated at 30°C. The instrument was

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Glycine: The Gift that Keeps on Giving

Boldyreva

2021

Israel Journal of Chemistry

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Glycine is a small molecule. It cannot change its conformation and is achiral. Despite the apparent simplicity, glycine shows endless diversity in its behavior over many phenomena. It was the first amino acid for which polymorphism was reported, first on crystallization and then on hydrostatic compression. The polymorphs differ in their physical properties and their biological activity. Glycine clusters persist in solution, leading to "solution memory". Phenomena at interfaces are critically important for crystal growth, dissolution, and for physical properties, which can be at times unexpected, like polarity in centrosymmetric αpolymorph. It is a great pleasure to remind of these remarkable phenomena in a special issue honoring professors Meir Lahav and Leslie Leiserowitz, who pioneered the study of the behavior of this unique molecule in many respects, and showed how complex and non-trivial phenomena can be at interfaces: between phases and between research fields.

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Mechanochemical synthesis of glycine oligomers in a virtual rotational diamond anvil cell

Abstract: Compressive shearing forces can induce mechanochemical oligomerization reactions in glycine.

Cited by 28 publications

References 83 publications

Mechanochemical Prebiotic Peptide Bond Formation**

Mechanochemical Prebiotic Peptide Bond Formation**

Mechanochemical Prebiotic Peptide Bond Formation**

Glycine: The Gift that Keeps on Giving

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