106-57-0Relevant articles and documents
A reaction network for triglycine synthesis under hydrothermal conditions
Mitsuzawa, Shigenobu,Yukawa, Tetsuyuki
, p. 965 - 973 (2004)
It has been hypothesized that chemical evolution leading to the origin of life might have occurred in hydrothermal environments on primitive Earth. To examine this hypothesis, we investigated how the polymerization of amino acids proceeds under high-temperature and high-pressure conditions. We investigated a reaction network consisting of glycine and oligoglycines up to trimer, and the condensation/hydrolysis reactions among these molecules. We determined the rate constants of these reactions in experiments employing a flow reactor at 200 °C and 25 MPa. We found that two condensation reactions of glycine, which yield diglycine and diketopiperazine as products, have larger equilibrium constants under these conditions than at 25 °C. This result supports the hypothesis that hydrothermal conditions are thermodynamically favorable for chemical evolution. We also found that triglycine formation is mediated by diketopiperazine at 200 °C and 25 MPa. This implies that diketopiperazine acts as an important intermediate in the polymerization process of amino acids, which might have occurred in hydrothermal environments on primitive Earth.
Osmium(VIII)-catalyzed oxidation of some cyclic amines by potassium hexacyanoferrate(III) in alkaline media: A kinetics and mechanistic study
Al-Subu,Jondi,Amer,Hannoun,Musmar
, p. 478 - 484 (2003)
Reactions of morpholine, piperidine, and piperazine with Os(VIII) -catalyzed hexacyanoferrate(III) in alkaline media to produce the corresponding lactam have been studied at constant temperature and ionic strength. The reactions followed first-order kinetics with respect to [amine] and [Os(VIII)] but were independent of [Fe(CN)63-] and [OH-]. The effects of introduced electrolytes, potassium hexacyanoferrate(II), relative permitivity, and temperature have also been studied. A mechanism accounting for these results has been proposed.
Robustness, Entrainment, and Hybridization in Dissipative Molecular Networks, and the Origin of Life
Cafferty, Brian J.,Wong, Albert S. Y.,Semenov, Sergey N.,Belding, Lee,Gmür, Samira,Huck, Wilhelm T. S.,Whitesides, George M.
, p. 8289 - 8295 (2020)
How simple chemical reactions self-assembled into complex, robust networks at the origin of life is unknown. This general problem-self-assembly of dissipative molecular networks-is also important in understanding the growth of complexity from simplicity in molecular and biomolecular systems. Here, we describe how heterogeneity in the composition of a small network of oscillatory organic reactions can sustain (rather than stop) these oscillations, when homogeneity in their composition does not. Specifically, multiple reactants in an amide-forming network sustain oscillation when the environment (here, the space velocity) changes, while homogeneous networks-those with fewer reactants-do not. Remarkably, a mixture of two reactants of different structure-neither of which produces oscillations individually-oscillates when combined. These results demonstrate that molecular heterogeneity present in mixtures of reactants can promote rather than suppress complex behaviors.
Addition reaction of 1,4-Dibromo-2,5-piperazinedione with 3,4-dihydro-2H-pyran
Itoh, Kuniaki,Sera, Akira
, p. 479 - 482 (1986)
Reaction of 1,4-dibromo-2,5-piperazinedione (1) with 3,4-dihydro-2H-pyran (2) under irradiation gave 1:1- and 1:2-addition products (3,4) and corresponding secondary products (5-7).The adducts were considered to be produced separately by photoinduced free radical addition as well as concomitant ionic addition reactions.
An efficient green synthesis of proline-based cyclic dipeptides under water-mediated catalyst-free conditions
Thajudeen, Habeebullah,Park, Kyungseok,Moon, Surk-Sik,Hong, In Seok
, p. 1303 - 1305 (2010)
l-Proline-based cyclic dipeptides were synthesized from N-Boc-protected dipeptide methyl esters under catalyst-free condition using water as a solvent. One-pot deprotection and cyclization have been used as the key steps, providing an efficient and environmentally friendly approach. Clean reaction conditions, easy isolation, and good yields of cyclic dipeptides are the salient features of the proposed methodology.
Selective formation of glycylglycine by dehydration of glycine adsorbed on silica gel
Ogawa, Haruo,Fujigaki, Tamiki,Chihara, Teiji
, p. 354 - 356 (1999)
Silica gel promotes the selective dehydration of glycine to form intermediate glycylglycine, with inhibition of the formation of stable glycine anhydride and polymer products. IR measurements indicate that glycine adsorbed on silica gel results in the formation of neutral species having C=O and NH2 groups. The species is considered to stimulate dehydration, leading to the reported selective dehydration. Copyright
Synthesis and mechanistic investigations of pH-responsive cationic poly(aminoester)s
Blake, Timothy R.,Ho, Wilson C.,Huttner, Melanie A.,Turlington, Christopher R.,Waymouth, Robert M.,Wender, Paul A.,Zang, Xiaoyu
, p. 2951 - 2966 (2020)
The synthesis and degradation mechanisms of a class of pH-sensitive, rapidly degrading cationic poly(α-aminoester)s are described. These reactive, cationic polymers are stable at low pH in water, but undergo a fast and selective degradation at higher pH to liberate neutral diketopiperazines. Related materials incorporating oligo(α-amino ester)s have been shown to be effective gene delivery agents, as the charge-altering degradative behavior facilitates the delivery and release of mRNA and other nucleic acids in vitro and in vivo. Herein, we report detailed studies of the structural and environmental factors that lead to these rapid and selective degradation processes in aqueous buffers. At neutral pH, poly(α-aminoester)s derived from N-hydroxyethylglycine degrade selectively by a mechanism involving sequential 1,5- A nd 1,6-O→N acyl shifts to generate bis(N-hydroxyethyl) diketopiperazine. A family of structurally related cationic poly(aminoester)s was generated to study the structural influences on the degradation mechanism, product distribution, and pH dependence of the rate of degradation. The kinetics and mechanism of the pH-induced degradations were investigated by 1H NMR, model reactions, and kinetic simulations. These results indicate that polyesters bearing α-ammonium groups and appropriately positioned N-hydroxyethyl substituents are readily cleaved (by intramolecular attack) or hydrolyzed, representing dynamic dual function materials that are initially polycationic and transform with changing environment to neutral products.
Superactivity of MOF-808 toward Peptide Bond Hydrolysis
Ly, Hong Giang T.,Fu, Guangxia,Kondinski, Aleksandar,Bueken, Bart,De Vos, Dirk,Parac-Vogt, Tatjana N.
, p. 6325 - 6335 (2018)
MOF-808, a Zr(IV)-based metal-organic framework, has been proven to be a very effective heterogeneous catalyst for the hydrolysis of the peptide bond in a wide range of peptides and in hen egg white lysozyme protein. The kinetic experiments with a series of Gly-X dipeptides with varying nature of amino acid side chain have shown that MOF-808 exhibits selectivity depending on the size and chemical nature of the X side chain. Dipeptides with smaller or hydrophilic residues were hydrolyzed faster than those with bulky and hydrophobic residues that lack electron rich functionalities which could engage in favorable intermolecular interactions with the btc linkers. Detailed kinetic studies performed by 1H NMR spectroscopy revealed that the rate of glycylglycine (Gly-Gly) hydrolysis at pD 7.4 and 60 °C was 2.69 × 10-4 s-1 (t1/2 = 0.72 h), which is more than 4 orders of magnitude faster compared to the uncatalyzed reaction. Importantly, MOF-808 can be recycled several times without significantly compromising the catalytic activity. A detailed quantum-chemical study combined with experimental data allowed to unravel the role of the {Zr6O8} core of MOF-808 in accelerating Gly-Gly hydrolysis. A mechanism for the hydrolysis of Gly-Gly by MOF-808 is proposed in which Gly-Gly binds to two Zr(IV) centers of the {Zr6O8} core via the oxygen atom of the amide group and the N-terminus. The activity of MOF-808 was also demonstrated toward the hydrolysis of hen egg white lysozyme, a protein consisting of 129 amino acids. Selective fragmentation of the protein was observed with 55% yield after 25 h under physiological pH.
Glycine homopeptides: The effect of the chain length on the crystal structure and solid state reactivity
Smith, Aaron J.,Ali, Farukh I.,Soldatov, Dmitriy V.
, p. 7196 - 7208 (2014)
A series of linear oligoglycines has been studied using X-ray diffraction, thermal analysis complemented with simultaneous FTIR spectroscopy, gas chromatography-mass spectrometry analysis, and 1H/13C NMR. The new and previously reported data are rationalized to reveal the effect of the chain size on the crystal structure, molecular conformation and thermal stability of the oligopeptides in the solid state, as well as thermally induced transformations (pyrolysis) in the solid state and the gaseous phase. Tetraglycine (4G) and pentaglycine (5G) form triclinic crystals, P1, where they adopt a zwitterionic form and fully extended chain conformation. The antiparallel β sheet arrangement is similar to that in β-triglycine (β3G) and α-diglycine (α2G) but differs from the Form I of polyglycine (polyG). The stability sequence α2G 2O(gas) is endothermic with ΔH = 63.7(4) kJ mol-1 at 492 K. The standard enthalpy of the reaction α2G(solid) = c2G(solid) + H2O(liquid) was estimated to be ΔH298 ≈ 18 kJ mol-1 meaning the reaction is thermodynamically unfavorable under ambient conditions. Finally, the cyclization reaction mechanisms are discussed for the whole series studied. This journal is the Partner Organisations 2014.
PHOTOINDUCED ADDITION REACTION OF 1,4-DIBROMO-2,5-PIPERAZINEDIONE WITH 1-ALKENES.
Itoh,Yamada,Sera
, p. 2140 - 2143 (1984)
Irradiation of 1,4-dibromo-2,5-piperazinedione with olefins in acetonitrile gave mixtures of addition products (1:1-adducts and 1:2-adducts). Addition of 1,2-epoxybutane (a hydrogen bromide scavenger) resulted in enhanced yields of the adducts. Structures of the adducts were elucidated and a reaction mechanism is discussed.
