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.
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.
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
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.
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.
Substitution of halogen atom in α-halonitro compounds of the aliphatic series 6. Preparation and reduction of alkyl α-halo- and α-sulfosubstituted α-nitrocarboxylates
Yurtanov, A. I.,Baidildaeva, S. K.,Chekhlov, A. N.,Zefirov, N. S.
, p. 816 - 820 (1994)
Ethyl α-halo-α-nitropropionate and -butyrate were prepared by alkylating ammonium salts of ethyl bromo- and chloronitroacetates.The addition of alkyl acrylates to alkyl chloronitroacetates or their salts gives dialkyl α-chloro-α-nitroglutarates.Sodium salts of ethyl α-nitro-α-sulfo-β-hydroxypropionate and -butyrate were obtained by the sulfodehalogenation of ethyl α-chloro-α-nitro-β-hydroxypropionate and -butyrate with sodium dithionite.Esters of α-amino acid hydrochlorides were prepared by the reduction of alkyl α-chloro-α-nitrocarboxylates.The hydrogenation of alkyl nitrosulfoacetates leads to the corresponding disodium salts of alkyl aminodisulfoacetates and piperazine-2,5-dione. - Key words: halonitrocarboxylates, alkylation, Michael reaction, sulfodehalogenation, catalytic hydrogenation; amino acids; alkyl aminodisulfoacetates.
Investigation of permeation of theophylline through skin using selected piperazine-2,5-diones
Pokorna, Aneta,Bobal, Pavel,Oravec, Michal,Rarova, Lucie,Bobalova, Janette,Jampilek, Josef
, (2019)
Transdermal administration of drugs that penetrate, in this case directly into the blood circulation, has many advantages and is promising for many drugs thanks to its easy application and good patient compliance. (S)-8-Methyl-6,9-diazaspiro[4.5]decan-7,10-dione (alaptide), has been studied as a potential chemical permeation enhancer. Based on its structure, four selected piperazine-2,5-diones were synthesized by means of multi-step synthetic pathways. All the compounds were investigated on their ability to enhance the permeation of the model drug theophylline from the hydrophilic medium propylene glycol:water (1:1). In vitro experiments were performed using vertical Franz diffusion cells at constant temperature 34 ± 0.5 ?C and using full-thickness pig (Sus scrofa f. domestica) ear skin. Withdrawn samples were analyzed by RP-HPLC for determination of the permeated amount of theophylline. All the compounds were applied in ratio 1:10 (w/w) relative to the amount of theophylline. One hour after application, the permeated amount of theophylline from formulations with alaptide and (3S,6S)-3,6-dimethylpiperazine-2,5-dione, was ca. 15- and 12-fold higher, respectively, than from the formulation without the tested compounds. Despite the enhancement ratio of both enhancers in a steady state was ca. 2.3, the pseudo-enhancement ratio in the time range from 1 to 3 h was 4.4. These enhancement ratios indicate that the compounds are able to enhance the permeation of agents through the skin; however, the short-term application of both compound formulations seems to be more advantageous. In addition, the screening of the cytotoxicity of all the prepared compounds was performed using three cell lines, and the compounds did not show any significant toxic effect.
Rates of uncatalyzed peptide bond hydrolysis in neutral solution and the transition state affinities of proteases
Radzicka,Wolfenden
, p. 6105 - 6109 (1996)
To assess the relative proficiencies of enzymes that catalyze the hydrolysis of internal and C-terminal peptide bonds, the rates of the corresponding nonenzymatic reactions were examined at elevated temperatures in sealed quartz tubes, yielding linear Arrhenius plots. The results indicate that in neutral solution at 25°C, peptide bonds are hydrolyzed with half-times of approximately 500 years for the C-terminal bond of acetylglycylglycine, 600 years for the internal peptide bond of acetylglycylglycine N-methylamide, and 350 years for the dipeptide glycylglycine. These reactions, insensitive to changing pH or ionic strength, appear to represent uncatalyzed attack by water on the peptide bond. Comparison of rate constants indicates very strong binding of the altered substrate in the transition states for the corresponding enzyme reactions, K(tx) attaining a value of less than 10-17 M in carboxypeptidase B. The half-life of the N-terminal peptide bond in glycylglycine N-methylamide, whose hydrolysis might have provided a reference for assessing the catalytic proficiency of an aminopeptidase, could not be determined because this compound undergoes relatively rapid intramolecular displacement to form diketopiperazine (t( 1/4 ) ~ 35 days at pH 7 and 37°C). The speed of this latter process suggests an evolutionary rationale for posttranslational N-acetylation of proteins in higher organisms, as a protection against rapid degradation.
Mechanochemical Prebiotic Peptide Bond Formation**
Cindro, Nikola,Grube?i?, Sa?a,Hernández, José G.,Me?trovi?, Ernest,Stolar, Tomislav,U?arevi?, Krunoslav
, p. 12727 - 12731 (2021)
The presence of amino acids on the prebiotic Earth, either stemming from endogenous chemical routes or delivered by meteorites, is consensually accepted. Prebiotically plausible pathways to peptides from inactivated amino acids are still unclear as most oligomerization approaches rely on thermodynamically disfavored reactions in solution. Now, a combination of prebiotically plausible minerals and mechanochemical activation enables the oligomerization of glycine at ambient temperature in the absence of water. Raising the reaction temperature increases the degree of oligomerization concomitantly with the formation of a commonly unwanted cyclic glycine dimer (DKP). However, DKP is a productive intermediate in the mechanochemical oligomerization of glycine. The findings of this research show that mechanochemical peptide bond formation is a dynamic process that provides alternative routes towards oligopeptides and establishes new synthetic approaches for prebiotic chemistry.
Oligomerization of glycine and alanine on metal(II) octacynaomolybdate(IV): Role of double metal cyanides in prebiotic chemistry
Kumar, Anand,Kamaluddin
, p. 2417 - 2429 (2012)
Condensation reactions of amino acid (glycine and alanine) on the surface of metal(II) octacyanomolybdate( IV) (MOCMo) complexes are investigated using highperformance liquid chromatography (HPLC) and electron spray ionizations-mass spectroscopy (ESI-MS). The series of MOCMo have been synthesized and the effect of outer sphere metal ions present in the MOCMo on the oligomerization of glycine and alanine at different temperature and time found out. Formation of peptides was observed to start after 7 days at 60°C. Maximum yield of peptides was found after 35 days at 90°C. It has been found that zinc(II) octacyanomolybdate( IV) and cobalt(II) were the most effective metal cations present in outer sphere of the MOCMo for the production of high yield of oligomerized products. Surface area of MOCMo seems to play dominating parameter for the oligomerization of alanine and glycine. The results of the present study reveal the role of MOCMo in chemical evolution for the oligomerization of biomolecules. Springer-Verlag 2012.
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Abderhalden,Schwab
, (1926)
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Lundgren et al.
, p. 1487 (1961)
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Cronin et al.
, p. 2096,2097,2098,2099 (1971)
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Reaction of amino acids in a supercritical water-flow reactor simulating submarine hydrothermal systems
Islam, Md. Nazrul,Kaneko, Takeo,Kobayashi, Kensei
, p. 1171 - 1178 (2003)
A novel supercritical water flow-reactor was constructed in order to simulate submarine hydrothermal systems. The temperature of fluid inside the reaction tube could be monitored with thermocouples, which was proved to be different from the temperature outside the reaction tube. Oligomers of glycine up to tetraglycine were formed when a 100 mM glycine solution was heated at 200-350 °C for 2 minutes. None of glycine peptides were produced at 400 °C. It was suggested, however, that the formation of glycine condensates at higher temperature, including supercritical conditions of water. The stability of some amino acids under hydrothermal conditions was examined. ω-Amino acids and glutamic acid, which can form intramolecular condensates, showed higher stability than other α-amino acids at higher temperature, including supercritical conditions.
Enantioselective Synthesis of Chiral Substituted 2,4-Diketoimidazolidines and 2,5-Diketopiperazines via Asymmetric Hydrogenation
Xiao, Guiying,Xu, Shuang,Xie, Chaochao,Zi, Guofu,Ye, Weiping,Zhou, Zhangtao,Hou, Guohua,Zhang, Zhanbin
supporting information, p. 5734 - 5738 (2021/08/01)
An enantioselective hydrogenation of 5-alkylidene-2,4-diketoimidazolidines (hydantoins) and 3-alkylidene-2,5-ketopiperazines catalyzed by the Rh/f-spiroPhos complex under mild conditions has been developed, which provides an efficient approach to the highly enantioselective synthesis of chiral hydantoins and 2,5-ketopiperazine derivatives with high enantioselectivities up to 99.9% ee.
