Chiral interactions of histidine in a hydrated vermiculite clay

Fraser, Dean; Greenwell, H. Christopher; Skipper, Neal T.; Smalley, M. V.; Wilkinson, Michael; Demé, Bruno; Heenan, Richard K.

doi:10.1039/c0cp01387k

Cited by 20 publications

(13 citation statements)

References 46 publications

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“…Other peak types are basically a combination of peak shapes of MMT and LDHs. It is similar to the XRD spectra of paminobenzene sulfonic acid intercalated LDHs-MMT complex in the literature [44]. The obtained characteristic peaks of the intercalation complexes from the above XRD spectrum simulation may provide some theoretical references for the experimental testing of material structure.…”

Section: Electronic Structural Property Of His-ldhs-mmtsupporting

confidence: 83%

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Structure Simulation and Host–Guest Interaction of Histidine-Intercalated Hydrotalcite–Montmorillonite Complex

Wang

Zhang

et al. 2018

Minerals

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The structures of histidine intercalated hydrotalcite-montmorillonite complex (His-LDHs-MMT) were studied using the DMol3 code, GGA/PW91 function, and DND basis set of the density functional theory (DFT). The geometries of His-LDHs-MMT were optimized, and their electronic properties were calculated. The results showed that the structure of the complex can be seen as that the quaternary ammonium group of histidine was adsorbed on the oxygen of MMT lamella, and its oxygen on the carboxylic acid anion was combined with the hydrogen atoms of the LDHs lamella. It was determined that the interaction mainly consisted in hydrogen bonding and electrostatic force. The average binding energies per histidine of His-LDHs and His-MMT were about −65.89 and −78.44 kcal/mol, respectively. The density of states of the complexes showed that the 2p orbitals of oxygen were dominant, and the 1s orbit of hydrogen near the Fermi level indicate the formation of hydrogen bonds in the complex. The charge density data displayed the density field of histidine carboxylic acid anion overlapped with that of hydrotalcite layer, indicating that a strong hydrogen bond interaction existed between histidine and hydrotalcite layer. The analysis of the electrostatic potential of complex indicated that the electrostatic interaction between histidine and MMT is obviously stronger than that of LDHs. The simulated XRD spectra showed the special diffraction peaks of LDHs and MMT layer in the complex.

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Section: Electronic Structural Property Of His-ldhs-mmtsupporting

confidence: 83%

“…Fraser et al [44] studied chiral differences in the effects of D-and L-histidine on the interlayer spacing of vermiculite clays. The results demonstrated that the effect of different enantiomers of an amino acid may alter physical and structural properties of clay systems at low amino acid concentrations and over a long length-range.…”

Section: Introductionmentioning

confidence: 99%

Structure Simulation and Host–Guest Interaction of Histidine-Intercalated Hydrotalcite–Montmorillonite Complex

Wang

Zhang

et al. 2018

Minerals

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“…The template-catalyzed polymerization of clay formation could be a possible amplification mechanism for the enrichment of chiral molecules in carbonaceous chondrite meteorites. In recent studies, Fraser et al (2011aFraser et al ( , 2011b provided experimental evidence for the chiral enrichment of amino acids on vermiculite crystals. It is therefore important from the point of view of prebiotic chemistry whether organic acids like oxalic acid might have catalyzed the formation of the phyllosilicate phases on these meteorites.…”

Section: Introductionmentioning

confidence: 99%

Formation of Replicating Saponite from a Gel in the Presence of Oxalate: Implications for the Formation of Clay Minerals in Carbonaceous Chondrites and the Origin of Life

et al. 2012

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The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

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“…The lysine data show a very small decrease in D/L that is just significant at the level of analytical precision. In addition to this significant difference in behaviour, and the implications of the DFT and MD simulations, neutron diffraction data showed no significant reverse shift in the dspacing on going from L-to D-enantiomer over the timescale of the whole experiment (~6 hours) 48 . All these data suggest that in the amino acid-clay system, there is a lack of short term reversibility and this lends support to the proposition that amino acids are bound directly and strongly to the clay surface.…”

Section: Discussionmentioning

confidence: 88%

Selective adsorption and chiral amplification of amino acids in vermiculite clay-implications for the origin of biochirality

Fraser

Fitz

Jakschitz

et al. 2011

Phys. Chem. Chem. Phys.

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Smectite clays are hydrated layer silicates that, like micas, occur naturally in abundance. Importantly, they have readily modifiable interlayer spaces that provide excellent sites for nanochemistry. Vermiculite is one such smectite clay and in the presence of small chain-length alkyl-NH 3 Cl ions, forms sensitive, 1-D ordered model clay systems with expandable nano-pore inter-layer regions. These inter-layers readily adsorb organic molecules. N-propyl NH 3 Cl vermiculite clay gels were used to determine the adsorption of alanine, lysine and histidine by chiral HPLC. The results show that during reaction with fresh vermiculite interlayers, significant chiral enrichment of either L-and D-enantiomers occurs depending on the amino acid. Chiral enrichment of the supernatant solutions is up to about 1% per pass. In contrast, addition to clay interlayers already reacted with amino acid solutions resulted in little or no change in D/L ratio during the time of the experiment. Adsorption of small amounts of amphiphilic organic molecules in clay inter-layers is known to produce Layer-by-Layer or Langmuir-Blodgett films. Moreover atomistic simulations show that self-organization of organic species in clay interlayers is important. These noncentrosymmetric, chirally active nanofilms may cause clays to act subsequently as chiral amplifiers, concentrating organic material from dilute solution and having different adsorption energetics for D-and L-enantiomers. The additional role of clays in RNA oligomerization already postulated by Ferris and others, together with the need for the organization of amphiphilic molecules and lipids noted by Szostak and others, suggests that such chiral separation by clays in lagoonal environments at normal biological temperatures might also have played a significant role in the origin of biochirality.2

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Chiral interactions of histidine in a hydrated vermiculite clay

Cited by 20 publications

References 46 publications

Structure Simulation and Host–Guest Interaction of Histidine-Intercalated Hydrotalcite–Montmorillonite Complex

Structure Simulation and Host–Guest Interaction of Histidine-Intercalated Hydrotalcite–Montmorillonite Complex

Formation of Replicating Saponite from a Gel in the Presence of Oxalate: Implications for the Formation of Clay Minerals in Carbonaceous Chondrites and the Origin of Life

Selective adsorption and chiral amplification of amino acids in vermiculite clay-implications for the origin of biochirality

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