Amino Acid Racemization Research Articles

Racemic Amino Acid Piezoelectric Transducer.

Single crystal L-amino acids can exhibit technologically useful piezoelectric and nonlinear optical properties. Here we predict, using density functional theory, the piezoelectric charge and strain and voltage tensors of the racemic amino acid DL alanine, and use the modeling data to guide the first macroscopic and nanoscopic piezoelectric measurements on DL-alanine single crystals and polycrystalline aggregates. We demonstrate voltage generation of up to 0.8V from DL-alanine crystal films under simple manual compression, twice as high as other amino acid crystals. Our results suggest that net molecular chirality is not a prerequisite for piezoelectric behavior in organic crystals. The transducer presented herein demonstrates that DL-alanine crystals can be used in applications such as temperature and force measurement in biosensors, data storage in flexible electronic devices, and mechanical actuation in energy harvesters.

Characterisation and quantification of protein oxidative modifications and amino acid racemisation in powdered infant milk formula

Modification of proteins in infant milk formula (IF) is of major concern to the dairy industry and consumers. Thermal treatment is required for microbiological safety, but heat, light, metal-ions and other factors may induce oxidative damage, and be a health risk. In this study protein modifications in IFs were quantified. IFs contained both reducible (disulphide) and non-reducible (di-tyrosine, lanthionine, lysinoalanine) protein cross-links. Dehydroalanine and the cross-linked species lanthionine and lysinoalanine were detected. Protein carbonyls were detected predominantly on high molecular mass materials. Oxidation products of phenylalanine (m-tyrosine), tryptophan (N-formylkynurenine, kynurenine, 3-hydroxykynurenine), tyrosine (di-tyrosine) and methionine (methionine sulphoxide) were detected, consistent with amino acid modification. Higher levels of most of the markers of protein modification were present in the hydrolysed protein brand, when compared to the conventional IF samples, indicative of increased damage during additional processing. Significant levels of racemised (D-) amino acids were present. These data indicate that amino acids in proteins in IFs are modified to a significant extent during manufacture, with hydrolysed IF being particularly prone.

Cholesterol-dependent effect of antidepressants on activation BDNF receptor (TRKB)

Enantiomeric excess of amino acids observed in the meteoritic samples of carbonaceous chondrites has incited many researchers to search for an extra-terrestrial origin of life on prebiotic Earth. However, in a non-catalytic environment, only racemic amino acids are synthesized. This computational quantum-mechanical study explores non-catalytic mechanistic pathways for stereoinversion in proteinogenic L-glutamic acid, which may be observable under gas-phase conditions of interstellar medium (ISM). The multi-step stereoinversion pathways proposed in this study are traced through a global reaction route mapping (GRRM) strategy utilizing density-functional and coupled-cluster theories. Notably, a few of the pathways are observed to proceed through simultaneous intramolecular hydrogen atom and proton transfer as well as through a proton-coupled electron transfer mechanism. The intermediates explored along the stereoinversion pathways resemble ammonium ylide and imine, the key ingredients in Strecker synthesis of amino acids. The thermodynamic and kinetic analysis of the stereoinversion pathways in different temperature regions of ISM are also carried out, predicting the streoinversion to proceed over any dissociation of intermediates and conformers of glutamic acid along the pathways. However, initial step of the pathways involves an unsurmountable energy barrier though the key step responsible for stereoinversion has a very low energy barrier and is predicted to proceeds with significant rates. The work suggests the possibility of observing stereoinversion of glutamic acid in the warmer regions of ISM.

Substrate-product analogue inhibitors of isoleucine 2-epimerase from Lactobacillus buchneri by rational design.

A rational approach that may be applied to a broad class of enzyme-catalyzed reactions to design enzyme inhibitors affords a powerful strategy, facilitating the development of drugs and/or molecular probes of enzyme mechanisms. A strategy for the development of substrate-product analogues (SPAs) as inhibitors of racemases and epimerases is elaborated using isoleucine 2-epimerase from Lactobacillus buchneri (LbIleE) as a model enzyme. LbIleE catalyzes the PLP-dependent, reversible, racemization or epimerization of nonpolar amino acids at the C-2 position. The enzyme plays an important role in the biosynthesis of branched-chain d-amino acids and is a potential target for the development of antimicrobial agents. 3-Ethyl-3-methyl-l-norvaline (Ki = 2.9 ± 0.2 mM) and 3-ethyl-3-methyl-d-norvaline (Ki = 1.5 ± 0.2 mM) were designed as SPAs based on the movement of the sec-butyl side chain of the substrate l-Ile during catalysis, and were competitive inhibitors with binding affinities exceeding that of l-Ile by 1.3- and 2.5-fold, respectively. Surprisingly, these compounds were not substrates, but the corresponding compounds lacking the 3-methyl group were substrates. Unlike serine, glutamate, and proline racemases, which exhibit stringent steric requirements at their active sites, the active site of LbIleE was amenable to binding bulky SPAs. Moreover, LbIleE bound the SPA 2,2-di-n-butylglycine (Ki = 11.0 ± 0.2 mM) as a competitive inhibitor, indicating that the hydrophobic binding pocket at the active site was sufficiently plastic to tolerate gem-dialkyl substitution at the α-carbon of an amino acid. Overall, these results reveal that amino acid racemases/epimerases are amenable to inhibition by SPAs provided that they possess a capacious active site.

Catalytic mechanism and properties of pyridoxal 5'-phosphate independent racemases: how enzymes alter mismatched acidity and basicity.

Covering: up to March 2019 Amino acid racemases and epimerases are key enzymes that invert the configuration of common amino acids and supply many corresponding d-isomers in living organisms. Some d-amino acids are inherently bioactive, whereas others are building blocks for important biomolecules, for example lipid II, the bacterial cell wall precursor. Peptides containing them have enhanced proteolytic stability and can act as important recognition elements in mammalian systems. Selective inhibition of certain amino acid racemases (e.g. glutamate racemase) is believed to offer a promising target for new antibacterial drugs effective against pathogens resistant to current antibiotics. Many amino acid racemases employ imine formation with pyridoxal phosphate (PLP) as a cofactor to accelerate the abstraction of the alpha proton. However, the group reviewed herein achieves racemization of free amino acids without the use of cofactors or metals, and uses a thiol/thiolate pair for deprotonation and reprotonation. All bacteria and higher plants contain such enzymes, for example diaminopimelate epimerase, which is required for lysine biosynthesis in these organisms. This process cannot be accomplished without an enzyme catalyst as the acidities of a thiol and the substrate α-hydrogen are inherently mismatched by at least 10 orders of magnitude. This review describes the structural and mechanistic studies on PLP-independent racemases and the evolving view of key enzymatic machinery that accomplishes these remarkable transformations.

Anatomy of a late Quaternary carbonate island: Constraints on timing and magnitude of sea-level fluctuations, West Caicos, Turks and Caicos Islands, BWI

The data set of the island of West Caicos consists of a combination of high-resolution lidar and digital imagery, radiometric data, and amino acid racemization (AAR) D/L values as well as extraordinary preservation of sedimentary and bio-constructed deposits on the island. Together with a well-established regional stratigraphic framework from the neighboring Bahamian island chain and detailed field mapping, the West Caicos data set provides an opportunity to advance our understanding of the link between carbonate stratigraphy and the controlling parameters of sea level, sediment supply, tectonics, and climate. The exceptionally well-preserved stratigraphic record of the mid–late Pleistocene from West Caicos allows recognition of marine isotope stages (MIS) 9/11, 5e, and Holocene. The west coast of the island provides a continuous 8.4 km exposure of the MIS 5e record that enhances our understanding of the intra-MIS 5e bipartite succession in this region and supports a sea-level lowering that occurred during the last interglacial (LIG).West Caicos accreted as a series of eolian, foreshore–shoreface, barrier-reef, and fringing-reef facies. Shoreline positions for all but the MIS 7 and MIS 5a/c deposits are now captured in the sub-meter geodetic-quality topobathy lidar survey. The Star Town unit of MIS 9/11 age forms the southern margin of the island as well as the central karst-modified spine, with uranium–thorium (UTh) coral ages of between 368 and 365 thousand years ago (ka) and a D/L Glu average of >0.60. Early MIS 5e strata include the Railroad Ridge unit in the center of the island, which was previously identified as one of the older units. The Railroad Ridge unit is a north–south linear dune ridge that has a D/L Glu average of 0.52 and indicates the onset of sediment sources from the east associated with a flooded central Caicos Platform. Approximately synchronously, the early MIS 5e South Reef unit (+3.75–4 m sea-level elevation) nucleated on the western coast of West Caicos, attached to the middle Pleistocene Star Town unit. The South Reef corals yield an average coral UTh age of 126.5 ka, with an average D/L Glu from skeletal matrix of 0.46. This transitional barrier/fringing reef is unconformably overlain by the late MIS 5e Boat Cove unit. Corals in the basal transgressive phase of this upper MIS 5e Boat Cove unit yield an average 120.6 ka UTh and average D/L Glu of 0.45. Shallow-marine, foreshore, and eolian facies of the late MIS 5e rest on a wave-cut terrace that cuts the early MIS 5e South Reef unit by as much as 3 m down to a +0.5 m above present sea-level elevation. The upper MIS 5e Boat Cove unit displays a maximum of +4.5 m elevation above present-day sea level, measured from the middle of the foreshore. This estimate may be a minimum value as the exposures on the west coast are part of a forced regressive foreshore sequence. Last stages of the upper MIS 5e deposition are seen in a series of regressive dune-beach ridge deposits referred to as the Northeast Ridges unit, with sea-level positions ranging from +4.5 m early in the central part of West Caicos, to +0.5 m on the far northeast coast, eventually building down below present-day sea level. This sea-level history fits well with previously documented records in the Bahamas and globally, and the extensive erosion supports a short-lived (between 126 and 120 ka) intra-MIS 5e relative-sea-level fall. Holocene deposition on West Caicos is restricted to northern and eastern margins of the island as a combination of strandplain and dune ridge mixed skeletal–oolitic units.Using the high-resolution digital elevation model (DEM) and linked digital geologic map makes it possible to compare areas of the different Pleistocene and Holocene units quantitatively and to constrain volumetric assessments and accumulation rates on the island for different units. The peak sediment volume production/accumulation rate—between 6.5 and 8 × 106 m3 or between 2.2 and 2.7 × 106 m3 per ka—is observed in the upper MIS 5e unit. This rate is 5 times greater than the 0.5 × 106 m3 per ka estimated for the Holocene ooid dune-ridge/strandplain complex, suggesting that the combination of higher sea level, greater wave and wind energy, and warmer ocean temperatures may have fostered the higher rate of chemically precipitated sediment supply.

Investigation of α-amino acid N-carboxyanhydrides by X-ray diffraction for controlled ring-opening polymerization

The need for a scalable synthesis of not sequence defined polypeptides as biomaterials is met by the ring-opening polymerization of α-amino acid N-carboxyanhydrides (NCAs). Even though this polymerization technique appears straight forward, it holds pitfalls in terms of reproducibility and overall control over the polymerization conditions, which depends, beside choice of solvent or initiator, significantly on reagent purity. In addition, the synthesis of monomers can lead to the formation of racemic amino acids. Thus, in this work, we describe the benefits of highly pure monomers in order to control nucleophilic ring-opening polymerization NCAs. Hereby, monomer purity is investigated by relating melting points of NCAs with single-crystal and powder X-ray diffraction crystallography data, which further proves retained stereo-information of NCAs.

A new method for enamel amino acid racemization dating: A closed system approach

Abstract Analysis of the predictable breakdown of proteins and amino acids in ancient biominerals enables age estimation over the Quaternary. We postulate that enamel is a suitable biomineral for the long-term survival of endogenous amino acids. Analysis of multiple amino acids for geochronological studies is typically achieved using a RP-HPLC method. However, the low concentrations of amino acids coupled with high concentrations of inorganic species make accurate determination of amino concentrations challenging. We have developed a method for the routine preparation of multiple enamel samples using biphasic separation. Furthermore, we have shown that amino acids that exhibit effectively closed system behaviour can be isolated from enamel through an exposure time of 72 h to bleach. Elevated temperature experiments investigating the processes of intra-crystalline protein degradation (IcPD) do not appear to match the patterns from fossil samples, reinforcing the need for a comprehensive understanding of the underlying mechanisms of protein degradation. This novel preparative method isolates intra-crystalline amino acids suitable for the development of mammalian geochronologies based on enamel protein degradation. The lower rates of racemization in enamel (cf. Bithynia opercula) suggest that the enamel AAR may be able to be used as a relative dating technique over time scales >2.8 Ma. Enamel AAR has the potential to directly date mammalian remains past the limit of all other current direct dating methods, providing an invaluable tool for geochronological studies.

Amino acid racemisation and uranium-series dating of a last interglacial raised beach, Kingscote, Kangaroo Island, southern Australia

ABSTRACTThe extent to which scleractinian coral inhabited southern Australia during the warm intervals of the Quaternary is poorly understood because identifiable corals from interglacial sedimentary records are scarce. Here we document the presence of a sub-tropical coral, Goniopora lobata, recovered together with warm water mollusc species from a raised cobble and boulder beach conglomerate at Kingscote, Kangaroo Island, dated by uranium-series and amino acid racemisation methods respectively to the last interglacial (MIS 5e). The presence of this assemblage preserved within the Glanville Formation at Kingscote suggests a 2–3° C higher than present last interglacial coastal water temperature for northern Kangaroo Island. The height of the last interglacial shoreline deposit was measured by theodolite, and points to a mean last interglacial sea level 3.1 ± 0.4 m higher than present.

Terahertz spectral of enantiomers and racemic amino acids by time-domain-spectroscopy technology

The absorption spectra of four amino acids were studied. These spectra are obtained by terahertz time-domain spectroscopy (TDS) technique. The four amino acids are alanine, methionine, leucine, and valine, respectively. The spectra of their enantiomers (l-, d-) and racemic compounds (dl-) were investigated. Although the two isomers have very similar structures, their absorption spectra are obviously different. The absorption coefficient of each structure is calculated by the density functional theory (DFT), and the simulated spectra of each structure are obtained. It is shown that the number of the calculated peaks is in good agreement with the experimental ones. The experimental spectra were compared with the theoretical spectra. The differences between the absorption spectra of isomers are presented, and the reasons for the differences were analyzed. The vibratory spectra of biomolecules were studied, and the correlation between molecular structure and function was further understood.

One-Pot Preparation of d-Amino Acids Through Biocatalytic Deracemization Using Alanine Dehydrogenase and ω-Transaminase

d-Amino acids are pharmaceutically important building blocks, leading to a great deal of research efforts to develop cost-effective synthetic methods. Preparation of d-amino acids by deracemization has been conceptually attractive owing to facile synthesis of racemic amino acids by Strecker synthesis. Here, we demonstrated biocatalytic deracemization of aliphatic amino acids into d-enantiomers by running cascade reactions; (1) stereoinversion of l-amino acid to a d-form by amino acid dehydrogenase and ω-transaminase and (2) regeneration of NAD+ by NADH oxidase. Under the cascade reaction conditions containing 100 mM isopropylamine and 1 mM NAD+, complete deracemization of 100 mM dl-alanine was achieved after 24 h with 95% reaction yield of d-alanine (> 99% eeD, 52% isolation yield).

A review of MIS 7 and MIS 5 terrace deposits along the Gulf of Taranto based on new stratigraphic and chronological data

We performed detailed geological and geomorphological analyses on a well-exposed series of marine terrace deposits located along a coastal area from the city of Taranto to the Bradano River in the northern Gulf of Taranto (southern Italy). Absolute dating was performed by applying amino acid racemisation (AAR) to ostracod shells and isoleucine epimerisation (D-aIle/L-Ile) to Glycymeris sp. shells. The combination of field geological surveys, remote sensing,digital terrain model analysis, and absolute dating allowed us to study a large number of stratigraphic sections as well as recognise and map three terrace deposits in the Apulian sector of the Gulf of Taranto that date to MIS 7.3, MIS 7.1 and MIS 5. A peculiar feature of the MIS 7.1terrace deposit is the presence of biohermal and biostromal limestones rich in Cladocora caespitosa, calcareous algae and bryozoans; this feature contrasts with general context of the prevailing siliciclastic deposits.Based on currently available data, we propose two hypotheses regarding the MIS 5 terrace deposit: 1) the MIS 5 terrace formed entirely during MIS 5.5; and 2) the MIS 5 terrace is a set of terraces that correlates to MIS 5.5, 5.3 and 5.1, in which the scarps and abrasion platforms have been partially masked by the superimposition of the so-called givoni, ridges that are elongated sub-parallel to the coastline.Our data, combined with an extensive critical review of age dates in the literature, allow us to exclude the presence of an emerged marine terrace deposit of MIS 3.We calculate the uplift rates of the MIS 7.3, 7.1, 5.5 and 5.3 palaeoshorelines. In the west sector, the mean uplift rates calculated for the recognised inner edges are MIS 7.3 = 0.65 mm/a, MIS 5.5 = 0.39 mm/a, MIS 5.3 = 0.31 mm/a; in the central sector the rates are MIS 7.3 = 0.485 mm/a, MIS 7.1 = 0.37 mm/a, MIS 5.5 = 0.35 mm/a, MIS 5.3 = 0.26 mm/a; in the east sector the rates are MIS 7.3 = 0.39 mm/a, MIS 5.5 = 0.25 mm/a, MIS 5.3 = 0.21 mm/a. These uplift ratesshow a uniform decreasing trend in time and space, proceeding from the western to the eastern sector, which allows us to hypothesise a slowing of the uplift phase characterising the foredeep, which began in the middle Pleistocene.

New interglacial deposits from Copenhagen, Denmark: marine Isotope Stage 7

During a pre‐site survey and construction of a new metro route and station in Copenhagen, fossiliferous organic‐rich sediments were encountered. This paper reports on multidisciplinary investigations of these organic sediments, which occurred beneath a sediment succession with a lower till, glacifluvial sand and gravel, an upper till and glacifluvial sand. The organic sediments were underlain by glacifluvial sand and gravel. The organic‐rich sediments, which were up to 0.5 m thick, accumulated in a low‐energy environment, possibly an oxbow lake. They were rich in plant fossils, which included warmth‐demanding trees and other species, such as Najas minor, indicating slightly higher summer temperatures than at present. Freshwater shells were also frequent. Bithynia opercula allowed the sediments to be put into an aminostratigraphical framework. The amino acid racemization (AAR) ratios indicate that the organic sediments formed during Marine Isotope Stage 7 (MIS 7), which is consistent with optically stimulated luminescence dating that gave ages of 206 and 248 ka from the underlying minerogenic deposit. The assemblages from Trianglen are similar to interglacial deposits from the former Free Port (1.4 km away) in Copenhagen, except that Corbicula and Pisidium clessini were not found at Trianglen. The presence of these bivalves at the Free Port and the ostracod Scottia tumida at Trianglen indicates a pre‐Eemian age. AAR data from archived Bithynia opercula from the Free Port were almost identical to those from Trianglen, indicating that the two sites are contemporary. We suggest the Trianglen interglacial be used as a local name for the MIS 7 interglacial deposits in Copenhagen. MIS 7 deposits have rarely been documented from the region, but MIS 7 deposits may have been mistaken for other ages. The use of AAR ratios in Bithynia opercula has a great potential for correlation of interglacial non‐marine deposits in mainland northern Europe.

Orbital-scale environmental and climatic changes recorded in a new ∼200,000-year-long multiproxy sedimentary record from Padul, southern Iberian Peninsula

Padul is one of the few wetland sites in southern Europe and the Mediterranean region that exhibits an unusually large temporal span (>100 kyr) and continuous Quaternary sedimentary record. Previous core-based studies from Padul yielded paleoecological datasets (i.e., pollen and organic geochemistry), but with a poor age control that resulted in rather arbitrary climate inferences. Therefore, precise age control and a multidisciplinary approach is necessary to understand long-term regional environmental and climate change and the associated local response of the Padul wetland environment. Here we present a new long sediment record (Padul-15-05) from this wetland in the southern Iberian Peninsula with the aim of improving the age control of the sedimentary sequence and carrying out up-to-date high-resolution multiproxy analyses. In this study the age control is based on 61 AMS radiocarbon dates for the last ca. 50 kyr BP and on the extent of amino acid racemization (AAR) in mollusc shells extending back ∼118 kyr BP. No numerical ages are available for the bottom part of the core but the sediment accumulation rates (SAR) and the cyclostratigraphic analysis of the multiproxy data suggest that the core preserves a continuous record of the last ∼197 kyr (from late MIS 7 to present) with millennial-scale time resolution. Sedimentological (lithology, magnetic susceptibility, XRD, color), geochemical (XRF, TOC, C/N, % carbonate content) and paleontological (pollen, charophytes, gastropods) data show co-varying cyclical paleoenvironmental changes linked to orbital-scale climatic variability. Silicon, magnetic susceptibility (MS) and total organic carbon (TOC) data show periodicities between ∼26.2–19.6 kyr linked to insolation, which is strongly dominated by precession cycles at this latitude. High values of Si and MS data have been related to high siliciclastic/detrital input from Sierra Nevada range during minima in insolation due to enhanced soil weathering/erosion during regional aridity and lower forest cover recorded by the arboreal pollen, which could also be favored by a minor biogenic productivity. In addition, warm climate conditions during maxima in insolation mostly resulted in negative precipitation/evapotranspiration balance and low lake levels, while cold glacial and stadial periods were mainly characterized by positive precipitation/evapotranspiration balance, and therefore, high lake levels. The improved chronology of the Padul sedimentary sequence along with a multiproxy study permitted us to better relate environmental and vegetation changes to climatic events and to demonstrate how both local (i.e., lake level, sedimentation) and regional (i.e., vegetation) environments responded to orbital-scale climate changes.

Complex-precipitation using functionalized chiral ionic liquids with L-proline anion and chromatographic analysis for enantioseparation of racemic amino acids.

As one kind of functionalized green medium, chiral ionic liquids (CILs) have been widely applied in fields of asymmetric catalysis, enantioseparation, and so on. In this study, four kinds of amino acid-based CILs were synthesized by using trimethylamine, N-methylpyrrolidine, N-methylimidazole, and tropine as cationic nucleus, respectively. Then their specific optical rotation and solubility in common solvents were determined for further resolution application. The effect of different cations in these CILs was explored on the separation of racemic phenylalanine in complex-precipitation way. Moreover, various factors were systematically investigated for their effects on resolution efficiency, including the type of additive copper salts, the molar ratio of Cu (II) to CIL, pH value, the amount of racemic phenylalanine, and temperature. Under the appropriate conditions, L-phenylalanine mainly existed in solid phase and could be separated from its enantiomers in liquid phase. Furthermore, the mechanism of resolution was studied by thermogravimetric analysis, infrared spectrum, and molecular simulation. The resolution system has characteristics of no organic solvent, fast separation speed, simple resolution process, and easy scale-up.

Modelling studies of enantioselective extraction of an amino acid derivative in slug flow capillary microreactors

This work shows that enantioselective liquid–liquid extraction in microreactors is attractive for chiral separation. A precise control over the residence time in microreactors results in high enantiopurities and low host inventories. Mathematical modelling has been presented to describe the experimental results on the enantioselective extraction of an aqueous racemic amino acid derivative (3,5-dinitrobenzoyl-(R,S)-leucine) with a cinchona alkaloid chiral host in 1-octanol using a slug flow capillary microreactor (at an aqueous to organic flow ratio of 1:1). A good agreement between the model predictions and experimental results was obtained by taking the enhancement of the mass transfer rates due to the reactions in the aqueous and organic phases into account. An enantiomeric excess of the (S)-enantiomer higher than the equilibrium value was observed especially at shorter residence times due to kinetic effects. The observed phenomena could be explained by an instantaneous rate of the complexation of the (S)-enantiomer with the host and a finite rate of the complexation of the (R)-enantiomer. The developed model was used to determine guidelines for multi-stage operation in microreactors in order to increase yield and enantiopurity.

One‐step Synthesis of α‐Keto Acids from Racemic Amino Acids by A Versatile Immobilized Multienzyme Cell‐free System

AbstractThe elevated value of α‐keto acids has pushed scientists to explore more efficient and less expensive alternatives for their synthesis. In this work, an immobilized tri‐enzyme system that produced α‐keto acids in “one‐pot” from l‐ or racemic mixtures of diverse amino acids was presented. The system combined a broad‐spectrum amino acid racemase (BsrV), a d‐amino acid oxidase (DAAO) and catalase (CAT). BsrV racemized l‐amino acids into their d‐enantiomers, DAAO catalyzed the stereospecific oxidative deamination of the d‐amino acids into their corresponding α‐keto acids, ammonium ion, and H2O2. Finally, CAT converted the inactivating H2O2 into H2O and O2, which can be reused by the oxidase reaction. BsrV thermal stability was improved 3,300‐fold by immobilizing the enzyme on glyoxyl‐activated agarose beads. DAAO and CAT were co‐immobilized on agarose beads functionalized with glutaraldehyde groups for enhancing their stabilities and eliminating H2O2 in a much more effective way. To show the versatility of this system, racemic mixtures of amino acids were converted in their corresponding α‐keto acids. The coupling of the three immobilized enzymes permitted conversions of approximately 99 % through a dynamic kinetic resolution process. This system conserved 100 % of its initial effectiveness after 8 reaction cycles. Collectively, our innovative tri‐enzyme system for the synthesis of α‐keto acids opens the door for a cheapening in the production of many pharmaceutical and cosmetics.

Micropalaeontological evidence for deglacial marine flooding of the ancient courses of the River Murray across the Lacepede Shelf, southern Australia

Abstract Previous sub-bottom profiling of the Lacepede Shelf, southern Australia, had inferred the course of the palaeo-River Murray during periods of low sea level. Micropalaeontological analysis of two cores taken during the SST-02-07 cruise, confirm these earlier observations, and reveal the past existence of permanently open, estuarine environments substantially larger than currently prevailing at the mouth of the terminal lakes of the River Murray, Australia's largest exorheic river. The characteristics of the sediment and contained microfossils provide substantial evidence for the repeated development of large, oxygen depleting algal blooms (sapropels). Detailed analyses of the ostracod and foraminifer microfaunas, together with other fossil remains such as pteropods, bryozoan, sponge spicules and echinoid spines, combined with the dating of selected ostracods and bivalve molluscs (by AMS radiocarbon) and bivalve molluscs (by amino acid racemization) reveal rapid sediment accumulation within the ancient channels of the River Murray under estuarine conditions. The oldest infill relates to the end of the rapid sea-level rise following Meltwater Pulse IA ~13,600 cal. years BP and the second one that coincides with the Meltwater Pulse IB at 11,500–11,000 cal. years BP; in both cases, marine microfauna confirm the presence of marine incursions. The palaeoenvironmental reconstructions based on microfossils presented here rely on the study of six southeastern Australian contemporaneous estuaries where foraminifers and ostracods were collected, together with some ecological data such as salinity, dissolved oxygen and presence/absence of aquatic vegetation.

P-8 - Characterization and quantification of protein oxidative modifications and amino acid racemization in powdered infant milk formula

Oxidation of dairy products, and especially infant formulas (IFs), is a major concern to the dairy industry and consumers. Thermal treatment is required for microbiological safety but may contribute to oxidative damage. Such modification may be a health risk for infants with IF as the sole source of nutrition. This study quantifies the extent of modification in commercial IFs. Protein modification in commercial IFs was examined by multiple analytical techniques. Aggregated proteins containing both reducible (disulfide) and non-reducible (di-tyrosine, lanthionine and lysinoalanine) cross-links were detected. Protein carbonyls (

Enantioselective Separation of Racemic Tryptophan with Sonochemically Prepared Egg Albumin Microspheres

AbstractNew approaches for chiral resolution are gaining importance and are of economic interest for the development of pharmaceuticals, agrochemicals, chiral sensors and food additives. Herein we disclose the first examples in which sonochemically prepared egg albumin microspheres (EAMs) were used for chiral resolution of an amino acid. When EAMs were in contact with an aqueous solution of racemic tryptophan (Trp) they selectively interacted with L‐Trp leading to 94% enantiomeric excess (ee) of D‐Trp. In a control experiment in which the egg protein, without applying ultrasonic waves to form microspheres, was dissolved and exposed to racemic Trp, no chiral resolution was observed. The effects of temperature and concentration were studied in detail. These preliminary results show that EAMs produced by sonication may provide a simple, cost‐effective an unconventional way to chiral separation of racemic amino acids.